Resin composition

Abstract

Provided are: a polyimide film which combines the characteristics of glass transition temperature, YI (yellowness), Young's modulus, and chemical resistance when cured at 430 DEG C or higher, and which can be used in display processes such as LTPS (low-temperature polycrystalline silicon) and LTPO (low-temperature polycrystalline oxide); and a resin composition, a laminate, and the like for forming the polyimide film. The present invention includes a resin, the resin including a structural unit represented by general formula (1) and / or (2), the resin being a block copolymer including a first block and a second block, the first block including a structural unit derived from a compound represented by general formula (4), and the second block including at least one structural unit selected from compounds represented by general formulas (6) and (7). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a resin composition and further relates to a method for producing a resin composition, a polyimide resin film, a laminate, a display, and a flexible device. Background Art

[0002] Polyimide resin is an insoluble, infusible, super heat-resistant resin with excellent properties such as thermal oxidation resistance, heat resistance, radiation resistance, low temperature resistance and chemical resistance. Therefore, polyimide resin is used in a wide range of fields including electronic materials. Examples of applications of polyimide resins in the field of electronic materials include insulating coating materials, insulating films, semiconductors, electrode protective films of thin-film transistor liquid crystal displays (TFT-LCDs), and the like. Recently, studies have also been conducted on the use of polyimide films, which are lightweight and flexible, to use them as flexible substrates to replace glass substrates that have been used in the field of display materials. In particular, in recent years, materials that can withstand high-temperature processes of 400°C or above, such as LTPS (Low-temperature polysilicon) and LTPO (Low-temperature polycrystalline oxide), have been sought.

[0003] Document 1 studies a polyimide precursor obtained by using BPAF (9,9-bis(3,4-dicarboxyphenyl)fluorene acid dianhydride), PMDA (pyromellitic anhydride), BPDA (3,3',4,4'-biphenyltetracarboxylic anhydride) as an acid dianhydride monomer, BAFL (9,9-bis(4-aminophenyl)fluorene) as a diamine monomer, and a silicon-containing compound. Document 2 studies a polyimide precursor obtained by using BPAF and BPDA as acid dianhydride monomers and BAFL and pPD (p-phenylenediamine) as diamine monomers. Documents 3 and 4 study a polyimide precursor obtained by using BPAF and PMDA as acid dianhydride monomers and BAFL and pPD as diamine monomers. Document 5 studies a polyimide obtained by using BPAF, BPDA, and BAFL as diamine monomers.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2020 / 241523

[0007] Patent Document 2: Taiwan Patent No. 607058

[0008] Patent Document 3: Taiwan Patent No. 573816

[0009] Patent Document 4: International Publication No. 2012 / 033213

[0010] Patent Document 5: International Publication No. 2019 / 188305 Summary of the invention

[0011] Problem that the invention aims to solve

[0012] However, in the case of the polyimide obtained by using only acid dianhydride monomers and diamine monomers used in the above-mentioned patent documents, the properties required for the display (taking into account the glass transition temperature when cured at 430°C, YI (yellowness), Young's modulus, chemical resistance, heat resistance of the laminate, etc.) are insufficient (see the following comparative example).

[0013] Therefore, the present invention is completed in view of the above situation, and its purpose is to provide a resin composition containing polyimide and the like that can be applied to displays (especially displays using LTPS (low temperature polycrystalline silicon) and LTPO (low temperature polycrystalline oxide)) by using specific acid dianhydride monomers and diamine monomers at a specific ratio (mol%). Specifically, the purpose of the present invention is to provide a polyimide film that takes into account the glass transition temperature, YI (yellowness), Young's modulus, and chemical resistance when cured at above 430°C and can be applied to display processes such as LTPS (low temperature polycrystalline silicon) and LTPO (low temperature polycrystalline oxide), and a resin composition, a laminate, etc. for forming the polyimide film. The purpose of the present invention is also to provide various manufacturing methods for a resin composition, a polyimide resin film, a laminate, a display, and a flexible device.

[0014] Solutions for solving problems

[0015] The present inventors have found that by using 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), pyromellitic anhydride (PMDA), etc. as acid dianhydride monomers, and using 9,9-bis(4-aminophenyl)fluorene (BAFL), p-phenylenediamine (pPD), etc. as diamine monomers, the obtained polyimide has excellent properties required for the following display applications: glass transition temperature, YI (yellowness), Young's modulus, chemical resistance, etc., especially when cured at above 430°C.

[0016] That is, the above-mentioned problems can be solved by the following technical means. [1]

[0018] A resin composition comprising a resin, wherein the resin comprises a structural unit represented by the following general formula (1) and / or general formula (2):

[0019]

[0020] In formula (1), P1 represents a divalent organic group, P2 represents a tetravalent organic group, and p represents a positive integer.

[0021]

[0022] In formula (2), P3 represents a divalent organic group, P4 represents a tetravalent organic group, q represents a positive integer,

[0023] The resin is a block copolymer comprising a first block and a second block,

[0024] The first block comprises a structural unit derived from a compound represented by the following general formula (4),

[0025]

[0026] The second block comprises at least one structural unit derived from the compound represented by the following general formula (6) and general formula (7),

[0027] [2]

[0029] The resin composition according to [1], wherein the first block further comprises a structural unit derived from an acid dianhydride other than the compounds represented by the general formula (6) and the general formula (7), and

[0030] The second block further includes a structural unit derived from a diamine other than the compound represented by the general formula (4). [3]

[0032] The resin composition according to [1] or [2], wherein the resin contains a structural unit derived from a fluorene derivative. [4]

[0034] The resin composition according to any one of [1] to [3], wherein the resin contains a structural unit represented by the following general formula (8):

[0035]

[0036] In formula (8), P5 and P6, when present in plural, each independently represent a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and r represents an integer of 1 to 200. [5]

[0038] The resin composition according to any one of [1] to [4], wherein the first block comprises a structural unit derived from a compound represented by the following general formula (5):

[0039]

[0040] In formula (5), Q1 and Q2, when present in plural, each independently represent a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group, X each independently represents at least one selected from the group consisting of an ether group, a carbonyl group, an ester group, and an amide group, and p is an integer of 0 or 1. [6]

[0042] The resin composition according to any one of [1] to [5], wherein the second block comprises a structural unit derived from a compound represented by the following general formula (3):

[0043]

[0044] In formula (3), Q3 and Q4, when present in plural numbers, each independently represent a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group. [7]

[0046] The resin composition according to any one of [1] to [6], wherein the second block comprises a structural unit represented by the following general formula (8):

[0047]

[0048] In formula (8), P5 and P6, when present in plural, each independently represent a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and r represents an integer of 1 to 200. [8]

[0050] The resin composition according to any one of [1] to [7], wherein the resin contains structural units represented by the general formula (1) and the general formula (2). [9]

[0052] The resin composition according to [8], wherein the first block is a structural unit represented by the general formula (1),

[0053] The second block is a structural unit represented by the general formula (2).

[10]

[0055] The resin composition according to [8], wherein the second block is a structural unit represented by the general formula (1),

[0056] The first block is a structural unit represented by the general formula (2).

[11]

[0058] The resin composition according to any one of [8] to

[10] , wherein in the resin, when the structure derived from the general formula (1) is L and the structure derived from the general formula (2) is M, a ratio L / M of L to M is 10 / 90 to 90 / 10,

[0059] Wherein, the unit of L is mol, the unit of M is mol, and the unit of L / M is mol%.

[12]

[0061] A resin composition comprising a resin, wherein the resin comprises a structural unit represented by the following general formula (1) and / or general formula (2):

[0062]

[0063] In formula (1), P1 represents a divalent organic group, P2 represents a tetravalent organic group, and p represents a positive integer.

[0064]

[0065] In formula (2), P3 represents a divalent organic group, P4 represents a tetravalent organic group, q represents a positive integer,

[0066] The P1 and / or P3 contain a structural unit derived from a compound represented by the following general formula (4),

[0067]

[0068] The P2 and / or P4 contain at least one structural unit derived from the compound represented by the following general formula (6) and formula (7),

[0069]

[0070]

[0071] In the resin composition, the ratio of at least one structural unit selected from the structural units represented by the following general formula (10), general formula (11), general formula (12) and general formula (13) is smaller than the ratio of structural units formed by acid dianhydride monomers and diamine monomers other than the above general formula (4), general formula (6) and formula (7) connected by amide bonds and / or imide bonds,

[0072] Wherein, the unit of the ratio is mol%.

[0073]

[13]

[0075] A method for producing a resin composition, wherein the resin composition comprises a resin, and the resin comprises structural units represented by the following general formula (1) and general formula (2):

[0076]

[0077] In formula (1), P1 represents a divalent organic group, P2 represents a tetravalent organic group, and p represents a positive integer.

[0078]

[0079] In formula (2), P3 represents a divalent organic group, P4 represents a tetravalent organic group, q represents a positive integer,

[0080] The method for preparing the resin composition comprises:

[0081] After synthesizing the resin 2 having the structural unit of the general formula (2),

[0082] A step of introducing the structural unit of the general formula (1) into the resin 2 by polycondensing a compound represented by the following general formula (4) and a compound represented by the following general formula (5),

[0083]

[0084] In formula (5), Q1 and Q2, when present in plural, each independently represent a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group, X each independently represents at least one selected from the group consisting of an ether group, a carbonyl group, an ester group, and an amide group, and p is an integer of 0 or 1;

[0085] or,

[0086] A step of introducing the structural unit of the general formula (1) into the resin 2 after synthesizing the resin 2 having the structural unit of the general formula (2) by polycondensing the compound of the general formula (4) and the compound of the general formula (5).

[14]

[0088] A method for producing a resin composition, wherein the resin composition comprises structural units represented by the following general formula (1) and general formula (2):

[0089]

[0090] In formula (1), P1 represents a divalent organic group, P2 represents a tetravalent organic group, and p represents a positive integer.

[0091]

[0092] In formula (2), P3 represents a divalent organic group, P4 represents a tetravalent organic group, q represents a positive integer,

[0093] The method for producing the resin composition comprises the steps of, after synthesizing a resin 2 having a structural unit of the general formula (2), introducing a structural unit of the general formula (1) into the resin 2.

[0094] The P1 or P3 comprises a structural unit derived from a compound represented by the following general formula (4),

[0095]

[15]

[0097] A method for producing a polyimide resin film, comprising:

[0098] a coating step of coating the resin composition described in any one of [1] to

[12] or the resin composition obtained by the method described in

[13] or

[14] on the surface of the support;

[0099] a film forming step of heating the resin composition to form a polyimide resin film;

[0100] a peeling step of peeling the polyimide resin film from the support; and

[0101] an irradiation step of irradiating the resin composition with a laser beam from the support side before the peeling step.

[16]

[0103] A method for manufacturing a display, comprising:

[0104] a coating step of coating the resin composition described in any one of [1] to

[12] or the resin composition obtained by the method described in

[13] or

[14] on the surface of the support;

[0105] a film forming step of heating the resin composition to form a polyimide resin film;

[0106] an element forming step of forming an element on the polyimide resin film; and

[0107] A peeling step is to peel the polyimide resin film on which the element is formed from the support.

[17]

[0109] A method for manufacturing a laminate, comprising:

[0110] a coating step of coating the resin composition described in any one of [1] to

[12] or the resin composition obtained by the method described in

[13] or

[14] on the surface of the support;

[0111] a film forming step of heating the resin composition to form a polyimide resin film; and

[0112] The device forming step is to form a device on the polyimide resin film.

[18]

[0114] A method for manufacturing a laminate, comprising:

[0115] a coating step of coating the resin composition described in any one of [1] to

[12] or the resin composition obtained by the method described in

[13] or

[14] on the surface of the support;

[0116] a film forming step of heating the resin composition to form a polyimide resin film;

[0117] an element forming step of forming an element on the polyimide resin film; and

[0118] a step of peeling the polyimide resin film on which the element is formed from the support.

[19]

[0120] A polyimide resin film having all of the following characteristics:

[0121] ·YI (yellowness index) is 15 or less (based on a film thickness of 10 μm)

[0122] · Degassing start temperature (TDS evaluation) is 440℃ or above

[0123] ·Residual stress is less than 35MPa (under nitrogen atmosphere)

[0124] Rth (retardation in the thickness direction) is 100 nm or less (based on a film thickness of 10 μm).

[20]

[0126] A flexible display comprises the polyimide resin film described in

[19] and LTPO (Low-temperature polycrystalline oxide). [twenty one]

[0128] A method for manufacturing a display, comprising: heating a laminate comprising a polyimide resin film and an inorganic film at 420° C. or higher, and then irradiating the laminate with an excimer laser.

[0129] The polyimide resin film satisfies all of the following properties:

[0130] ·YI (yellowness index) is 15 or less (based on a film thickness of 10 μm)

[0131] The degassing start temperature (TDS evaluation) is 440°C or higher. [twenty two]

[0133] The method for manufacturing a display according to

[20] , wherein the polyimide resin film satisfies all of the following characteristics:

[0134] ·Residual stress is less than 35MPa (under nitrogen atmosphere)

[0135] Rth (retardation in the thickness direction) is 100 nm or less (based on a film thickness of 10 μm). [twenty three]

[0137] A method for manufacturing a display using a laminate comprising a polyimide resin film and an inorganic film, wherein the polyimide resin film satisfies all of the following characteristics:

[0138] ·YI (yellowness index) is 15 or less (based on a film thickness of 10 μm)

[0139] · Degassing start temperature (TDS evaluation) is 440℃ or above

[0140] ·Residual stress is less than 35MPa (under nitrogen atmosphere)

[0141] Rth (thickness direction retardation) is less than 100nm (converted to a film thickness of 10μm),

[0142] The method for manufacturing the display includes a dehydrogenation treatment step, an excimer laser irradiation step, an ion implantation step, and a heating and annealing step at 400° C. or higher.

[0143] Effects of the Invention

[0144] According to the present invention, by using specific acid dianhydride monomers and diamine monomers in a specific ratio (mol %), a resin composition containing polyimide etc. that can be suitable for displays (especially displays using LTPS (low temperature polycrystalline silicon) and LTPO (low temperature polycrystalline oxide)) can be provided.

[0145] Specifically, the object of the present invention is to provide a polyimide film that takes into account the glass transition temperature, YI (yellowness), Young's modulus, and chemical resistance when cured at 430°C or above and is applicable to display processes such as LTPS (low temperature polycrystalline silicon) and LTPO (low temperature polycrystalline oxide), and a resin composition and laminate for forming the polyimide film. The present invention can also provide methods for manufacturing a resin composition, a polyimide resin film, a laminate, a display, and a flexible device.

[0146] It should be noted that the above description is not considered to disclose all embodiments of the present invention and all advantages related to the present invention. Further embodiments of the present invention and their advantages will become clear by referring to the following description. BRIEF DESCRIPTION OF THE DRAWINGS

[0147] Figure 1 This is a schematic diagram of the structure of the upper portion of the polyimide substrate of a top emission type flexible organic EL display shown as an example of the display of this embodiment. DETAILED DESCRIPTION

[0148] Hereinafter, an exemplary embodiment of the present invention (hereinafter referred to as "the present embodiment") is described. The present invention is not limited to the present embodiment, and various modifications can be made within the scope of the present invention. In the present specification, the upper limit and lower limit of each numerical range can be arbitrarily combined.

[0149] 《Resin composition》

[0150] <Polyimide precursor / polyimide>

[0151]

[0152] <A-1>

[0153] The resin composition of the present embodiment includes a resin, and the resin includes a structural unit represented by the following general formula (1) and / or (2):

[0154]

[0155] {In the formula, P1 represents a divalent organic group, P2 represents a tetravalent organic group, and p represents a positive integer.}

[0156]

[0157] {wherein, P3 represents a divalent organic group, P4 represents a tetravalent organic group, and q represents a positive integer.},

[0158] The above resin is a block copolymer including a first block and a second block,

[0159] The first block comprises a structural unit derived from a compound represented by the following general formula (4):

[0160]

[0161] The second block includes at least one structural unit derived from the compound represented by the following general formula (6) and (7):

[0162]

[0163] When the block copolymer comprises a first block and a second block, the first block comprises a structural unit derived from a compound represented by general formula (4), and the second block comprises at least one structural unit derived from a compound represented by general formula (5) and general formula (6), the obtained polyimide has various properties when cured at 430° C. or above, such as glass transition temperature, YI (yellowness), Young's modulus, and chemical resistance, and is therefore preferred.

[0164] The first block of the resin composition of this embodiment may further include a structural unit derived from an acid dianhydride other than the compounds represented by general formulae (6) and (7), and the second block may further include a structural unit derived from a diamine other than the compound represented by general formula (4).

[0165] The resin of the resin composition of the present embodiment may include a structural unit derived from a fluorene derivative.

[0166] In addition, the resin of the resin composition of the present embodiment may include a structural unit represented by the following general formula (8):

[0167]

[0168] {In the formula, P5 and P6, when present in plural numbers, each independently represent a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and r represents an integer of 1 to 200.}

[0169] In the resin composition of the present embodiment, the first block may include a structural unit derived from a compound represented by the following general formula (5):

[0170]

[0171] (In the formula, Q1 and Q2, when present in plural, each independently represent a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group, X each independently represents at least one selected from the group consisting of an ether group, a carbonyl group, an ester group, and an amide group, and p is an integer of 0 or 1.)

[0172] In the resin composition of the present embodiment, the second block may include a structural unit derived from a compound represented by the following general formula (3):

[0173]

[0174] (In the formula, Q3 and Q4, when present in plural, each independently represents a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group.)

[0175] In addition, the second block of the resin composition of the present embodiment may include a structural unit represented by the following general formula (8):

[0176]

[0177] {wherein, P5 and P6, when present in plural numbers, each independently represent a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and r represents an integer of 1 to 200}.

[0178] In the resin composition of the present embodiment, the resin may include structural units represented by the general formulae (1) and (2).

[0179] Specifically, for example, the first block of the resin composition of the present embodiment may be a structural unit represented by the above general formula (1), and the second block may be a structural unit represented by the above general formula (2).

[0180] Furthermore, for example, the second block of the resin composition of the present embodiment may be a structural unit represented by the above general formula (1), and the first block may be a structural unit represented by the above general formula (2).

[0181] In the above resin, when the structure derived from the general formula (1) is L (mol) and the structure derived from the general formula (2) is M (mol), the ratio L / M of L to M is preferably 10 / 90 to 90 / 10 (mol%).

[0182] <A-2>

[0183] The resin composition of the present embodiment includes a resin, and the resin includes a structural unit represented by the following general formula (1) and / or (2):

[0184]

[0185] {In the formula, P1 represents a divalent organic group, P2 represents a tetravalent organic group, and p represents a positive integer.}

[0186]

[0187] {wherein, P3 represents a divalent organic group, P4 represents a tetravalent organic group, and q represents a positive integer.},

[0188] The above-mentioned P1 and / or P3 contain a structural unit derived from a compound represented by the following general formula (4):

[0189]

[0190] The above-mentioned P2 and / or P4 contain at least one structural unit derived from a compound represented by the following general formula (6) and formula (7):

[0191]

[0192]

[0193] The ratio (mol %) of at least one structural unit selected from the group consisting of the structural units represented by the following general formulae (10), (11), (12) and (13) in the resin composition is smaller than the ratio (mol %) of structural units formed by connecting acid dianhydride monomers and diamine monomers other than the general formulae (4), (6) and (7) via amide bonds and / or imide bonds:

[0194]

[0195] When P1 and / or P3 contain structural units derived from a compound represented by general formula (4), P2 and / or P4 contain at least one structural unit derived from a compound represented by the following general formula (6) and formula (7), and the ratio (mol %) of at least one structural unit selected from the following general formula (10), general formula (11), general formula (12) and general formula (13) in the resin composition is less than the ratio (mol %) of structural units formed by acid dianhydride monomers and diamine monomers other than the above general formula (4), general formula (6) and formula (7) connected by amide bonds and / or imide bonds, the obtained polyimide takes into account the various properties of glass transition temperature, YI (yellowness), Young's modulus and chemical resistance when cured at 430°C or above, so it is preferred.

[0196] <A-3>

[0197] The resin composition of the present embodiment includes a structural unit represented by the following general formula (1) or (2):

[0198]

[0199] {In the formula, P1 represents a divalent organic group, P2 represents a tetravalent organic group, and p represents a positive integer.}

[0200]

[0201] {wherein, P3 represents a divalent organic group, P4 represents a tetravalent organic group, and q represents a positive integer.},

[0202] The above P1 or P3 contains at least one structural unit derived from the following general formula (3) or general formula (4):

[0203]

[0204] (In the formula, Q3 and Q4, when present in plural, each independently represent a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group.)

[0205]

[0206] The above P2 or P4 contains at least one structural unit derived from the following general formula (5) or general formula (6):

[0207]

[0208] (In the formula, Q1 and Q2, when present in plural, each independently represents a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group, X each independently represents at least one selected from the group consisting of an ether group, a carbonyl group, an ester group, and an amide group, and p is an integer of 0 or 1.)

[0209]

[0210] When P1 or P3 contains at least one structural unit derived from the compounds represented by the above-mentioned general formula (3) and general formula (4), and P2 or P4 contains at least one structural unit derived from the compounds represented by general formula (5) and general formula (6), the obtained polyimide takes into account the various properties of glass transition temperature, YI (yellowness), Young's modulus, and chemical resistance when cured at above 430°C, so it is preferred.

[0211] From the viewpoint of heat resistance, 9,9-bis(4-aminophenyl)fluorene (hereinafter also referred to as BAFL) in which Q3 and Q4 of the above general formula (3) are both hydrogen atoms is preferred, and from the viewpoint of heat resistance, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (hereinafter also referred to as BPAF) in which Q1 and Q2 of the above general formula (5) are both hydrogen atoms and p is 0 is preferred.

[0212] In addition, the above P2 or P4 of the resin composition of the present embodiment may include a structural unit derived from the following general formula (7):

[0213]

[0214] In addition, the resin composition of this embodiment may contain at least a structural unit derived from the general formula (4) in P1 or P3, and a structural unit derived from the general formula (5) in P2 or P4, and the structural unit derived from the general formula (4) accounts for less than 80 mol% of all diamine monomers, or the structural unit derived from the general formula (5) accounts for more than 15 mol% of all acid dianhydride monomers.

[0215] By setting the structural unit derived from the general formula (4) to 80 mol % or less, the YI of the obtained polyimide film can be reduced. By setting the structural unit derived from the general formula (5) to 15 mol % or more, the YI and Rth of the obtained polyimide film can be reduced.

[0216] The resin composition of the present embodiment may contain at least a structural unit derived from the general formula (3) in P1 or P3, and / or a structural unit derived from the general formula (7) in P2 or P4.

[0217] The resin composition of this embodiment may contain at least one structural unit derived from general formula (3) and general formula (4) in P1 or P3, and contain a structural unit derived from general formula (5) in P2 or P4, wherein the structural unit derived from general formula (3) accounts for more than 20 mol% of all diamine monomers.

[0218] By setting the content of the structural unit derived from the general formula (3) to 20 mol % or more, the YI and Rth of the obtained polyimide film can be lowered.

[0219] The resin composition of this embodiment may contain at least one structural unit derived from the general formula (3) and the general formula (4) in P1 or P3, and at least one structural unit derived from the general formula (5) and the general formula (7) in P2 or P4.

[0220]

[0221] The resin composition of the present embodiment includes structural units represented by the following general formulae (1) and (2):

[0222]

[0223] {In the formula, P1 represents a divalent organic group, P2 represents a tetravalent organic group, and p represents a positive integer.}

[0224]

[0225] {wherein, P3 represents a divalent organic group, P4 represents a tetravalent organic group, and q represents a positive integer.},

[0226] The above P1 and / or P3 contain at least one structural unit derived from the following general formula (3) or general formula (4):

[0227]

[0228] (In the formula, Q3 and Q4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group.)

[0229]

[0230] The above P2 and / or P4 contain at least one structural unit derived from the following general formula (5) or general formula (6):

[0231]

[0232] (In the formula, Q1 and Q2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group.)

[0233]

[0234] When P1 and / or P3 contain at least one structural unit derived from the compounds represented by general formula (3) and general formula (4), and P2 and / or P4 contain at least one structural unit derived from the compounds represented by general formula (5) and general formula (6), the obtained polyimide takes into account the glass transition temperature, YI (yellowness), Young's modulus, and chemical resistance when cured above 430°C, and is therefore preferred.

[0235] From the viewpoint of heat resistance, it is preferred that Q3 and Q4 of the above general formula (3) are both hydrogen atoms and 9,9-bis(4-aminophenyl)fluorene (hereinafter also referred to as BAFL), and from the viewpoint of heat resistance, it is preferred that Q1 and Q2 of the above general formula (5) are both hydrogen atoms and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (hereinafter also referred to as BPA).

[0236] In addition, the above P2 and / or P4 of the resin composition of the present embodiment may include a structural unit derived from the following general formula (7):

[0237]

[0238] In the resin having the structure of the above-mentioned general formula (1) and the above-mentioned general formula (2), when the structure (amide unit) derived from the general formula (1) is set to L (mol) and the structure (imide unit) derived from the general formula (2) is set to M (mol), the ratio L / M of L to M is (5 / 95) to (95 / 5), preferably (10 / 90) to (90 / 10).

[0239] From the viewpoint of storage stability of the varnish, the molar fraction of the imide unit M is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more, and particularly preferably 20 mol% or more. In addition, from the viewpoint of turbidity and whitening of the varnish, the molar fraction of the amide unit L is preferably 95% or less, more preferably 90 mol% or less, further preferably 85 mol% or less, and particularly preferably 80 mol% or less.

[0240] The ratio L / M of L to M can be calculated from the amount of each monomer added and the synthesis conditions, or can be calculated by the following method.

[0241] The obtained resin composition (for example, a partially imidized polyimide precursor) is measured. 13 C-NMR. In addition, all the polyimide precursors and all the polyimide resins were synthesized using the same monomers as the resin at the same ratio (mol%), and the respective resins were measured in the same manner. 13 C-NMR: L / M can be calculated by comparing the integrated values ​​of the obtained graphs (for example, the integrated value of the peak of C of the carbonyl group of the amide / imide bond).

[0242] In addition, in the above resin, P1 and / or P3 may contain a structural unit derived from the following general formula (3):

[0243]

[0244] (wherein, Q3 and Q4, when present in plural, each independently represent a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group.)

[0245] The above P2 and / or P4 may contain a structural unit derived from the following general formula (5):

[0246]

[0247] (In the formula, Q1 and Q2, when present in plural, each independently represents a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group, X each independently represents at least one selected from the group consisting of an ether group, a carbonyl group, an ester group, and an amide group, and p is an integer of 0 or 1.)

[0248] This resin can maintain the solvent solubility of the resin while taking into account low YI, high heat resistance, and low Rth, so it is preferred. On the other hand, if the ratio of the above-mentioned general formula (3) and / or (5) in the whole resin is high, the chemical resistance becomes poor, so it is not preferred. The reason is not yet clear, but it is believed that the reason is that the compound of the general formula (3) or (5) has an alicyclic part, and the chemical resistance of this part is poor. Similarly, the chemical resistance of the resin using an alicyclic monomer (such as CpODA, etc.) is also poor.

[0249] In addition, in the above resin, the above P1 and / or P3 may contain a structural unit derived from the following general formula (4):

[0250]

[0251] And the above P2 and / or P4 contain structural units derived from the following general formula (5):

[0252]

[0253] (In the formula, Q1 and Q2, when present in plural, each independently represent a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group, X each independently represents at least one selected from the group consisting of an ether group, a carbonyl group, an ester group, and an amide group, and p is an integer of 0 or 1.)

[0254] Such a resin is preferred because it can achieve low YI, high heat resistance, and high Young's modulus while maintaining the solvent solubility of the resin.

[0255] In addition, the resin composition of this embodiment may contain at least structural units derived from the general formula (4) in P1 and / or P3, and structural units derived from the general formula (5) in P2 and / or P4, and the structural units derived from the general formula (4) account for less than 80 mol% of all diamine monomers, or the structural units derived from the general formula (5) account for more than 15 mol% of all acid dianhydride monomers.

[0256] By setting the structural unit derived from the general formula (4) to 80 mol % or less, the YI of the obtained polyimide film can be reduced, and by setting the structural unit derived from the general formula (5) to 15 mol % or more, the heat resistance and Young's modulus of the obtained polyimide film can be increased.

[0257] The resin composition of this embodiment may contain at least a structural unit derived from the general formula (3) in P1 and / or P3, and / or a structural unit derived from the general formula (7) in P2 and / or P4.

[0258] P1 and / or P3 of the resin composition of this embodiment contain at least one structural unit derived from general formula (3) and general formula (4), and P2 and / or P4 contain a structural unit derived from general formula (5). The structural unit derived from general formula (3) may account for more than 20 mol% of all diamine monomers.

[0259] By setting the content of the structural unit derived from the general formula (3) to 20 mol % or more, the YI and Rth of the obtained polyimide film can be lowered.

[0260] The resin composition of this embodiment may contain at least one structural unit derived from general formula (3) and general formula (4) in P1 and / or P3, and at least one structural unit derived from general formula (5) and general formula (7) in P2 or P4.

[0261] The resin described in and may include a structure represented by the following general formula (8):

[0262]

[0263] {wherein, P5 and P6, when present in plural numbers, each independently represent a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and r represents an integer of 1 to 200}.

[0264] When the structure of the general formula (8) is contained, the Rth and residual stress of the obtained polyimide film become good, which is preferred.

[0265] In order to make the resin have the structure of the general formula (8), the above P1, P2, P3, and P4 may contain a structural unit derived from a silicon-containing compound represented by the following general formula (14):

[0266]

[0267] {In the formula, R3 is independently a single bond or a divalent organic group having 1 to 10 carbon atoms, R4 and R5 are independently monovalent organic groups having 1 to 10 carbon atoms, at least one of which is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, R6 and R7 are independently monovalent organic groups having 1 to 10 carbon atoms, at least one of which is a monovalent aromatic group having 6 to 10 carbon atoms, R8 and R9 are independently monovalent organic groups having 1 to 10 carbon atoms, L1 and L2 are independently amino groups or acid anhydride groups, i is an integer of 1 to 200, j and k are independently integers of 0 to 200, and 0≤j / (i+j+k)≤0.50.}

[0268] Regarding the silicon-containing compound represented by the above general formula (14) in the resin composition,

[0269] When all diamines are taken as 100 mol %, it is 20 mol % or less; or

[0270] When all acid dianhydrides are taken as 100 mol %, it is 20 mol % or less.

[0271] If the silicon-containing compound is within the above range, it is preferred from the viewpoint of the filterability of the obtained polyimide precursor or polyimide resin composition. From the viewpoint of further improving filterability, when all diamines or all acid dianhydrides of the resin composition are set to 100 mol %, the silicon-containing compound is more preferably 20.0 mol % or less, 19.0 mol % or less, 18.0 mol % or less, 17.0 mol % or less, 16.0 mol % or less, 15.0 mol % or less, or 14.0 mol % or less. When all diamines or all acid dianhydrides of the resin composition are set to 100 mol %, the silicon-containing compound may exceed 0 mol %.

[0272] The polyimide can be obtained by thermally imidizing a polyimide precursor (including a partially imidized polyimide precursor), or chemically imidizing. From the perspective of the transparency of the obtained polyimide film, thermal imidization is preferred. In addition, the resin composition may contain an imidization accelerator.

[0273] (Diamine)

[0274] The resin composition may contain at least one structural unit derived from a compound represented by the following general formula (3)' and the following general formula (4):

[0275] 9,9-Bis(4-aminophenyl)fluorene(BAFL)

[0276]

[0277] Phenylenediamine (pPD, mPD)

[0278]

[0279] The content of the structure derived from the general formula (3)' in all diamine monomers (excluding compounds in which L1 and L2 in the above general formula (14) are amino groups) is preferably 20 mol% or more, more preferably 30 mol% or more, particularly preferably 40 mol% or more, preferably 95 mol% or less, more preferably 90 mol% or less.

[0280] By setting the content to 20 mol % or more, the YI and Rth of the obtained polyimide film can be lowered, and by setting the content to 90 mol % or less, the residual stress can be reduced.

[0281] The content of the structure derived from the general formula (4) in all diamine monomers (excluding compounds in which L1 and L2 in the general formula (14) are amino groups) is preferably 4 mol% or more, more preferably 10 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less. By setting it to 4 mol% or more, the Young's modulus of the obtained polyimide film can be increased, and by setting it to 80 mol% or less, the YI can be reduced.

[0282] Among the phenylenediamine compounds represented by the general formula (4), the compound represented by the following general formula (9) (p-phenylenediamine) is preferred from the viewpoint of heat resistance and Young's modulus of the polyimide film:

[0283]

[0284] The resin composition may contain a diamine other than the diamine compound represented by the general formula (3)' or the general formula (4) as needed. Examples of diamines other than general formula (3)' and general formula (4) include 2,2'-dimethylbenzidine (mTB), 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4- Bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane and 1,4-bis(3-aminopropyldimethylsilyl)benzene, 1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene (BiSAM), 1,4-cyclohexanediamine (CHDA), etc.

[0285] From the viewpoint of heat resistance and mechanical strength of the polyimide resin film, the diamine other than the general formula (3)′ and the general formula (4) is preferably at least one selected from the group consisting of 1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene (BiSAM) and 1,4-cyclohexanediamine (CHDA).

[0286] On the other hand, as a diamine, from the perspective of laser peelability of the polyimide film, and from the perspective of balancing laser peelability and Rth, it is not preferred to use 2,2'-bis(trifluoromethyl)benzidine (TFMB) or 2,2"-bis(trifluoromethyl)[1,1':4',1"-terphenyl]-4,4"-diamine as a diamine monomer.

[0287] (Acid dianhydride)

[0288] The resin composition contains a structural unit derived from a compound represented by the following general formula (5)':

[0289] 9,9-Bis(3,4-dicarboxyphenyl)fluorene dianhydride(BPAF)

[0290]

[0291] Pyromellitic anhydride (PMDA)

[0292]

[0293] Biphenyltetracarboxylic dianhydride (BPDA)

[0294]

[0295] The presence of such a structural unit is preferred because the obtained polyimide can achieve a good balance among glass transition temperature, YI (yellowness), Young's modulus, and chemical resistance, particularly when cured at 430° C. or higher.

[0296] The content of the general formula (5)' in all acid dianhydride monomers (including compounds in which L1 and L2 in the above general formula (14) are acid anhydride groups) is preferably 15 mol% or more, more preferably 20 mol% or more, particularly preferably 30 mol% or more, preferably 90 mol% or less, more preferably 80 mol% or less.

[0297] By setting the content to 15 mol % or more, the YI and Rth of the obtained polyimide film can be lowered, and by setting the content to 90 mol % or less, the residual stress can be reduced.

[0298] The content of the compound of the general formula (6) in all acid dianhydride monomers (including compounds in the above general formula (14) where L1 and L2 are acid anhydride groups) is preferably 5 mol% or more, more preferably 15 mol% or more, preferably 90 mol% or less, more preferably 80 mol% or less.

[0299] By setting the content to 5 mol % or more, the Tg of the obtained polyimide film can be increased, and by setting the content to 90 mol % or less, the YI can be decreased.

[0300] The content of the compound of the general formula (7) in all acid dianhydride monomers (including compounds in the above general formula (14) where L1 and L2 are acid anhydride groups) is preferably 10 mol% or more, more preferably 15 mol% or more, preferably 90 mol% or less, more preferably 80 mol% or less.

[0301] By setting the content to 10 mol % or more, the obtained polyimide film can have a lower YI and a higher Tg.

[0302] From the viewpoint of YI and Tg of the polyimide film, among the biphenyltetracarboxylic dianhydrides represented by the general formula (7), the compound having the following structure (3,3',4,4'-biphenyltetracarboxylic dianhydride) is preferred:

[0303]

[0304] In addition, the resin composition may contain at least one structural unit derived from a compound represented by the following general formula (15) or the following general formula (16):

[0305]

[0306] By including at least one structural unit derived from the compounds represented by the above-mentioned general formula (5)' and general formula (6), and including at least one structural unit derived from the compounds represented by general formula (15) and (16), the YI of the obtained polyimide can be reduced and the Tg can be increased, thereby making the Rth and laser peeling properties good, which is preferred.

[0307] The content of the general formula (15) or (16) in all acid dianhydrides (including compounds in which L1 and L2 in the above general formula (14) are acid anhydride groups) may be greater than 10 mol %, greater than 20 mol %, greater than 50 mol %, greater than 70 mol %, or greater than 90 mol %.

[0308] The resin composition may contain an acid dianhydride other than the compound represented by the general formula (5)', (6), (7), (15), or (16) as needed.

[0309] Examples of acid dianhydrides other than the general formula (5), (6), (7), (15) and (16) include 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 3,3',4,4'-benzophenonetetracarboxylic anhydride, 2,2',3,3'-benzophenonetetracarboxylic anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic anhydride, methylene-4,4'-diphthalic anhydride, 1,1-ethylidene-4,4'-diphthalic anhydride, 2,2-propylidene-4,4'-diphthalic anhydride, Phthalic anhydride, 1,2-ethylene-4,4'-diphthalic anhydride, 1,3-trimethylene-4,4'-diphthalic anhydride, 1,4-tetramethylene-4,4'-diphthalic anhydride, 1,5-pentamethylene-4,4'-diphthalic anhydride, 4,4'-oxydiphthalic anhydride, p-phenylenebis(trimellitic anhydride), thio-4,4'-diphthalic anhydride, sulfonyl-4,4'-diphthalic anhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, ,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-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride and 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride (ODPA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), a compound having the following structure (BzDA);

[0310]

[0311] The compound with the following structure (BNBDA), etc.

[0312]

[0313] The acid dianhydride other than the above general formula (5)', (6), (7), (15) and (16) is preferably at least one selected from the group consisting of HPMDA, BzDA and BNBDA. The acid dianhydride may be used alone or in combination of two or more.

[0314] It should be noted that in the resin composition of the present embodiment, when the structural unit derived from the general formula (4) is bonded adjacently (via an amide bond or an imide bond) to the structural unit derived from the following general formula (6) and / or general formula (7), the obtained polyimide has high heat resistance, but is colored and has poor YI and transmittance.

[0315]

[0316] Therefore, the present inventors have found that heat resistance and low YI can be maintained by not allowing the structural unit derived from the general formula (4) to be adjacently bonded to the structural unit derived from the general formula (6) and / or the general formula (7) or by allowing them to be separately bonded.

[0317] Specifically, the resin composition contains the structural unit represented by the following general formula (1) and / or (2):

[0318]

[0319] {In the formula, P1 represents a divalent organic group, P2 represents a tetravalent organic group, and p represents a positive integer.}

[0320]

[0321] {wherein, P3 represents a divalent organic group, P4 represents a tetravalent organic group, and q represents a positive integer.},

[0322] It is preferred that the ratio (mol %) of at least one structural unit selected from the following general formulas (10), (11), (12), and (13) in the above-mentioned resin composition is smaller than the ratio of structural units formed by acid dianhydride monomers and diamine monomers other than the above-mentioned general formulas (4), (6), and (7) connected by amide bonds / imide bonds, so that the obtained polyimide can have both high heat resistance and low YI.

[0323]

[0324] It should be noted that the ratio of the structural units formed by connecting the acid dianhydride monomer and the diamine monomer via amide bonds / imide bonds can be calculated based on the feed amount and feed order of each monomer, and can also be determined by the following measurement. 13C-NMR was calculated from the integrated value of the C peak of the carbonyl group of the amide / imide bond between pPD / PMDA and pPD / BPDA and the integrated value of the C peak of the carbonyl group of the amide / imide bond between other monomers.

[0325] Furthermore, a resin in which the structural unit derived from the above general formula (4) and the structural unit derived from the general formula (6) and / or the general formula (7) are not adjacently bonded or they are separately bonded can be synthesized by the following method.

[0326] That is, the synthesis of the resin of the general formula (1) and / or general formula (2) is performed without adding the compound of the general formula (6) and / or general formula (7) to the solution containing the compound of the general formula (4).

[0327]

[0328] Here, the above synthesis also includes polycondensing the compound of the general formula (4) with an acid dianhydride monomer other than the general formula (6) or (7), and then polycondensing a diamine monomer other than the general formula (4) with the compound of the general formula (6) or (7).

[0329] In addition, as a solution containing the compound of the general formula (4), in addition to a solution containing the compound of the general formula (4) alone or a solution containing other diamine monomers, it also includes the following situations: before this process, the acid dianhydride monomer is condensed with the diamine monomer containing the compound of the general formula (4), and the ratio of the diamine monomer (mol%) is high, so that the diamine monomer remains.

[0330] Furthermore, in the polycondensation reaction of the compound of the general formula (4) and the acid dianhydride monomer other than the general formula (6) or the general formula (7), when the molar fraction of the former (the compound of the general formula (4)) is less than the molar fraction of the latter (the acid dianhydride monomer other than the general formula (6) or the general formula (7)), it is understood that the compound of the general formula (4) is consumed in its polycondensation reaction and the compound of the general formula (4) does not exist alone. Therefore, after the above polycondensation reaction, adding the compound of the general formula (6) and / or (7) meets the requirement of "not adding the compound of the general formula (6) and / or (7) to the solution containing the compound of the general formula (4)".

[0331] In such a synthesis method, specifically, for example, a compound of the following general formula (3)' can be used as a diamine monomer:

[0332]

[0333] And / or a compound of the following general formula (5)' is used as the acid dianhydride monomer.

[0334]

[0335] In addition, a resin containing structural units represented by the above-mentioned general formulae (1) and (2), in which the structural unit derived from the above-mentioned general formula (4) is not adjacently bonded to the structural unit derived from the above-mentioned general formula (6) and / or the above-mentioned general formula (7) or they are separately bonded, can also be synthesized by the following method.

[0336] That is, after synthesizing the structural unit of the above general formula (2),

[0337] The structural unit of the general formula (1) is synthesized by polycondensing a compound of the following general formula (4) and a compound of the following general formula (5)′.

[0338]

[0339] Alternatively, after synthesizing the structural unit of the general formula (2),

[0340] The structural unit of the general formula (1) is synthesized by polycondensing the compound of the general formula (3)' below with the compound of the general formula (6) and / or the general formula (7) below.

[0341]

[0342] <Block copolymer structure>

[0343] The resin in the present invention has a block copolymer structure including a first block and a second block. The first block includes at least one structural unit derived from the general formula (4).

[0344]

[0345] Here, the first block does not contain a structure derived from the following general formula (6) and / or (7), and the second block does not contain a structure derived from the general formula (4). It should be noted that the structures derived from the general formula (6) and the general formula (7) may be block structures or may not be block structures. In addition, the resin of the present invention contains a first block having a structure derived from the general formula (4) and a second block having a structure derived from the general formula (6) and / or the general formula (7), and the structure derived from other monomers may be a block or may not be a block.

[0346]

[0347] This block copolymer structure can be obtained by the following method: after synthesizing the first block polymer, the raw material of the second block copolymer is added to the same reaction vessel for synthesis. In addition, the first block copolymer can also be synthesized in a reactor, mixed with the second block copolymer synthesized in another reactor, and heated for synthesis. However, considering simplicity and economy, it is preferably synthesized in the same reaction vessel.

[0348] The resin of the present invention includes a (solvent-soluble) all-polyimide precursor structure (hereinafter also referred to as PAA), a all-polyimide structure (hereinafter also referred to as PI), and a partially imidized polyimide precursor structure (hereinafter also referred to as PAI), but any of the structures are block copolymers and the synthesis methods are different.

[0349] In the case of PAA, the first block copolymer can be synthesized at room temperature for 24 hours, and then the second block copolymer can be synthesized at room temperature for 24 hours. In the case of PI, the first block can be synthesized at 180°C, cooled to room temperature, and the raw material of the second block can be added at room temperature, and the synthesis can be carried out at 180°C to prepare a block structure. In the case of PAI, the first block (containing a structure derived from the general formula (4)) can be reacted at 180°C to synthesize an imide unit, and then the temperature is restored to room temperature, and the raw material of the second block (containing a structure derived from the general formula (6) and / or (7)) can be added to synthesize an amide unit, or the second block (containing a structure derived from the general formula (6) and / or (7)) can be reacted at 180°C to synthesize an imide unit, and then the temperature is restored to room temperature, and the raw material of the second block (containing a structure derived from the general formula (4)) can be added to synthesize an amide unit.

[0350] Thus, by making the first block containing the structure derived from the general formula (4) and the second block containing the structure derived from the general formula (6) and / or the general formula (7) different blocks, it is possible to prevent the residues of pPD and PMDA / BPDA from being adjacently bonded. Thus, the obtained polyimide resin film can avoid the deterioration of YI and transmittance (the residues of pPD and PMDA / BPDA are adjacently bonded), and can achieve both high heat resistance and high mechanical properties (the residues of pPD and PMDA / BPDA are adjacently bonded).

[0351] On the other hand, when the above-mentioned synthesis method is not adopted, and the above-mentioned general formula (6) (PMDA) and / or the above-mentioned general formula (7) (BPDA) are added (at once) to the solution containing the above-mentioned general formula (4) (pPD) to carry out the reaction (Comparative Examples 4 to 6 described below), the first block containing the structure derived from the above-mentioned general formula (4) and the second block derived from the above-mentioned general formulas (6) and (7) are not formed. As a result, the structure derived from pPD and the structure derived from PMDA and / or BPDA are adjacently bonded, and the YI and transmittance are deteriorated.

[0352] <Silicon-containing compounds>

[0353] In the resin of this embodiment, in particular, the structural unit of the general formula (2) may include a structure derived from a silicon-containing compound represented by the following general formula (8):

[0354]

[0355] {wherein, P5 and P6, when present in plural numbers, each independently represent a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and r represents an integer of 1 to 200}.

[0356] Therefore, the silicon-containing compound used for the synthesis of the polyimide precursor in the present embodiment may be a compound having a reactive group that can be co-condensed with at least one of tetracarboxylic dianhydride and diamine.

[0357] Examples of such silicon-containing compounds include compounds represented by the following formula (17) (hereinafter also referred to as (17)):

[0358]

[0359] {where,

[0360] R1 is independently a single bond or a divalent organic group having 1 to 10 carbon atoms,

[0361] R2 and R3 are each independently a monovalent organic group having 1 to 10 carbon atoms, at least one of R2 and R3 is a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms,

[0362] R4 and R5 are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of R4 and R5 is a monovalent aromatic group having 6 to 10 carbon atoms.

[0363] R6 and R7 are each independently a monovalent organic group having 1 to 10 carbon atoms, and at least one of R6 and R7 is preferably an organic group containing an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms.

[0364] L1 and L2 are each independently a monovalent organic group containing an acid anhydride structure, an amino group, an isocyanate group, a carboxyl group, an alkoxycarbonyl group, a halogenated carbonyl group, a hydroxyl group, an epoxy group, or a mercapto group,

[0365] i is an integer from 1 to 200,

[0366] j and k are each independently an integer of 0 to 200, j is preferably an integer of 1 to 200, and,

[0367] 0≤j / (i+j+k)≤0.50, preferably satisfying the relationship of 0.05≤j / (i+j+k)≤0.50}.

[0368] R1 in formula (17) is 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. Specifically, as divalent aliphatic hydrocarbon groups having 1 to 10 carbon atoms, for example, straight-chain or branched alkylene groups such as methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, tert-butylene, n-pentylene, neopentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, and n-decylene may be mentioned; and cycloalkylene groups such as cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, and cyclooctylene may be mentioned. As divalent aliphatic hydrocarbon groups having 1 to 10 carbon atoms, at least one selected from the group consisting of ethylene, n-propylene, and isopropylene may be mentioned. The unsaturated group may be any of an unsaturated aliphatic group and an unsaturated aromatic group.

[0369] In the formula (17), R2 and R3 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.

[0370] The monovalent organic group having 1 to 10 carbon atoms may be any of linear, cyclic, and branched, and may be saturated or unsaturated. For example, as the monovalent organic group having 1 to 10 carbon atoms, there may be mentioned: linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; aromatic groups such as phenyl, tolyl, xylyl, α-naphthyl, and β-naphthyl.

[0371] 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. For example, as the monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, there may be mentioned: linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, and neopentyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, and cyclopentyl. As the monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, at least one selected from the group consisting of methyl, ethyl, and n-propyl is preferred.

[0372] R4 and R5 in formula (17) 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. For example, as the monovalent organic group having 1 to 10 carbon atoms, there may be mentioned: linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; aromatic groups such as phenyl, tolyl, xylyl, α-naphthyl, and β-naphthyl; and the like. Examples of the monovalent aromatic group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, α-naphthyl and β-naphthyl, and preferably phenyl, tolyl or xylyl.

[0373] R6 and R7 in formula (17) are independently monovalent organic groups 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. Examples of the monovalent organic group having 1 to 10 carbon atoms include: linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; aromatic groups such as phenyl, tolyl, xylyl, 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.

[0374] The organic group having an unsaturated aliphatic hydrocarbon group may be an unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms, and may be any of a linear, cyclic, and branched chain. As the unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms, for example, vinyl, allyl, 1-propenyl, 3-butenyl, 2-butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, octenyl, nonenyl, decenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, etc. are exemplified. As the unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms, it is preferably at least one selected from the group consisting of vinyl, allyl, and 3-butenyl.

[0375] A part or all of the hydrogen atoms of R1 to R7 in the formula (17) may be substituted with a substituent such as a halogen atom such as F, Cl, or Br, or may be unsubstituted.

[0376] L1 and L2 in formula (17) are each independently a monovalent organic group containing an acid anhydride structure (also referred to as an acid anhydride group), an amino group, an isocyanate group, a carboxyl group, an alkoxycarbonyl group, a halogenated carbonyl group, a hydroxyl group, an epoxy group, or a mercapto group.

[0377] As the monovalent organic group containing an acid anhydride structure, for example, there can be mentioned a 2,5-dioxotetrahydrofuran-3-yl group represented by the following formula:

[0378]

[0379] {In the above formula, "*" represents a connecting bond.}.

[0380] Among these, an amino group and an acid anhydride group are preferred, and an amino group is more preferred from the viewpoint of viscosity stability of the resin composition.

[0381] The alkoxy group in the alkoxycarbonyl group may be an alkoxy group having 1 to 6 carbon atoms, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc.

[0382] The halogen atom in the halogenated carbonyl group is preferably a halogen atom other than a fluorine atom, and more preferably a chlorine atom or an iodine atom.

[0383] From the viewpoint of the filterability of the resin composition, the functional group equivalent of the silicon-containing compound shown in formula (17) is preferably 800 or more, more preferably 1000 or more, and further preferably 1500 or more. On the other hand, when the functional group equivalent is 500 or less, there is a case where the filterability deteriorates. Here, the functional group equivalent is the molecular weight of the silicon-containing compound per 1 mol of functional group (unit: g / mol). The functional group equivalent can be measured by a known method according to existing standards, etc. In addition, when the functional group equivalent of the silicon-containing compound is 800 or more, the residual stress of the polyimide film under a nitrogen atmosphere is small, so it is preferred. It is believed that the reason is that when the functional group equivalent is above a specific value, the organosilicon region increases and the stress is relaxed.

[0384] i in formula (17) is an integer of 1 to 200, preferably an integer of 2 to 100, more preferably an integer of 4 to 80, and further preferably an integer of 8 to 40. j and k are each independently an integer of 0 to 200, j may be an integer of 1 to 200, and j and k are preferably integers of 0 to 50, more preferably integers of 0 to 20, and further preferably integers of 0 to 50.

[0385] If the resin in the resin composition has a structure derived from formula (17), the residual stress of the polyimide film measured in a nitrogen atmosphere is good (small), so it is preferred. The reason for measuring in a nitrogen atmosphere is that in the process of display, when an inorganic film such as SiO and SiN is formed on the polyimide film, there is a situation where it is exposed to a nitrogen atmosphere, so the residual stress in a nitrogen atmosphere is required to be small.

[0386] From the perspective of the type of monomer, cost, and molecular weight of the obtained polyimide precursor, the silicon-containing compound of general formula (17) is preferably a silicon-containing diamine. As the silicon-containing diamine, for example, a diamino (poly)siloxane represented by the following formula (18) is preferred:

[0387]

[0388] {In the formula, P5 each independently represents a divalent hydrocarbon group and may be the same or different, P3 and P4 are the same as R2 and R3 defined in the general formula (17), and l represents an integer of 1 to 200.}

[0389] Preferred structures of P3 and P4 in the general formula (18) include methyl, ethyl, propyl, butyl, and phenyl groups, among which methyl is preferred.

[0390] In the general formula (18), l is an integer of 1 to 200, and is preferably an integer of 3 to 200 from the viewpoint of heat resistance of a polyimide obtained by using the silicon-containing diamine represented by the formula (17).

[0391] The preferred range of the functional group equivalent of the compound represented by the general formula (18) is the same as that of the silicon-containing compound represented by the general formula (17).

[0392] Relative to the total mass of polyimide precursor / polyimide, the copolymerization ratio of silicon-containing diamine is preferably 0.5-30 mass %, more preferably 1.0 mass %-25 mass %, and further preferably 1.5 mass %-20 mass %. When the silicon-containing diamine is 0.5 mass % or more, the residual stress generated between the support body can be effectively reduced. When the silicon-containing diamine is 30 mass % or less, the transparency (especially low HAZE) of the obtained polyimide film is good, and it is preferred from the viewpoint of achieving high total light transmittance and high glass transition temperature.

[0393] The silicon-containing compound used as a monomer for the polyimide precursor / polyimide can be synthesized using the technical knowledge at the time of application as described above, or commercially available products can be used. Examples of commercially available products include: methylphenyl silicone oil modified with amine at both ends (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-1660B-3 (functional group equivalent 2200), X22-9409 (functional group equivalent 670)), methylphenyl silicone oil modified with anhydride at both ends (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-168-P5-B (functional group equivalent 2100)), methylphenyl silicone oil modified with epoxy at both ends (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-2000 (functional group equivalent weight 620)), dimethyl silicone modified with amino groups at both ends (manufactured by Shin-Etsu Chemical Co., Ltd.: PAM-E (functional group equivalent weight 130), X22-161A (functional group equivalent weight 800), X22-161B (functional group equivalent weight 1500), KF8012 (functional group equivalent weight 2200), manufactured by Dow Corning Toray: BY16-853U (functional group equivalent weight 450), manufactured by JNC: Silaplane FM3311 (number average molecular weight 1000)), both-end epoxy-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd.: X-22-163A (functional group equivalent 1750), both-end alicyclic epoxy-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd.: X-22-169B (functional group equivalent 1700)), both-end hydroxyl-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd.: KF-6000), both-end mercapto-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd.: X-22-167B (functional group equivalent 1700)), both-end acid anhydride-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd.: X-22-168A (functional group equivalent 1000)), etc. Among these, both-end amine-modified dimethyl silicone oil is preferred from the viewpoints of price, improved chemical resistance, and improved Tg.

[0394] <Solvent>

[0395] The resin composition typically contains a solvent. As the solvent, it is preferred that the solubility of the polyimide / polyimide precursor is good and the solution viscosity of the resin composition can be controlled to an appropriate solvent, and the reaction solvent of the polyimide precursor can be used as the solvent of the composition. Among them, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), Equamide M100, Equamide B100, etc. are preferred. As a specific example of the solvent composition, N-methyl-2-pyrrolidone (NMP) alone, or a mixed solvent of N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone (GBL) can be cited. The mass ratio of NMP to GBL can be, for example, NMP:GBL (mass ratio) = 10:90 to 90:10.

[0396] <Additional ingredients>

[0397] The resin composition of the present embodiment may further contain additional components in addition to the polyimide / polyimide precursor, the low molecular weight cyclic siloxane, and the solvent. Examples of the additional components include surfactants and alkoxysilane compounds.

[0398] (Surfactant)

[0399] By adding a surfactant to the resin composition of the present embodiment, the coating properties of the resin composition can be improved. Specifically, the generation of streaks in the coating film can be prevented.

[0400] Examples of such surfactants include silicone surfactants, fluorine surfactants, and nonionic surfactants other than these. Examples of silicone surfactants include: organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, X-70-093 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.); SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (trade names, manufactured by Dow Corning Toray Silicone Co., Ltd.); SILWET L-77, L-7001, FZ-2105, FZ-2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (trade names, manufactured by Nippon Unicar Co., Ltd.); DBE-814, DBE-224, DBE-621, CMS-626, CMS-222, KF-352A, KF-354L, KF-355A, KF-6020, DBE-821, DBE-712 (Gelest), BYK-307, BYK-310, BYK-378, BYK-333 (trade names, manufactured by BYK-Chemie Japan); Glanol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). Examples of fluorine-based surfactants include MEGAFAC F171, F173, R-08 (trade names, manufactured by Dainippon Ink & Chemicals Co., Ltd.); Fluorad FC4430, FC4432 (trade names, manufactured by Sumitomo 3M Co., Ltd.). Examples of the nonionic surfactants other than these include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and polyoxyethylene octylphenol ether.

[0401] Among these surfactants, silicone surfactants and fluorine surfactants are preferred from the viewpoint of the coating property (striping suppression) of the resin composition, and silicone surfactants are preferred from the viewpoint of reducing the influence of oxygen concentration on YI value and total light transmittance during the curing process. When a surfactant is used, its blending amount is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the polyimide precursor in the resin composition.

[0402] (Alkoxysilane compound)

[0403] In the case where the polyimide film obtained by the resin composition of the present embodiment is used for a flexible substrate, etc., the resin composition may contain 0.01 to 20 parts by mass of an alkoxysilane compound relative to 100 parts by mass of a polyimide precursor in order to obtain good adhesion between the support and the polyimide film. By making the content of the alkoxysilane compound relative to 100 parts by mass of a polyimide precursor 0.01 parts by mass or more, good adhesion can be obtained between the support and the polyimide film. In addition, from the perspective of the 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 relative to 100 parts by mass of a polyimide precursor, more preferably 0.05 to 10 parts by mass, and further preferably 0.1 to 8 parts by mass. By using an alkoxysilane compound, in addition to the above-mentioned improvement in adhesion, the coating properties of the resin composition are also improved (suppression of streaking unevenness), and the influence of oxygen concentration during curing on the YI value of the polyimide film can also be reduced.

[0404] Examples of the alkoxysilane compound include 3-ureidopropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, γ-aminoethyltriethoxysilane, γ-aminoethyltripropoxysilane, γ-aminoethyltributoxysilane, γ-aminobutyltriethoxysilane, γ-aminobutyltrimethoxysilane, γ-aminobutyltripropoxysilane, γ-aminobutyltributoxysilane, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and alkoxysilane compounds represented by the following structures, respectively.

[0405]

[0406] The alkoxysilane compounds may be used alone or in combination of two or more.

[0407] 《Method for producing resin composition》

[0408] The method for producing the resin composition in the present embodiment is not particularly limited, and for example, the following method can be used.

[0409] <Purification of Silicon-Containing Compounds>

[0410] The resin composition of the present embodiment can be manufactured by subjecting the polycondensation components containing acid dianhydride, diamine and silicon-containing compound to polycondensation reaction. As a method for reducing the total amount of cyclic silicon-containing compounds contained in the resin composition of the present embodiment, for example, the total amount of cyclic silicon-containing compounds can be reduced by purifying the silicon-containing compounds before the polycondensation reaction. Alternatively, the total amount of cyclic silicon-containing compounds can be reduced by purifying the resin composition during or after the polycondensation reaction.

[0411] As a method for purifying silicon-containing compounds, for example, stripping is performed while blowing an inert gas such as nitrogen into the silicon-containing compound in any container. As the stripping temperature, it is preferably above 200°C and below 300°C, more preferably above 220°C and below 300°C, and further preferably above 240°C and below 300°C. As the steam pressure of the stripping, the lower the better, it is below 1000Pa, more preferably below 300Pa, further preferably below 200Pa, and further preferably below 133.32Pa (1mmHg)Pa. As the stripping time, it is preferably above 4 hours and below 12 hours, and more preferably above 6 hours and below 10 hours. By adjusting to the above conditions, cyclic silicon-containing compounds can be efficiently removed, and the total amount of cyclic silicon-containing compounds can be controlled within a preferred range.

[0412] <Synthesis of polyimide / polyimide precursor>

[0413] The polyimide precursor of the present embodiment can be synthesized by subjecting a polycondensation component including an acid dianhydride, a diamine, and a silicon-containing compound to a polycondensation reaction. In connection with the synthesis of polyimide / polyimide precursor, a method for producing a resin composition including, for example, any of the following steps is provided:

[0414] A step of subjecting at least one compound selected from the general formulae (3) and (4), at least one compound selected from the general formulae (5) and (6), and other compounds to a polycondensation reaction to provide a polyimide precursor and / or a polyimide;

[0415] A step of subjecting at least one compound selected from the general formulae (3) and (4), at least one compound selected from the general formulae (5) and (6), a compound represented by the general formula (7), and other compounds to a polycondensation reaction to provide a polyimide precursor and / or a polyimide;

[0416] A step of subjecting at least one compound selected from the general formulae (3) and (4), at least one compound selected from the general formulae (5) and (6), at least one compound selected from the general formulae (15) and (16), and other compounds to a polycondensation reaction to provide a polyimide precursor and / or a polyimide;

[0417] A step of subjecting at least one compound selected from the general formulae (3) and (4), at least one compound selected from the general formulae (5) and (6), a compound represented by the general formula (7), at least one compound selected from the general formulae (15) and (16), and other compounds to a polycondensation reaction to provide a polyimide precursor and / or a polyimide;

[0418] A step of subjecting at least one compound selected from the general formulae (3) and (4), at least one compound selected from the general formulae (5) and (6), a silicon-containing compound represented by the general formula (17), and other compounds to a polycondensation reaction to provide a polyimide precursor and / or a polyimide;

[0419] A step of subjecting at least one compound selected from the general formulae (3) and (4), at least one compound selected from the general formulae (5) and (6), a compound represented by the general formula (7), a silicon-containing compound represented by the general formula (17), and other compounds to a polycondensation reaction to provide a polyimide precursor and / or a polyimide;

[0420] A step of subjecting at least one compound selected from the general formulae (3) and (4), at least one compound selected from the general formulae (5) and (6), at least one compound selected from the general formulae (15) and (16), a silicon-containing compound represented by the general formula (17), and other compounds to a polycondensation reaction to provide a polyimide precursor and / or a polyimide;

[0421] A step of subjecting at least one compound selected from the general formulae (3) and (4), at least one compound selected from the general formulae (5) and (6), a compound represented by the general formula (7), at least one compound selected from the general formulae (15) and (16), a silicon-containing compound represented by the general formula (17), and other compounds described above to a condensation polymerization reaction to provide a polyimide precursor and / or a polyimide.

[0422] In addition, the silicon-containing compound preferably uses the purified silicon-containing compound described above. In a preferred embodiment, the polycondensation component comprises an acid dianhydride, a diamine and a silicon-containing compound. The polycondensation reaction is preferably carried out in an appropriate solvent. Specifically, for example, the following method can be cited: after dissolving a predetermined amount of a diamine component and a silicon-containing compound in a solvent, a predetermined amount of an acid dianhydride is added to the obtained diamine solution and stirred. The imidization during the synthesis of the polyimide may be thermal imidization or chemical imidization using an imidization catalyst.

[0423] In addition, the present invention provides a method for producing a resin composition, wherein the resin composition comprises a resin, wherein the resin comprises structural units represented by the general formulae (1) and (2) described above, and the method for producing the resin composition comprises: after synthesizing a resin 2 having a structural unit represented by the general formula (2), polycondensing a compound represented by the general formula (4) described above with a compound represented by the general formula (5) to introduce the structural unit represented by the general formula (1) into the resin 2; or, after synthesizing a resin 2 having a structural unit represented by the general formula (2) by polycondensing a compound represented by the general formula (4) with a compound represented by the general formula (5), introducing the structural unit represented by the general formula (1) into the resin 2.

[0424] In addition, the present invention provides a method for producing a resin composition, which resin composition contains structural units represented by the general formulas (1) and (2) described above, and the method for producing the resin composition includes: after synthesizing a resin 2 having a structural unit of the general formula (2), the structural unit of the general formula (1) is introduced into the above-mentioned resin 2, and the above-mentioned P1 or P3 contains a structural unit derived from a compound represented by the general formula (4).

[0425] From the viewpoint of increasing the molecular weight of the polyimide precursor resin and the slit coating characteristics of the resin composition, the molar ratio of the acid dianhydride to the diamine when synthesizing the polyimide / polyimide precursor is preferably in the range of acid dianhydride: diamine = 100:90 to 100:110 (0.90 to 1.10 mol parts of diamine relative to 1 mol part of the acid dianhydride), and more preferably in the range of 100:92 to 100:101 (0.92 to 1.01 mol parts of diamine relative to 1 mol part of the acid dianhydride).

[0426] The molecular weight of the polyimide / polyimide precursor can be controlled by the types of acid dianhydride, diamine and silicon-containing compound, the adjustment of the molar ratio of acid dianhydride to diamine, the addition of end-capping agent, the adjustment of reaction conditions, etc. 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 higher the molecular weight of the polyimide precursor can be.

[0427] As the acid dianhydride component and the diamine component, it is recommended to use a high-purity product. As its purity, it is preferably 98% by mass or more, more preferably 99% by mass or more, and further preferably 99.5% by mass or more. By reducing the water content in the acid dianhydride component and the diamine component, it can also be made highly purified. In the case of using a variety of acid dianhydride components and / or a variety of diamine components, it is preferred that the acid dianhydride component as a whole and the diamine component as a whole have the above-mentioned purity, and it is more preferred that all types of acid dianhydride components and diamine components used have the above-mentioned purity respectively.

[0428] The solvent for the reaction is not particularly limited as long as it can dissolve the acid dianhydride component, the diamine component and the generated polyimide / polyimide precursor and obtain a high molecular weight polymer. Examples of such solvents include aprotic solvents, phenolic solvents, ethers and glycol solvents.

[0429] Examples of the aprotic solvent include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, 1,3-dimethylimidazolidinone, tetramethylurea, and amide solvents of the following general formula:

[0430]

[0431] {In the formula, R 12 = Equamide M100 (trade name: manufactured by KJ Chemicals Corporation) represented by methyl group, and R 12 =Equamide B100 represented by n-butyl (trade name: manufactured by KJ Chemicals Corporation); lactone solvents such as γ-butyrolactone and γ-valerolactone; phosphorus-containing amide solvents such as hexamethylphosphoramide and hexamethylphosphoric triamide; sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide, and cyclopentane; ketone solvents such as cyclohexanone and methylcyclohexanone; tertiary amine solvents such as picoline and pyridine; ester solvents such as (2-methoxy-1-methylethyl) acetate, etc.

[0432] Examples of the phenolic solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol and 3,5-xylenol.

[0433] Examples of the ether and glycol solvents include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, and 1,4-dioxane.

[0434] These solvents may be used alone or in combination of two or more.

[0435] The boiling point of the solvent used in the synthesis of the polyimide / polyimide precursor at normal pressure is preferably 60 to 300°C, more preferably 140 to 280°C, and further preferably 170 to 270°C. By making the boiling point of the solvent lower than 300°C, the drying process becomes short. If the boiling point of the solvent is above 60°C, it is not easy to produce roughness on the surface of the resin film during the drying process, and it is not easy for bubbles to mix into the resin film, etc., and a more uniform film can be obtained. From the perspective of solubility and reduction of edge abnormalities during coating, it is preferred 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 one or more of the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), and the compound represented by the general formula (6).

[0436] In order to make the polycondensation reaction proceed well, the water content in the solvent is, for example, preferably less than 3,000 mass ppm. In the resin composition in the present embodiment, the content of the molecule with a molecular weight less than 1,000 is less than 5 mass %. It is believed that the reason is that the situation in which there is a molecule with a molecular weight less than 1,000 in the resin composition is related to the moisture content of the solvent or raw material (acid dianhydride, diamine) used during synthesis. That is, it is believed that the reason is that the anhydride group of a part of the acid dianhydride monomer can be hydrolyzed into a carboxyl group due to moisture, and will not be high molecular weight, but remain in a low molecular state. Therefore, the less the moisture content of the solvent used in the above-mentioned polycondensation reaction, the more preferred. The moisture content of the solvent is preferably less than 3,000 mass ppm, more preferably less than 1,000 mass ppm. Similarly, the moisture content contained in the raw material is also preferably less than 3,000 mass ppm, more preferably less than 1,000 mass ppm.

[0437] The water content of the solvent is believed to be related to the grade of the solvent used (dehydrated grade, general grade, etc.), the solvent container (bin, 18L tank, canister, etc.), the storage state of the solvent (whether or not a rare gas is enclosed), the time from opening to use (use immediately after opening, or use after a period of time after opening, etc.). It is also believed to be related to whether or not the reactor is replaced with a rare gas before synthesis, whether or not a rare gas is circulated during synthesis, etc. Therefore, when synthesizing a polyimide precursor, it is preferred to use a high-purity product as a raw material, use a solvent with a small amount of water, and take measures such as avoiding mixing of moisture from the environment into the system before and during the reaction.

[0438] When each polycondensation component is dissolved in a solvent, heating may be performed as required. From the viewpoint of obtaining a polyimide precursor having a higher degree of polymerization, the reaction temperature during the synthesis of the polyimide precursor may preferably be 0°C to 120°C, 40°C to 100°C, or 60 to 100°C, and the polymerization time may preferably be 1 to 100 hours, or 2 to 10 hours. By setting the polymerization time to more than 1 hour, a polyimide precursor having a uniform degree of polymerization may be obtained, and by setting the polymerization time to less than 100 hours, a polyimide precursor having a high degree of polymerization may be obtained.

[0439] The resin composition of the present embodiment may contain other additional polyimide precursors in addition to the polyimide / polyimide precursor in the present embodiment. However, from the viewpoint of reducing the oxygen dependence of the YI value and the total light transmittance of the polyimide film, the mass ratio of the additional polyimide / polyimide precursor is preferably 30% by mass or less, and more preferably 10% by mass or less relative to the total amount of the polyimide / polyimide precursor in the resin composition.

[0440] The polyimide precursor in the present embodiment may be partially imidized (partially imidized). By partially imidizing the polyimide precursor, the viscosity stability during storage of the resin composition can be improved. From the perspective of balancing the solubility of the polyimide precursor in the resin composition with the storage stability of the solution, the imidization rate in this case is preferably 5% or more, more preferably 8% or more, and preferably 90% or less, more preferably 80% or less, and further preferably 70% or less. The partial imidization is obtained by heating the polyimide precursor to dehydrate and close the ring. The heating can be preferably carried out at a temperature of preferably 120 to 200°C, more preferably 150 to 185°C, and further preferably 150 to 180°C for preferably 15 minutes to 20 hours, more preferably 30 minutes to 10 hours.

[0441] As the polyimide precursor of the present embodiment, a substance obtained by esterifying part or all of the carboxylic acid by adding N,N-dimethylformamide dimethyl acetal or N,N-dimethylformamide diethyl acetal to the polyimide / polyimide precursor obtained by the above reaction and heating can be used. By esterification, the viscosity stability during storage can be improved. These ester-modified polyamic acids can also be obtained by the following method: reacting the above-mentioned acid dianhydride component with a monohydric alcohol having 1 equivalent relative to the acid anhydride group, and a dehydration condensation agent such as thionyl chloride and dicyclohexylcarbodiimide in sequence, and then performing a condensation reaction with a diamine component.

[0442] <Synthesis of polyimide>

[0443] As a more preferred embodiment, the polyimide varnish can be prepared in the form of a polyimide solution (also referred to as a polyimide varnish) containing polyimide and a solvent by dissolving the acid dianhydride component and the diamine component in a solvent, such as an organic solvent, adding an azeotropic solvent such as toluene, and removing the water generated during imidization to the outside of the system. Here, the conditions during the reaction are not particularly limited, for example, the reaction temperature is 0°C to 190°C, and the reaction time is 3 to 72 hours. In order to fully carry out the reaction with the diamines containing the sulfonic group, it is preferably heated at 180°C for about 12 hours. In addition, an inert atmosphere such as argon or nitrogen is preferably used during the reaction.

[0444] <Preparation of resin composition>

[0445] When the solvent used in the synthesis of the polyimide precursor is the same as the solvent contained in the resin composition, the synthesized polyimide / polyimide precursor solution can be used directly as a resin composition. As required, the resin composition can also be prepared by adding a further solvent and one or more additional components to the polyimide precursor within a temperature range of room temperature (25°C) to 80°C, and stirring and mixing. The stirring and mixing can be carried out using appropriate devices such as a Three-One Motor (made by Shinto Chemical Co., Ltd.) equipped with a stirring blade, a rotation and revolution stirrer, etc. As required, the resin composition can be heated to 40°C to 100°C.

[0446] On the other hand, when the solvent used in the synthesis of the polyimide / polyimide precursor is different from the solvent contained in the resin composition, the solvent in the synthesized polyimide precursor solution can be removed by an appropriate method such as reprecipitation, solvent distillation, etc., to separate the polyimide / polyimide precursor. Then, the desired solvent and additional components as needed are added to the separated polyimide precursor at a temperature range of room temperature (25° C.) to 80° C., and stirred and mixed to prepare the resin composition.

[0447] After the resin composition is prepared as described above, a portion of the polyimide precursor can be dehydrated and imidized to the extent that the polymer does not precipitate (partial imidization) by heating the resin composition at, for example, 130 to 200° C. for, for example, 5 minutes to 2 hours. The imidization rate can be controlled by controlling the heating temperature and the heating time. By partially imidizing the polyimide precursor, the viscosity stability of the resin composition during storage can be improved.

[0448] From the viewpoint of slit coating performance, the solution viscosity of the resin composition is preferably 500 to 100,000 mPa·s, more preferably 1,000 to 50,000 mPa·s, and further preferably 3,000 to 20,000 mPa·s. Specifically, from the viewpoint of not easily leaking from the slit nozzle, it is preferably 500 mPa·s or more, more preferably 1,000 mPa·s or more, and further preferably 3,000 mPa·s or more. From the viewpoint of not easily clogging the slit nozzle, it is preferably 100,000 mPa·s or less, more preferably 50,000 mPa·s or less, and further preferably 20,000 mPa·s or less.

[0449] Regarding the solution viscosity of the resin composition during the synthesis of polyimide / polyimide precursor, if it is higher than 200,000 MPa·s, there is a concern that stirring during synthesis becomes difficult. However, even if the solution becomes highly viscous during synthesis, a resin composition with a viscosity that is easy to handle 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 (e.g., VISCONICE HD, manufactured by Toki Industry).

[0450] From the viewpoint of viscosity stability during storage of the resin composition, the water content of the resin composition of the present embodiment is preferably 3,000 mass ppm or less, more preferably 2,500 mass ppm or less, further preferably 2,000 mass ppm or less, further preferably 1,500 mass ppm or less, particularly preferably 1,000 mass ppm or less, particularly preferably 500 mass ppm or less, particularly preferably 300 mass ppm or less, and particularly preferably 100 mass ppm or less.

[0451] "Polyimide film and method for producing the same"

[0452] The resin composition of the present embodiment can be used to provide a polyimide film (hereinafter also referred to as a polyimide resin film). The method for producing the polyimide film of the present embodiment includes: a coating step of coating the resin composition of the present embodiment on the surface of a support; a film forming step of heating the resin composition to form a polyimide resin film; and a stripping step of stripping the polyimide resin film from the support.

[0453] <Coating process>

[0454] In the coating process, the resin composition of the present embodiment is coated on the surface of the support. The support is not particularly limited as long as it has heat resistance to the heating temperature in the subsequent film forming process (heating process) and good peeling properties in the peeling process. Examples of the support include glass substrates, such as alkali-free glass substrates; silicon wafers; resin substrates such as PET (polyethylene terephthalate), OPP (stretched polypropylene), polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyamide-imide, polyetherimide, polyetheretherketone, polyethersulfone, polyphenylsulfone, and polyphenylene sulfide; and metal substrates such as stainless steel, alumina, copper, and nickel.

[0455] When forming a thin film of polyimide molding, for example, a glass substrate, a silicon wafer, etc. are preferred, and when forming a thick film or sheet of polyimide molding, for example, a support formed of PET (polyethylene terephthalate), OPP (oriented polypropylene), etc. is preferred.

[0456] As coating methods, generally, there can be cited: coating methods such as blade coaters, air knife coaters, roller coaters, spin coaters, flow coaters, die coaters, rod coaters, etc.; coating methods such as spin coating, spray coating, and dip coating; printing techniques represented by screen printing and gravure printing. For the resin composition of this embodiment, slit coating is preferred. The coating thickness should be appropriately adjusted according to the desired thickness of the resin film and the content of the polyimide precursor in the resin composition, preferably about 1 to 1,000 μm. The temperature in the coating process can be room temperature. In order to reduce the viscosity and improve the workability, the resin composition can be heated to, for example, 40°C to 80°C.

[0457] <Optional Drying Process>

[0458] After the coating process, a drying process may be performed, or the drying process may be omitted and the subsequent film forming process (heating process) may be directly performed. The drying process is performed for the purpose of removing the organic solvent in the resin composition. In the case of performing the drying process, suitable devices such as a heating plate, a box-type dryer, and a conveyor-type dryer may be used. The temperature of the drying process is preferably 80°C to 200°C, more preferably 100°C to 150°C. The implementation time of the drying process is preferably 1 minute to 10 hours, more preferably 3 minutes to 1 hour. A coating film containing a polyimide precursor is formed on a support in the above manner.

[0459] <Film formation process>

[0460] Next, a film forming process (heating process) is performed. The heating process is a process for removing the organic solvent contained in the above-mentioned coating film and simultaneously performing an imidization reaction of the polyimide precursor in the coating film to obtain a polyimide resin film. As a heating method, hot air drying, infrared heaters, hot air drying and infrared heaters, etc. can be used. Infrared rays can also use far infrared rays. The heating process can be performed using devices such as an inert gas oven, a hot plate, a box-type dryer, a conveyor belt type dryer, etc. This process can be performed simultaneously with the drying process, or two processes can be performed in sequence.

[0461] The heating process can be carried out under an air atmosphere, and from the viewpoint of obtaining safety, good transparency of the obtained polyimide film, low thickness direction retardation (Rth) and low YI value, it is preferably carried out under an inert gas atmosphere. As an inert gas, for example, nitrogen, argon, etc. can be listed. The heating temperature is appropriately set according to the type of polyimide precursor and the type of solvent in the resin composition, preferably 250°C to 550°C, more preferably 300°C to 450°C. If it is more than 250°C, imidization is well carried out, and if it is less than 550°C, it is possible to avoid the undesirable conditions such as reduced transparency and deterioration of heat resistance of the obtained polyimide film. The heating time is preferably about 0.1 hour to 10 hours.

[0462] In this embodiment, from the viewpoint of transparency and YI value of the obtained polyimide film, the oxygen concentration of the surrounding atmosphere in the above-mentioned heating step is preferably 2,000 mass ppm or less, more preferably 100 mass ppm or less, and further preferably 10 mass ppm or less. By heating in an atmosphere with an oxygen concentration of 2,000 mass ppm or less, the YI value of the obtained polyimide film can be made 30 or less.

[0463] <Peeling process>

[0464] In the peeling step, the polyimide resin film on the support is peeled off after being cooled to, for example, about room temperature (25° C.) to about 50° C. As the peeling step, for example, the following methods (1) to (4) may be mentioned.

[0465] (1) After a structure comprising a polyimide resin film / support is prepared by the above method, a laser is irradiated from the support side of the structure to ablate the interface between the support and the polyimide resin film, thereby peeling off the polyimide resin. Examples of the type of laser include solid (YAG) lasers, gas (UV excimer) lasers, etc. Preferably, a spectrum with a wavelength of 308 nm is used (see Japanese Patent Publication No. 2007-512568, Japanese Patent Publication No. 2012-511173, etc.).

[0466] (2) Before coating the resin composition on the support, a release layer is formed on the support, and then a structure comprising a polyimide resin film / release layer / support is obtained, and the polyimide resin film is released. Examples of the release layer include Parylene (registered trademark, manufactured by Japan PARYLENE Contract Co., Ltd.) and tungsten oxide; a release agent such as a vegetable oil-based, silicone-based, fluorine-based, or alkyd-based release agent may also be used (see Japanese Patent Publication No. 2010-067957, Japanese Patent Publication No. 2013-179306, etc.).

[0467] This method (2) may be used in combination with the laser irradiation of method (1).

[0468] (3) A method of obtaining a polyimide resin film by etching the metal using an etchable metal substrate as a support body to obtain a structure including a polyimide resin film / support body. The metal can be, for example, copper (as a specific example, electrolytic copper foil "DFF" manufactured by Mitsui Mining & Smelting Co., Ltd.), aluminum, etc. As an etchant, ferric chloride can be used for copper, and dilute hydrochloric acid can be used for aluminum.

[0469] (4) After obtaining a structure including a polyimide resin film / support by the above method, an adhesive film is attached to the surface of the polyimide resin film, the adhesive film / polyimide resin film is separated from the support, and then the polyimide resin film is separated from the adhesive film.

[0470] Among these stripping methods, from the perspective of the difference in refractive index between the front and back sides of the obtained polyimide resin film, the YI value and the elongation, method (1) or (2) is preferred. From the perspective of the difference in refractive index between the front and back sides of the obtained polyimide resin film, method (1) is more preferred, that is, before the stripping process, an irradiation process of irradiating a laser from the support side is performed. It should be noted that in method (3), when copper is used as a support, it can be seen that the YI value of the obtained polyimide resin film becomes larger and the elongation tends to decrease. This can be considered to be the influence of copper ions.

[0471] The thickness of the obtained polyimide film is not limited, but is preferably 1 to 200 μm, more preferably 5 to 100 μm.

[0472] 《Polyimide (cured resin film)》

[0473]

[0474] The structure of the polyimide contained in the polyimide resin film formed from the polyimide precursor of the above embodiment is represented by the following general formula (20).

[0475]

[0476] {In general formula (20), P1 and P2 are the same as P1 and P2 in general formula (1) or general formula (2), or P3 and P4 in general formula (2), and m is a positive integer.}

[0477] For the same reason, preferred P1 and P2 in the general formula (1) or (2) are also preferred in the polyimide of the general formula (20). The number m of repeating units in the general formula (20) is not particularly limited and may be an integer of 2 to 150.

[0478]

[0479] The structure of the polyimide contained in the polyimide resin film formed from the polyimide precursor composition of the above embodiment is represented by the following general formula (21).

[0480]

[0481] {In the general formula (21), P3 and P4 are the same as P1 and P2 in the general formula (1), and in the general formula (21), P5 and P6 are the same as P3 and P4 in the general formula (2), and m and n are positive integers.}

[0482] For the same reason, preferred P1 and P2 in formula (1) and preferred P3 and P4 in formula (2) are also preferred in the polyimide of formula (21). The number of repeating units m and n in formula (21) is not particularly limited and may be an integer of 2 to 150.

[0483] The polyimide resin film of this embodiment preferably satisfies the following properties:

[0484] ·YI (yellowness index) is 15 or less (based on a film thickness of 10 μm)

[0485] · Degassing start temperature (TDS) is above 420℃

[0486] The residual stress is 35 MPa or less (under nitrogen atmosphere) or the Rth (retardation in the thickness direction) is 100 nm or less (based on a film thickness of 10 μm).

[0487] Therefore, the polyimide resin film of the present embodiment is suitable for use in displays (particularly displays using LTPS (low temperature polycrystalline silicon) or LTPO (low temperature polycrystalline oxide)).

[0488] 《Application of polyimide film》

[0489] The polyimide film obtained by the resin composition of the present embodiment can be used as, for example, a semiconductor insulating film, a thin film transistor liquid crystal display (TFT-LCD) insulating film, an electrode protective film, and can also be used as a transparent substrate for display devices such as a liquid crystal display, an organic electroluminescent display, a field emission display, and electronic paper. In particular, the polyimide film obtained by the resin composition of the present embodiment can be suitably used as a substrate for a thin film transistor (TFT) substrate, a color filter substrate, a touch panel substrate, and a transparent conductive film (ITO, Indium Thin Oxide) in the manufacture of a flexible device. As a flexible device to which the polyimide film in the present embodiment can be applied, for example, a flexible display TFT device, a flexible solar cell, a flexible touch panel, a flexible lighting, a flexible battery, a flexible printed substrate, a flexible color filter, and a surface covering lens for smartphone use can be listed.

[0490] Typically, the process of forming TFTs on a flexible substrate using a polyimide film is performed at a wide temperature range of 150° C. to 650° C. Specifically, when amorphous silicon is used to make a TFT device, a process temperature of 250° C. to 350° C. is generally required, and the polyimide film of this embodiment needs to be able to withstand this temperature. Therefore, specifically, it is necessary to appropriately select a polymer structure having a glass transition temperature and a thermal decomposition start temperature above the process temperature.

[0491] When using metal oxide semiconductors (IGZO, etc.) to manufacture TFT devices, a process temperature of 320°C to 400°C is generally required. The polyimide film of this embodiment needs to be able to withstand this temperature. Therefore, it is necessary to appropriately select a polymer structure having a glass transition temperature and a thermal decomposition start temperature that are higher than the highest temperature of the TFT manufacturing process.

[0492] When LTPS (low temperature polysilicon) or LTPO (low temperature polycrystalline oxide) is used to make TFT devices, a process temperature of 380°C to 520°C is usually required. The polyimide film of this embodiment needs to be able to withstand this temperature. Therefore, it is necessary to appropriately select a glass transition temperature and a thermal decomposition start temperature above the highest temperature of the TFT manufacturing process. On the other hand, due to these thermal histories, the more the polyimide film is exposed to a high temperature process, the more the optical properties (especially transmittance, delay characteristics and YI value) of the polyimide film tend to decrease. However, the polyimide obtained from the polyimide precursor of this embodiment has good optical properties even after a thermal history.

[0493] Hereinafter, as an example of application of the polyimide film of the present embodiment, a method for producing a display and a laminate will be described.

[0494] <Method for manufacturing display>

[0495] The manufacturing method of the display of the present embodiment includes: a coating step, which is to coat the resin composition of the present embodiment on the surface of the support; a film forming step, which is to heat the above-mentioned resin composition to form a polyimide resin film; an element forming step, which is to form an element on the above-mentioned polyimide resin film; and a peeling step, which is to peel off the above-mentioned polyimide resin film on which the above-mentioned element is formed from the above-mentioned support.

[0496] Manufacturing example of flexible organic EL display

[0497] Figure 1 FIG. 1 is a schematic diagram showing the structure of a top-emission type flexible organic EL display above a polyimide substrate as an example of the display of this embodiment. Figure 1 The organic EL structure 25 of the embodiment is described. For example, an organic EL element 250a emitting red light, an organic EL element 250b emitting green light, and an organic EL element 250c emitting blue light are arranged as one unit in a matrix, and a partition wall (bank) 251 is used to divide the light-emitting area of ​​each organic EL element. Each organic EL element is composed of a lower electrode (anode) 252, a hole transport layer 253, a light-emitting layer 254, and an upper electrode (cathode) 255. On the lower layer 2a representing a CVD multilayer film (multi-barrier layer) formed of silicon nitride (SiN) and silicon oxide (SiO), a plurality of TFTs 256 (selected from low-temperature polycrystalline silicon (LTPS), metal oxide semiconductor (IGZO, etc.)) for driving the organic EL element, an interlayer insulating film 258 having a contact hole 257, and a lower electrode 259 are provided. The organic EL element is sealed by a sealing substrate 2b, and a hollow portion 261 is formed between each organic EL element and the sealing substrate 2b.

[0498] The manufacturing process of the flexible organic EL display includes: making a polyimide film on a glass substrate support, and making a Figure 1 The process of manufacturing the organic EL substrate shown in the figure; the process of manufacturing the sealing substrate; the assembly process of bonding the two substrates together; and the process of peeling off the organic EL display made on the polyimide film from the glass substrate support. The organic EL substrate manufacturing process, the sealing substrate manufacturing process and the assembly process can apply known manufacturing processes. An example thereof is listed below, but it is not limited to this. The peeling process is the same as the above-mentioned polyimide film peeling process.

[0499] For example, if you refer to Figure 1 First, a polyimide film is prepared on a glass substrate support by the above method, and a multi-barrier layer (SiN) formed by a multilayer structure of silicon nitride (SiN) and silicon oxide (SiO) is prepared on the top thereof by a CVD method or a sputtering method. Figure 1The lower substrate 2a in the middle is used to make a metal wiring layer for driving TFT on its upper part using photoresist or the like. An active buffer layer such as SiO is made on its upper part using CVD method, and a TFT device such as metal oxide semiconductor (IGZO) or low temperature polycrystalline silicon (LTPS) is made on its upper part ( Figure 1 After the TFT substrate for the flexible display is manufactured, an interlayer insulating film 258 having a contact hole 257 is formed by using a photosensitive acrylic resin or the like. An ITO film is formed by a sputtering method or the like to form a lower electrode 259 in a manner matching the TFT.

[0500] Next, after forming a partition wall (bank) 251 using photosensitive polyimide or the like, a hole transport layer 253 and a light-emitting layer 254 are formed in each space 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 (bank) 251. Thereafter, an organic EL material (which is the same as the red light) emitting layer is evaporated by a known method using a fine metal mask or the like as a mask. Figure 1 The organic EL element 250a emitting red light in the embodiment corresponds to the organic EL element 250a emitting red light), the organic EL material emitting green light (corresponding to the organic EL element 250a emitting red light in the embodiment Figure 1 The organic EL element 250b emitting green light in the embodiment corresponds to the organic EL element 250b emitting green light and the organic EL material emitting blue light (corresponding to Figure 1 The organic EL substrate is manufactured by sealing the organic EL substrate with a sealing film or the like ( Figure 1 The device above the polyimide substrate is separated from the glass substrate support by a known separation method such as laser separation, thereby making a top-emitting flexible organic EL display. When the polyimide of this embodiment is used, a transparent (see-through) flexible organic EL display can be made. A bottom-emitting flexible organic EL display can be made by a known method.

[0501] Manufacturing example of flexible liquid crystal display

[0502] The polyimide film of this embodiment can be used to make a flexible liquid crystal display. As a specific production method, a polyimide film is produced on a glass substrate support using the above method, and a TFT substrate formed of, for example, amorphous silicon, a metal oxide semiconductor (IGZO, etc.) and low-temperature polycrystalline silicon (LTPS) is produced using the above method. Separately, according to the coating process and film formation process of this embodiment, a polyimide film is produced on a glass substrate support, and a color filter glass substrate (CF substrate) having a polyimide film is produced according to a known method and using a color resist, etc. For one of the TFT substrate and the CF substrate, a sealing material including a thermosetting epoxy resin or the like is applied by screen printing into a frame-shaped pattern lacking a liquid crystal injection port, and spherical spacers having a diameter equivalent to the thickness of the liquid crystal layer and formed of plastic or silicon dioxide are scattered on the other substrate.

[0503] Next, the TFT substrate and the CF substrate are attached to solidify the sealing material. In addition, the liquid crystal material is injected into the space surrounded by the TFT substrate, the CF substrate and the sealing material by decompression, and 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 glass substrate on the CF side and the glass substrate on the TFT side are peeled off at the interface between the polyimide film and the glass substrate by laser peeling or the like, thereby making it possible to produce a flexible liquid crystal display.

[0504] In particular, in the present embodiment, by including a process of heating a laminate comprising a polyimide resin film / inorganic film having a YI (yellowness index) of 15 or less (calculated as a film thickness of 10 μm) at above 420° C., a display having sufficient characteristics required as a display (taking into account characteristics such as glass transition temperature when cured at above 420° C., YI, Young's modulus, chemical resistance, and heat resistance of the laminate, etc.) can be manufactured.

[0505] Furthermore, in this embodiment, by making the polyimide film satisfy the following characteristics, a display having sufficient characteristics required for the above-mentioned display can be manufactured:

[0506] · Degassing start temperature (TDS) is above 420℃

[0507] The residual stress is 35 MPa or less (under nitrogen atmosphere) or the Rth (retardation in the thickness direction) is 100 nm or less (based on a film thickness of 10 μm).

[0508] Furthermore, in this embodiment, a display having sufficient characteristics required for a display such as the above can be manufactured by including a step of heating a laminate including a polyimide resin film and an inorganic film satisfying all of the following characteristics at 420° C. or higher and then irradiating with an excimer laser:

[0509] ·YI (yellowness index) is 15 or less (based on a film thickness of 10 μm)

[0510] The degassing start temperature (TDS evaluation) is 440°C or higher.

[0511] Furthermore, in this embodiment, by making the polyimide resin film satisfy all of the following characteristics, a display having sufficient characteristics as the characteristics required for the above-mentioned display can be manufactured:

[0512] ·Residual stress is less than 35MPa (under nitrogen atmosphere)

[0513] Rth (retardation in the thickness direction) is 100 nm or less (based on a film thickness of 10 μm).

[0514] Furthermore, in this embodiment, a laminate including a polyimide resin film and an inorganic film that satisfies all of the following properties is used:

[0515] ·YI (yellowness index) is 15 or less (based on a film thickness of 10 μm)

[0516] · Degassing start temperature (TDS evaluation) is 440℃ or above

[0517] ·Residual stress is less than 35MPa (under nitrogen atmosphere)

[0518] Rth (thickness direction retardation) is less than 100nm (converted to a film thickness of 10μm),

[0519] The process includes a dehydrogenation treatment step, an excimer laser irradiation step, an ion implantation step,

[0520] By performing the heating and annealing step at 400° C. or higher and the dehydrogenation treatment step at 420° C. or higher, a display having sufficient characteristics required for the above-mentioned display can be manufactured.

[0521] <Method for producing laminate>

[0522] The manufacturing method of the laminated body of the present embodiment includes: a coating step, which is to coat the resin composition of the present embodiment on the surface of a support body; a film forming step, which is to heat the above-mentioned resin composition to form a polyimide resin film; and an element forming step, which is to form an element on the above-mentioned polyimide resin film.

[0523] As the element in the laminate, the element exemplified in the manufacture of flexible devices such as the above-mentioned flexible display can be cited. As the support, for example, a glass substrate can be used. The preferred specific order of the coating process and the film forming process is the same as that described in the method for manufacturing the above-mentioned polyimide film. In the element forming process, the above-mentioned element is formed on the polyimide resin film as a flexible substrate formed on the support. Then, the polyimide resin film and the element can be arbitrarily peeled off from the support in the peeling process.

[0524] Example

[0525] Hereinafter, the embodiment of the present invention will be described in detail using Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

[0526] 《Measurement and evaluation methods》

[0527] <Weight average molecular weight>

[0528] The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) under the following conditions.

[0529] As a solvent, NMP (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography, prepared by adding 24.8 mmol / L of lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5%) and 63.2 mmol / L of phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography) and dissolving the mixture immediately before measurement) was used. A standard curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).

[0530] Column: Shodex KD-806M (manufactured by Showa Denko Co., Ltd.)

[0531] Flow rate: 1.0mL / min

[0532] Column temperature: 40°C

[0533] Pump: PU-2080Plus (manufactured by JASCO)

[0534] Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO) and UV-2075Plus (UV-VIS: ultraviolet visible absorptometer, manufactured by JASCO)

[0535] <Glass transition temperature (Tg)>

[0536] As a support, a 6-inch (15.24 cm) silicon wafer substrate with an aluminum vapor-deposited layer on the surface was used. On the surface of the aluminum vapor-deposited layer, the resin composition prepared in each embodiment and comparative example was spin-coated in such a way that the film thickness after curing (thin filming) became 10 μm to form a coating film. After pre-baking the coating film at 100° C. for 6 minutes, a vertical curing furnace (manufactured by Koyo Thermo Systems Co., Ltd., model name "VF-2000B") in which the oxygen concentration in the furnace was adjusted to less than 10 mass ppm was used, and it was cured at 430° C. for 30 minutes to form a polyimide film on the wafer. The wafer with the obtained polyimide film was immersed in a dilute hydrochloric acid aqueous solution overnight, and the polyimide film sheet was peeled off and dried.

[0537] The obtained polyimide film (3 mm wide and 10 mm long) was used to measure the elongation at break of the polyimide film in the range of 50 to 500° C. under a load of 5 g and a heating rate of 10° C. / min under a nitrogen flow (flow rate of 20 ml / min). Based on the measurement results, the temperature dependency of the elongation at break was plotted, and the inflection point of the plot was evaluated as the glass transition temperature (Tg). The evaluation was then performed according to the following criteria.

[0538] A: Tg is above 450℃ "Excellent"

[0539] B: Tg is 425°C or higher and less than 450°C "Good"

[0540] C: Tg is less than 425℃ "bad"

[0541] <Yellowness(YI)>

[0542] On an alkali-free glass substrate (hereinafter also referred to as "glass substrate" or simply "substrate") of 100 mm in length × 100 mm in width × 0.5 mm in thickness, the resin composition of the embodiment and the comparative example is applied in an area 5 mm inward from the end of the glass substrate in such a way that the film thickness after curing becomes 10 μm. A slit coater (LC-R300G, manufactured by SCREEN Finetech Solutions) is used for coating. A reduced pressure dryer (manufactured by Tokyo Ohka Industry) is used to remove the solvent from the obtained glass substrate with a coating at 80°C, 100 Pa, and 30 minutes to obtain a glass substrate with a resin composition coating. The obtained glass substrate with a resin composition coating is heated at 430°C for 30 minutes in a nitrogen atmosphere (oxygen concentration of less than 300 ppm) using an oven (INH-9N1, manufactured by Koyo Thermo Systems Co., Ltd.) to form a polyimide resin film on the glass substrate. The obtained sample was used as a test piece, and the yellowness (YI) value was measured using a spectrophotometer (manufactured by Nippon Denshoku Industries Co., Ltd., model name "SE600") and a D65 light source. The obtained results were converted to a film thickness of 10 μm, and were evaluated according to the following criteria.

[0543] A: YI is below 10, “Excellent”

[0544] B: YI is more than 10 and less than 15 "good"

[0545] C: YI over 15 “bad”

[0546] <Young's modulus>

[0547] Similar to "<Glass transition temperature (Tg)>", a polyimide film is formed on the aluminum vapor-deposited layer of a 6-inch (15.24 cm) silicon wafer substrate having an aluminum vapor-deposited layer on the surface. A 3 mm wide slit is formed in the obtained polyimide film using a dicing saw (manufactured by DISCO Co., Ltd., trade name "DAD 3350"), and then the wafer with the polyimide film is immersed in a dilute hydrochloric acid aqueous solution overnight, the polyimide film sheet is peeled off, and it is dried to obtain a polyimide sheet with a width of 3 mm. It is cut into a length of 50 mm to obtain a polyimide measurement sample with a width of 3 mm and a length of 50 mm. The Young's modulus of the polyimide measurement sample is measured at a test speed of 40 mm / min and an initial load of 0.5 fs using TENSILON (manufactured by Orientec Co., Ltd., model name "UTM-II-20"), and evaluated according to the following criteria.

[0548] A: Young's modulus is 3.5 GPa or above "excellent"

[0549] B: Young's modulus is 2.5 GPa or more and less than 3.5 GPa "Good"

[0550] C: Young's modulus less than 2.5GPa "poor"

[0551] <Chemical resistance>

[0552] Similar to "<Glass transition temperature (Tg)>", a polyimide film having a thickness of 10 μm after curing was prepared on a glass substrate. A portion of the surface of the polyimide film was peeled off using a cutter, and the film thickness of the portion was measured using a contact profilometer. Using the sample prepared in this manner, a chemical resistance test was performed under the following conditions;

[0553] Conditions: Immerse in a solution of dimethyl sulfoxide / monoethanolamine (70 / 30 (wt%)) for 120 seconds at room temperature

[0554] After the test, the sample was dried in a hot air oven at 50° C. for 30 minutes, and then the peeled portion was observed with an optical microscope. The film thickness after the test was measured by the same method as above and evaluated according to the following criteria.

[0555] A: No cracks were observed and the film thickness did not decrease "Excellent"

[0556] B: Cracks were observed, but the film thickness did not decrease. "Good"

[0557] C: Cracks observed, film thickness reduced by 5% or more "poor"

[0558] <Evaluation over time of a laminate having an inorganic film formed thereon (heat resistance of the laminate)>

[0559] A 6-inch (15.24 cm) silicon wafer substrate was used as a support, and a polyimide film with a thickness of 10 μm was formed on one surface of the wafer in the same manner as in "<Glass transition temperature (Tg)>". A silicon nitride (SiNx) film (inorganic film) with a thickness of 100 nm was formed on the obtained polyimide film by CVD, thereby obtaining a laminated body in which a wafer, a polyimide film, and a silicon nitride film were sequentially stacked.

[0560] Next, the obtained laminate was placed in an atmosphere of 23° C. and 50% RH for 3 days. Thereafter, a heat treatment was performed at 430° C. for 60 minutes using a vertical curing furnace (manufactured by Koyo Thermo Systems, Inc., model name “VF-2000B”) in which the oxygen concentration in the furnace was adjusted to 10 mass ppm or less, and the surface of the silicon nitride film was observed with the naked eye and an optical microscope, and evaluated according to the following criteria.

[0561] A: No wrinkles or swelling were observed (heat resistance after aging was evaluated as "good")

[0562] B: Wrinkles and / or swelling were observed (heat resistance after aging was evaluated as "acceptable")

[0563] C: Wrinkles and / or swelling and coloring were observed (heat resistance after aging was evaluated as "failed")

[0564] <Residual stress>

[0565] The resin composition prepared in the examples and comparative examples was applied by a spin coater on a 6-inch (15.24 cm) silicon wafer having a thickness of 625 μm ± 25 μm and the “warpage amount” of which was measured in advance, and pre-baked at 100° C. for 7 minutes. Thereafter, a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) was used to adjust the oxygen concentration in the furnace to 10 mass ppm or less, and a heat curing treatment (curing treatment) was performed at 430° C. for 30 minutes to produce a silicon wafer with a polyimide resin film having a thickness of 10 μm after curing.

[0566] The amount of warpage of the wafer was measured using a residual stress measuring device (manufactured by Tencor Corporation, model name FLX-2320), and the residual stress generated between the silicon wafer and the resin film “under a nitrogen atmosphere” was evaluated.

[0567] <Rth(Retardation in thickness direction)>

[0568] The resin composition of the embodiment and the comparative example is coated on a 200 mm square alkali-free glass substrate (hereinafter also referred to as a glass substrate) in a manner that the film thickness becomes 10 μm after curing to form a coating film. The coating is carried out using a slit coater (TN25000, Tokyo Ohka Industry). For one of the glass substrates having a coating film of the obtained polyimide precursor composition, the solvent is removed by drying at 100 ° C for 30 minutes in an oven (KLO-30NH, Koyo Thermo Systems) under a nitrogen atmosphere (oxygen concentration of less than 300 ppm). Afterwards, the polyimide resin film is formed on the glass substrate by heating at 430 ° C for 30 minutes under a nitrogen atmosphere (oxygen concentration of less than 300 ppm).

[0569] The polyimide film produced in this manner was measured for Rth (based on a film thickness of 10 μm) using a birefringence retardation measuring device (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.) The wavelength of the measuring light was set to 589 nm.

[0570] <Degassing start temperature (TDS evaluation)>

[0571] Similar to "<Yellowness (YI)>", a polyimide film is formed on a 6-inch silicon wafer substrate. The obtained silicon wafer with a polyimide film is cut into 1 cm squares as samples for TDS (Thermal Desorption Spectrometry) measurement. The samples prepared in this way are evaluated for TDS using EMD-WA1000 (manufactured by Electronic Science Co., Ltd.) to determine the degassing start temperature. The stage is heated from 50°C to 500°C, and the heating rate at this time is set to 10°C / min. The value at which the pressure in the chamber is stable under the condition of a stage temperature of 50°C to 400°C is set as the baseline. The pressure in the chamber rises from the baseline by 1.0×10 -7 The temperature at Pa was defined as the degassing start temperature.

[0572] 《Example 1》

[0573] Nitrogen gas was introduced into a separable flask with a stirring bar, and NMP (183 g) as a solvent and BAFL (13.7 g; 39.2 mmol) as a diamine as shown in Table 1 were added while stirring, followed by PMDA (4.4 g; 20.0 mmol) as a dianhydride, and the mixture was stirred at room temperature for 24 hours.

[0574] Then, pPD (6.4 g; 58.8 mmol) was added as a diamine while stirring, and then BPAF (36.7 g; 80.0 mmol) was added as an acid dianhydride. The mixture was stirred at room temperature for 24 hours to obtain an NMP solution of a polyimide precursor (hereinafter also referred to as a varnish). The obtained varnish was stored in a freezer (set to -20°C, the same below), thawed during evaluation, and NMP was added so that the solid content became 15 wt% for use.

[0575] 《Examples 4 and 7》

[0576] The same procedure as in Example 1 was carried out except that the types and amounts of the solvent, the acid dianhydride, and the diamine were changed to those shown in Table 1.

[0577] 《Example 2》

[0578] Nitrogen gas was introduced into a separable flask with a stirring rod having a Dean-Stark tube and a reflux tube at the upper part, and NMP (183 g) as a solvent, toluene (19 g), and BAFL (13.7 g; 39.2 mmol) as a diamine as shown in Table 1 were added while stirring, and then PMDA (4.4 g; 20.0 mmol) as a dianhydride was added at room temperature, and the mixture was heated to reflux at 180°C for 3 hours to carry out imidization, and then the temperature was returned to room temperature.

[0579] Then, pPD (6.4 g; 58.8 mmol) as a diamine was added under stirring at room temperature, followed by BPAF (36.7 g; 80.0 mmol) as an acid dianhydride, and the mixture was heated under reflux at 180°C for 3 hours to carry out imidization. Thereafter, the reaction was continued for 1 hour at 180°C while toluene was extracted.

[0580] After the reaction, the oil bath was removed and the temperature was restored to room temperature to obtain a polyimide NMP solution (hereinafter also referred to as varnish). The obtained varnish was stored in a freezer (set to -20°C, the same below), and NMP was added to give a solid content of 15 wt%, and the varnish was thawed and used during evaluation.

[0581] 《Examples 5, 8, 12, 13》

[0582] The same procedure as in Example 2 was carried out except that the types and amounts of the solvent, the acid dianhydride, and the diamine were changed to those described in Table 1.

[0583] 《Example 3》

[0584] Nitrogen gas was introduced into a separable flask with a stirring bar, and NMP (205 g) as a solvent and BAFL (13.4 g; 38.5 mmol) as a diamine as shown in Table 1 were added while stirring, followed by the addition of PMDA (4.4 g; 20.0 mmol) as an acid dianhydride, and the mixture was stirred at room temperature for 24 hours.

[0585] Then, pPD (6.2 g; 57.8 mmol) and 7.50 g of the silicon-containing compound (1) were added as diamines while stirring, and then BPAF (36.7 g; 80.0 mmol) was added as acid dianhydride. Then, the mixture was stirred at room temperature for 24 hours to obtain an NMP solution of a polyimide precursor (hereinafter also referred to as varnish). The obtained varnish was stored in a freezer (set to -20°C, the same below), and NMP was added so that the solid content became 15 wt% during evaluation, and the varnish was thawed and used.

[0586] 《Examples 9 and 16》

[0587] The same procedure as in Example 3 was carried out except that the types and amounts of the solvent, the acid dianhydride, the diamine, and the silicon-containing compound were changed to those shown in Table 1.

[0588] Example 6

[0589] Nitrogen gas was introduced into a separable flask with a stirring rod having a Dean-Stark tube and a reflux tube at the upper part, and NMP (210 g) and toluene (22 g) as a solvent and BAFL (13.4 g; 38.5 mmol) as a diamine as shown in Table 1 were added while stirring. Then, BPDA (5.9 g; 20.0 mmol) as a dianhydride was added at room temperature, and the mixture was heated to reflux at 180°C for 3 hours to carry out imidization, and then cooled to room temperature.

[0590] Then, pPD (6.2 g; 57.8 mmol) and silicon-containing compound (1) (7.69 g) were added as diamines at room temperature with stirring, followed by BPAF (36.7 g; 80.0 mmol) as dianhydride, and the mixture was heated under reflux at 180°C for 3 hours to carry out imidization. Thereafter, the reaction was continued for 1 hour at 180°C while toluene was extracted.

[0591] After the reaction, the oil bath was removed and the temperature was returned to room temperature to obtain a polyimide NMP solution (hereinafter also referred to as varnish). The obtained varnish was stored in a freezer (set to -20°C, the same below), thawed during evaluation, and NMP was added so that the solid content became 15 wt%.

[0592] 《Examples 10, 14, 15, 17, 18》

[0593] The same procedure as in Example 6 was carried out except that the types and amounts of the solvent, the acid dianhydride, the diamine, and the silicon-containing compound were changed to those shown in Table 1.

[0594] Example 11

[0595] Nitrogen gas was introduced into a separable flask with a stirring rod having a Dean-Stark tube and a reflux tube at the upper part, and NMP (193 g) and toluene (20 g) as a solvent and BAFL (13.7 g; 39.2 mmol) as a diamine as shown in Table 1 were added while stirring. Then, BPDA (5.7 g; 19.5 mmol) and PMDA (2.1 g; 9.8 mmol) as dianhydride were added at room temperature, and the mixture was heated to reflux at 180°C for 3 hours to carry out imidization, and then cooled to room temperature.

[0596] Then, pPD (6.4 g; 58.8 mmol) was added as a diamine at room temperature with stirring, followed by BPAF (31.4 g; 68.4 mmol) and silicon-containing compound (2) (7.33 g) as an acid dianhydride, and the mixture was heated under reflux at 180°C for 3 hours to carry out imidization. Thereafter, the reaction was continued for 1 hour at 180°C while removing toluene.

[0597] After the reaction, the oil bath was removed and the temperature was returned to room temperature to obtain a polyimide NMP solution (hereinafter also referred to as varnish). The obtained varnish was stored in a freezer (set to -20°C, the same below), thawed during evaluation, and NMP was added so that the solid content became 15 wt%.

[0598] Comparative Example 1

[0599] Nitrogen was introduced into a separable flask with a stirring rod, and NMP (284 g) as a solvent, BAFL (31.8 g; 91.3 mmol) as a diamine, and a silicon-containing compound (1) (17.10 g) as described in Table 1 were added while stirring, and then BPAF (45.8 g; 100.0 mmol) as an acid dianhydride was added, and the mixture was stirred at room temperature for 48 hours to obtain an NMP solution of polyamic acid (hereinafter also referred to as varnish). The obtained varnish was stored in a freezer (set to -20°C, the same below), thawed during evaluation, and NMP was added so that the solid content became 15 wt% before use.

[0600] 《Comparative Examples 2 and 3》

[0601] The same procedure as in Comparative Example 1 was carried out except that the types and amounts of the solvent, acid dianhydride, diamine, and silicon-containing compound were changed to those shown in Table 1.

[0602] 《Comparative Example 4》

[0603] Nitrogen was introduced into a separable flask with a stirring rod, and NMP (175 g) as a solvent, BAFL (3.5 g) as a diamine, and pPD (9.7 g) as described in Table 1 were added while stirring, and then BPAF (43.6 g) and BPDA (1.5 g) as an acid dianhydride were added, and the mixture was stirred at room temperature for 24 hours to obtain an NMP solution of polyamic acid (hereinafter also referred to as varnish). The obtained varnish was stored in a freezer (set to -20°C, the same below), thawed during evaluation, and NMP was added so that the solid content became 15wt% and used.

[0604] 《Comparative Example 5》

[0605] Nitrogen was introduced into a separable flask with a stirring rod, and NMP (120 g) as a solvent, BAFL (1.5 g; 4.2 mmol) as a diamine, and pPD (10.4 g; 95.8 mmol) as described in Table 1 were added while stirring, and then BPDA (24.0 g; 81.6 mmol) and PMDA (4.0 g; 18.4 mmol) as an acid dianhydride were added, and the mixture was stirred at room temperature for 24 hours to obtain an NMP solution of polyamic acid (hereinafter also referred to as varnish). The obtained varnish was stored in a freezer (set to -20°C, the same below), thawed during evaluation, and NMP was added in a manner that the solid content became 15wt% and used.

[0606] 《Comparative Examples 6, 9, and 10》

[0607] The same procedure as in Comparative Example 5 was performed except that the types and amounts of the solvent, acid dianhydride, and diamine were changed to those shown in Table 1.

[0608] 《Comparative Example 7》

[0609] Into a 1 L five-necked round-bottom flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen inlet pipe, a Dean-Stark apparatus equipped with a condenser, a thermometer, and a glass end cap, BAFL (34.8 g; 100 mmol) and NMP 98.8 g were added, and stirred at a temperature of 70° C. in a nitrogen atmosphere at a rotation speed of 150 rpm to obtain a solution.

[0610] After adding BPAF (22.9 g; 50 mmol), BPDA (14.7 g; 50 mmol) and NMP 24.2 g at once, 0.506 g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) as an imidization catalyst was added, and the mixture was heated by a mantle heater to raise the temperature in the reaction system to 190° C. over about 20 minutes. The components to be distilled off were collected, and the rotation speed was adjusted according to the increase in viscosity while maintaining the temperature in the reaction system at 190° C. and refluxed for 3 hours. Thereafter, 94.0 g of NMP was added, and the temperature in the reaction system was cooled to 120° C., and then stirred for about 3 hours to make it uniform, thereby obtaining a polyimide varnish.

[0611] 《Comparative Example 8》

[0612] The same procedure as in Comparative Example 7 was carried out except that the types and amounts of the solvent, the acid dianhydride, and the diamine were changed to those described in Table 1.

[0613] 《Example 19》

[0614] Nitrogen was introduced into a separable flask with a stirring rod equipped with a Dean-Stark tube and a reflux tube at the top, and NMP (183 g) and toluene (19 g) as solvents and BAFL (13.7 g; 39.2 mmol) as diamines as shown in Table 3 were added while stirring, and then PMDA (4.4 g; 20 mmol) and BPAF (9.2 g; 20 mmol) as acid dianhydrides were added at room temperature. Thereafter, the internal temperature was raised to 180°C, and reflux was heated at 180°C for 3 hours to carry out imidization. Then, the reaction was continued for 1 hour while toluene was extracted at 180°C, and then cooled to room temperature.

[0615] Then, pPD (6.4 g; 58.8 mmol) as a diamine was added under stirring at room temperature, followed by BPAF (27.5 g; 60.0 mmol) as an acid dianhydride, and the mixture was stirred at room temperature for 24 hours to obtain an NMP solution (hereinafter also referred to as varnish) of a partially imidized (the above L / M=60 / 40 mol%) polyimide precursor (hereinafter also referred to as PAI). The obtained varnish was stored in a freezer (set to -20°C, the same below), thawed during evaluation, and used by adding NMP in a manner that the solid content was 15 wt%.

[0616] 《Examples 21, 23, 30》

[0617] The same procedure as in Example 19 was carried out except that the types and amounts of the solvent, the acid dianhydride and the diamine were changed to those shown in Table 3.

[0618] 《Example 24》

[0619] Nitrogen was introduced into a separable flask with a stirring rod equipped with a Dean-Stark tube and a reflux tube at the top, and NMP (201 g), toluene (21 g), BAFL (13.1 g; 37.5 mmol) and silicon-containing compound (1) (7.37 g) as solvents as shown in Table 3 were added while stirring. Then, BPDA (5.9 g; 20 mmol), PMDA (2.2 g; 10 mmol) and BPAF (4.6 g; 10 mmol) as acid dianhydrides were added at room temperature. Thereafter, the internal temperature was raised to 180°C, and reflux was heated at 180°C for 3 hours to carry out imidization. Then, the reaction was continued for 1 hour while toluene was extracted at 180°C, and then cooled to room temperature.

[0620] Then, pPD (6.4 g; 58.8 mmol) as a diamine was added under stirring at room temperature, followed by BPAF (27.5 g; 60.0 mmol) as an acid dianhydride, and the mixture was stirred at room temperature for 24 hours to obtain a partially imidized (L / M=60 / 40 mol%) polyimide precursor (hereinafter also referred to as PAI) NMP solution. The obtained varnish was stored in a freezer (set to -20°C, the same below), thawed during evaluation, and used by adding NMP in a manner that the solid content was 15 wt%.

[0621] 《Examples 20, 22, 32 to 35》

[0622] The same procedure as in Example 24 was carried out except that the types and amounts of the solvent, the acid dianhydride and the diamine were changed to those shown in Table 3.

[0623] 《Example 25》

[0624] Nitrogen was introduced into a separable flask with a stirring rod equipped with a Dean-Stark tube and a reflux tube at the top, and NMP (200 g) as a solvent, toluene (21 g), BAFL (13.7 g; 39.2 mmol) as a diamine as shown in Table 3 were added while stirring, and then BPDA (5.5 g; 18.9 mmol), PMDA (2.1 g; 9.4 mmol), BPAF (4.3 g; 9.4 mmol), and silicon-containing compound (2) (7.35 g) were added at room temperature as acid dianhydrides. Thereafter, the internal temperature was raised to 180°C, and reflux was heated at 180°C for 3 hours to carry out imidization. Then, the reaction was continued for 1 hour while toluene was extracted at 180°C, and then cooled to room temperature.

[0625] Then, pPD (6.4 g; 58.8 mmol) as a diamine was added under stirring at room temperature, followed by BPAF (27.5 g; 60.0 mmol) as an acid dianhydride, and the mixture was stirred at room temperature for 24 hours to obtain a partially imidized (L / M=60 / 40 mol%) polyimide precursor (hereinafter also referred to as PAI) NMP solution. The obtained varnish was stored in a freezer (set to -20°C, the same below), thawed during evaluation, and used by adding NMP in a manner that the solid content was 15 wt%.

[0626] 《Example 26》

[0627] Nitrogen was introduced into a separable flask with a stirring rod equipped with a Dean-Stark tube and a reflux tube at the top, and NMP (202 g) and toluene (21 g) as solvents and BAFL (13.7 g; 39.2 mmol) as diamines as shown in Table 3 were added while stirring, and then BPDA (5.9 g; 20.0 mmol), PMDA (2.2 g; 10.0 mmol), and BPAF (4.6 g; 10.0 mmol) as acid dianhydrides were added at room temperature. Thereafter, the internal temperature was raised to 180°C, and reflux was heated at 180°C for 3 hours to carry out imidization. Then, the reaction was continued for 1 hour while toluene was extracted at 180°C, and then cooled to room temperature.

[0628] Then, pPD (6.2 g; 57.1 mmol) and silicon-containing compound (1) (7.42 g) were added as diamines at room temperature while stirring, followed by BPAF (27.5 g; 60.0 mmol) as dianhydride, and the mixture was stirred at room temperature for 24 hours to obtain a partially imidized (L / M=60 / 40 mol%) polyimide precursor (hereinafter also referred to as PAI) NMP solution. The obtained varnish was stored in a freezer (set to -20°C, the same below), thawed during evaluation, and used by adding NMP so that the solid content became 15 wt%.

[0629] 《Example 27》

[0630] Nitrogen was introduced into a separable flask with a stirring rod equipped with a Dean-Stark tube and a reflux tube at the top, and NMP (210 g) as a solvent, toluene (22 g), BAFL (30.7 g; 88.2 mmol) as a diamine as shown in Table 3 were added while stirring, and then BPDA (7.6 g; 26 mmol), PMDA (3.1 g; 14 mmol), and BPAF (22.9 g; 50 mmol) as acid dianhydrides were added at room temperature. Thereafter, the internal temperature was raised to 180°C, and reflux was heated at 180°C for 3 hours to carry out imidization. Then, the reaction was continued for 1 hour while toluene was extracted at 180°C, and then cooled to room temperature.

[0631] Then, pPD (1.1 g; 9.8 mmol) as a diamine was added under stirring at room temperature, followed by BPAF (4.6 g; 10 mmol) as an acid dianhydride, and the mixture was stirred at room temperature for 24 hours to obtain a partially imidized (L / M=10 / 90 mol%) polyimide precursor (hereinafter also referred to as PAI) NMP solution. The obtained varnish was stored in a freezer (set to -20°C, the same below), thawed during evaluation, and used by adding NMP in a manner that the solid content was 15 wt%.

[0632] 《Example 28》

[0633] Nitrogen was introduced into a separable flask with a stirring rod equipped with a Dean-Stark tube and a reflux tube at the top, and NMP (234 g) as a solvent, toluene (24 g), BAFL (30.1 g; 86.3 mmol) as a diamine, and silicon-containing compound (1) (8.57 g) as shown in Table 3 were added while stirring, and then BPDA (7.6 g; 26 mmol), PMDA (3.1 g; 10 mmol), and BPAF (22.9 g; 50 mmol) as acid dianhydrides were added at room temperature. Thereafter, the internal temperature was raised to 180°C, and reflux was heated at 180°C for 3 hours to carry out imidization. Then, the reaction was continued for 1 hour while toluene was extracted at 180°C, and then cooled to room temperature.

[0634] Then, pPD (1.1 g; 9.8 mmol) as a diamine was added under stirring at room temperature, followed by BPAF (4.6 g; 10 mmol) as an acid dianhydride, and the mixture was stirred at room temperature for 24 hours to obtain a partially imidized (L / M=10 / 90 mol%) polyimide precursor (hereinafter also referred to as PAI) NMP solution. The obtained varnish was stored in a freezer (set to -20°C, the same below), thawed during evaluation, and used by adding NMP in a manner that the solid content was 15 wt%.

[0635] 《Example 29》

[0636] Nitrogen was introduced into a separable flask with a stirring rod equipped with a Dean-Stark tube and a reflux tube at the top, and NMP (239 g), toluene (24 g), BAFL (4.2 g; 12 mmol) and silicon-containing compound (1) (6.16 g) as solvents as shown in Table 3 were added while stirring, and then BPDA (1.5 g; 5 mmol) and PMDA (1.1 g; 5 mmol) as acid dianhydrides were added at room temperature. Thereafter, the internal temperature was raised to 180°C, and reflux was heated at 180°C for 3 hours to carry out imidization. Then, the reaction was continued for 1 hour while toluene was extracted at 180°C, and then cooled to room temperature.

[0637] Then, pPD (1.8 g; 16.9 mmol) and BAFL (23.6 g; 67.7 mmol) as diamines were added under stirring at room temperature, followed by BPAF (41.3 g; 90 mmol) as dianhydride, and the mixture was stirred at room temperature for 24 hours to obtain a partially imidized (L / M=90 / 10 mol%) polyimide precursor (hereinafter also referred to as PAI) NMP solution. The obtained varnish was stored in a freezer (set to -20°C, the same below), thawed during evaluation, and used by adding NMP so that the solid content became 15 wt%.

[0638] 《Example 31》

[0639] Nitrogen was introduced into a separable flask with a stirring rod equipped with a Dean-Stark tube and a reflux tube at the top, and NMP (208 g), toluene (21 g), BAFL (31.1 g; 89.3 mmol) and silicon-containing compound (1) (7.62 g) as solvents as shown in Table 3 were added while stirring, and then BPDA (16.8 g; 57 mmol) and PMDA (6.1 g; 28 mmol) as acid dianhydrides were added at room temperature. Thereafter, the internal temperature was raised to 180°C, and reflux was heated at 180°C for 3 hours to carry out imidization. Then, the reaction was continued for 1 hour while toluene was extracted at 180°C, and then cooled to room temperature.

[0640] Then, pPD (0.8 g; 7 mmol) was added as a diamine while stirring at room temperature, followed by BPAF (6.9 g; 15 mmol) as an acid dianhydride, and the mixture was stirred at room temperature for 24 hours to obtain a partially imidized (L / M=15 / 85 mol%) polyimide precursor (hereinafter also referred to as PAI) NMP solution. The obtained varnish was stored in a freezer (set to -20°C, the same below), thawed during evaluation, and used by adding NMP so that the solid content became 15 wt%.

[0641] 《Example 36》

[0642] Nitrogen was introduced into a separable flask with a stirring rod equipped with a Dean-Stark tube and a reflux tube at the top, and NMP (201 g), toluene (21 g), pPD (4.1 g; 37.8 mmol) and silicon-containing compound (1) (8.0 g) as solvents as shown in Table 3 were added while stirring, and then BPAF (22.9 g; 50.0 mmol) as acid dianhydride was added at room temperature. Thereafter, the internal temperature was raised to 180°C, and reflux was heated at 180°C for 3 hours to carry out imidization. Then, the reaction was continued for 1 hour while toluene was extracted at 180°C, and then cooled to room temperature.

[0643] Then, BAFL (22.5 g; 49.0 mmol) was added as a diamine while stirring at room temperature, followed by BPDA (11.8 g; 40.0 mmol) as an acid dianhydride, and the mixture was stirred at room temperature for 24 hours to obtain a partially imidized (L / M=44 / 56 mol%) polyimide precursor (hereinafter also referred to as PAI) NMP solution. The obtained varnish was stored in a freezer (set to -20°C, the same below), thawed during evaluation, and NMP was added so that the solid content became 15 wt% before use.

[0644] 《Example 37, Comparative Examples 11 and 12》

[0645] Make as Figure 1 The organic EL substrate shown.

[0646] In Example 37, the resin composition of Example 24 (characteristics of the polyimide resin film: YI: 11, degassing start temperature (TDS evaluation): 465°C, residual stress: 33 MPa (under nitrogen atmosphere), Rth (thickness direction retardation): 52 nm) was used, and in Comparative Example 11, the resin composition of Comparative Example 7 (characteristics of the polyimide resin film: YI: 10, degassing start temperature (TDS evaluation): 450°C, residual stress: 62 MPa (under nitrogen atmosphere), Rth In Comparative Example 12, the resin composition of Comparative Example 8 (characteristics of polyimide resin film: YI: 2, degassing start temperature (TDS evaluation): 430°C, residual stress: 32MPa (under nitrogen atmosphere), Rth (thickness direction retardation): 127nm) was used, and applied on a mother glass substrate (thickness 0.7mm) using a bar coater so that the film thickness after curing was 10μm, and then pre-baked at 140°C for 60 minutes. Then, a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) was used to adjust the oxygen concentration in the furnace to 10 mass ppm or less, and a heat curing treatment was performed at 430°C for 30 minutes to produce a glass substrate with a polyimide resin film formed thereon.

[0647] Next, a SiN layer is formed into a film with a thickness of 100 nm by a CVD (Chemical Vapor Deposition) method.

[0648] Next, a titanium film is formed by sputtering, and then patterned by photolithography to form scanning signal lines.

[0649] Next, a SiN layer with a thickness of 100 nm is formed by CVD on the entire glass substrate on which the scanning signal lines are formed. (This is referred to as the lower substrate 2a)

[0650] Next, an amorphous silicon layer 256 is formed on the lower substrate 2a, and dehydrogenation treatment is performed at 420°C or 430°C for 1 hour to form an LTPS layer. Next, after ion implantation, annealing treatment is performed under the following two conditions to activate the ions, thereby forming an LTPS layer.

[0651] 1) Excimer Laser Annealing (ELA) (without heating)

[0652] 2) Rapid Thermal Annealing (RTA) at 400°C in a furnace

[0653] After that, a photosensitive acrylic resin is applied to the entire surface of the lower substrate 2a, and exposure and development are performed by photolithography to form 258 having a plurality of contact holes 257. At this time, a solution of dimethyl sulfoxide / monoethanolamine (70 / 30 (wt%)) is used as a solution for removing the photoresist. Through the contact holes 257, a portion of each LTPS 256 is exposed.

[0654] Next, an ITO film is formed by sputtering on the entire surface of the lower substrate 2a on which the interlayer insulating film 258 is formed, exposed and developed by photolithography, and patterned by etching to form lower electrodes 259 in pairs with each LTPS.

[0655] It should be noted that, in each contact hole 257 , the lower electrode 252 penetrating the interlayer insulating film 258 is electrically connected to the LTPS 256 .

[0656] Next, after forming the partition walls 251, the hole transport layer 253 and the light emitting layer 254 are formed in each space partitioned by the partition walls 251. In addition, the upper electrode 255 is formed so as to cover the light emitting layer 254 and the partition walls 251. The organic EL substrate 25 is manufactured through the above steps.

[0657] Next, an ultraviolet curing resin is applied around the sealing substrate 2b on which the glass substrate, the polyimide film of this embodiment, and the SiN layer are sequentially formed, and the sealing substrate 2b is bonded to the organic EL substrate in an argon atmosphere, thereby sealing the organic EL element in. Thus, a hollow portion 261 is formed between each organic EL element and the sealing substrate 2b.

[0658] The laminated body thus formed was irradiated with excimer laser light (wavelength 308 nm, repetition frequency 300 Hz) from the lower substrate 2a side and the sealing substrate 2b side, and peeled off with the minimum energy required for peeling off the entire surface.

[0659] The laminate was subjected to observation and evaluation of the laminate using an optical microscope and various evaluations of a lighting test.

[0660] For the laminate of Example 37, no abnormality was observed in the observation evaluation under any of the annealing conditions of 420°C / 430°C and any of the annealing conditions of ELA and RTA, and lighting was confirmed in all of them in the lighting test. In particular, in the case of the annealing condition of RTA, there was no yellowing of the polyimide resin film, and the image quality was the best.

[0661] On the other hand, for the laminates of Comparative Examples 11 and 12, expansion, cracks, coloring, etc. were observed in the observation evaluation under any of the annealing conditions of 420°C / 430°C and ELA and RTA, and none of them lit up in the lighting test. Although the reason is not clear, it is understood that it is related to the poor chemical resistance of Comparative Examples 11 and 12 and the poor heat resistance of the laminate of Comparative Example 12. In particular, it is understood that the reason is that Comparative Example 12 uses an alicyclic monomer, and the polyimide resin film is damaged in the annealing process.

[0662] The compositions of the polyimides / polyimide precursors of Examples 1 to 18 and Comparative Examples 1 to 10 are shown in Table 1, and the evaluation results are shown in Table 2.

[0663] In addition, about the polyimide precursors of Examples 19 to 36, the compositions are shown in Table 3, and the evaluation results are shown in Table 3.

[0664] 《Explanation of the abbreviations in Table 1 and Table 3》

[0665] <Acid dianhydride>

[0666] BPAF: 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride

[0667] PMDA: Pyromellitic anhydride

[0668] BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

[0669] aBPDA: 2,3,3',4'-biphenyltetracarboxylic dianhydride

[0670] CpODA: Norbornane 2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride

[0671] <Diamine>

[0672] BAFL: 9,9-bis(4-aminophenyl)fluorene

[0673] pPD: p-phenylenediamine

[0674] mPD: meta-phenylenediamine

[0675] <Silicon-containing compounds>

[0676] Silicon-containing compound (1): (a compound in which L1 and L2 are amino groups (-NH2), R1 is trimethylene (-CH2CH2CH2-), R2 and R3 are methyl groups, j and k are 0, and the functional group equivalent is 2200 in the general formula (17))

[0677] Silicon-containing compound (2): (a compound in which L1 and L2 are anhydride groups (-CHCH2(C=O)2O), R1 is a trimethylene group (-CH2CH2CH2-), R2 and R3 are methyl groups, j and k are 0, and the functional group equivalent is 1600 in the general formula (17))

[0678] Silicon-containing compound (3): (a compound in which L1 and L2 are amino groups (-NH2), R1 is trimethylene (-CH2CH2CH2-), R2 and R3 are methyl groups, j and k are 0, and the functional group equivalent is 1500 in the general formula (17))

[0679] <Solvent>

[0680] NMP: N-methylpyrrolidone

[0681] <Polymer Type>

[0682] PAA: Polyimide Precursor

[0683] PI: Polyimide

[0684] PAI: partially imidized polyimide precursor

[0685] <Block copolymer>

[0686] Block: A block copolymer comprising a first block comprising a structural unit derived from the above general formula (4) and a second block comprising a structural unit derived from the above general formula (6) and / or the above general formula (7)

[0687] -: does not contain the first block and the second block

[0688] [Table 1]

[0689]

[0690] [Table 2]

[0691]

[0692] [Table 3]

[0693]

[0694] [Table 4]

[0695]

[0696] As shown in Tables 1 to 4, the polyimide obtained from the resin composition of the embodiment has various properties when cured at 430°C or above, including glass transition temperature, YI (yellowness), Young's modulus, and chemical resistance, as compared to the comparative example, and is excellent in the properties required for display applications.

[0697] Description of Reference Numerals

[0698] 2a lower base plate

[0699] 2b Sealing substrate

[0700] 25 Organic EL structure

[0701] 250a Organic EL element emitting red light

[0702] 250b Organic EL element emitting green light

[0703] 250c Organic EL element that emits blue light

[0704] 251 Dividing wall (embankment)

[0705] 252 lower electrode (anode)

[0706] 253 Hole transport layer

[0707] 254 Luminous Layer

[0708] 255 Upper electrode (cathode)

[0709] 256 TFT

[0710] 257 Contact hole

[0711] 258 interlayer insulation film

[0712] 259 Lower electrode

[0713] 261 Hollow

Claims

1. A resin composition comprising a resin, wherein the resin comprises a structural unit represented by the following general formula (1) and / or general formula (2), In formula (1), P1 represents a divalent organic group, P2 represents a tetravalent organic group, and p represents a positive integer. In formula (2), P3 represents a divalent organic group, P4 represents a tetravalent organic group, q represents a positive integer, The resin is a block copolymer comprising a first block and a second block, The first block comprises a structural unit derived from a compound represented by the following general formula (4), The second block comprises at least one structural unit derived from the compound represented by the following general formula (6) and general formula (7), 2. The resin composition according to claim 1, wherein The first block further comprises a structural unit derived from an acid dianhydride other than the compounds represented by the general formula (6) and the general formula (7), and The second block further includes a structural unit derived from a diamine other than the compound represented by the general formula (4).

3. The resin composition according to claim 1 or 2, wherein The resin includes a structural unit derived from a fluorene derivative.

4. The resin composition according to claim 1 or 2, wherein The resin comprises a structural unit represented by the following general formula (8): In formula (8), P5 and P6, when present in plural, each independently represent a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and r represents an integer of 1 to 200.

5. The resin composition according to claim 1 or 2, wherein The first block comprises a structural unit derived from a compound represented by the following general formula (5), In formula (5), Q1 and Q2, when present in plural, each independently represent a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group, X each independently represents at least one selected from the group consisting of an ether group, a carbonyl group, an ester group, and an amide group, and p is an integer of 0 or 1.

6. The resin composition according to claim 1 or 2, wherein The second block comprises a structural unit derived from a compound represented by the following general formula (3), In formula (3), Q3 and Q4, when present in plural numbers, each independently represent a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group.

7. The resin composition according to claim 1 or 2, wherein The second block comprises a structural unit represented by the following general formula (8): In formula (8), P5 and P6, when present in plural numbers, each independently represent a monovalent aliphatic hydrocarbon group having 1 to 5 carbon atoms or a monovalent aromatic group having 6 to 10 carbon atoms, and r represents an integer of 1 to 200.

8. The resin composition according to claim 1 or 2, wherein The resin includes the structural units represented by the general formula (1) and the general formula (2).

9. The resin composition according to claim 8, wherein The first block is a structural unit represented by the general formula (1), The second block is a structural unit represented by the general formula (2).

10. The resin composition according to claim 8, wherein The second block is a structural unit represented by the general formula (1), The first block is a structural unit represented by the general formula (2).

11. The resin composition according to claim 8, wherein In the resin, when the structure derived from the general formula (1) is L and the structure derived from the general formula (2) is M, the ratio L / M of L to M is 10 / 90 to 90 / 10, Wherein, the unit of L is mol, the unit of M is mol, and the unit of L / M is mol%.

12. A resin composition comprising a resin, wherein the resin comprises a structural unit represented by the following general formula (1) and / or general formula (2), In formula (1), P1 represents a divalent organic group, P2 represents a tetravalent organic group, and p represents a positive integer. In formula (2), P3 represents a divalent organic group, P4 represents a tetravalent organic group, q represents a positive integer, The P1 and / or P3 contain a structural unit derived from a compound represented by the following general formula (4), The P2 and / or P4 contain at least one structural unit derived from the compound represented by the following general formula (6) and formula (7), In the resin composition, the ratio of at least one structural unit selected from the structural units represented by the following general formula (10), general formula (11), general formula (12) and general formula (13) is smaller than the ratio of structural units formed by acid dianhydride monomers and diamine monomers other than the above general formula (4), general formula (6) and formula (7) connected by amide bonds and / or imide bonds, in, The unit of the ratio is mol%.

13. A method for producing a resin composition, wherein: The resin composition comprises a resin, wherein the resin comprises structural units represented by the following general formula (1) and general formula (2), In formula (1), P1 represents a divalent organic group, P2 represents a tetravalent organic group, and p represents a positive integer. In formula (2), P3 represents a divalent organic group, P4 represents a tetravalent organic group, q represents a positive integer, The method for preparing the resin composition comprises: After synthesizing the resin 2 having the structural unit of the general formula (2), a compound represented by the following general formula (4) and a compound represented by the following general formula (5) are polycondensed to introduce the structural unit of the general formula (1) into the resin 2. In formula (5), Q1 and Q2, when present in plural, each independently represent a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic group having 6 to 14 carbon atoms, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, or an amide group, X each independently represents at least one selected from the group consisting of an ether group, a carbonyl group, an ester group, and an amide group, and p is an integer of 0 or 1; or, A step of introducing the structural unit of the general formula (1) into the resin 2 after synthesizing the resin 2 having the structural unit of the general formula (2) by polycondensing the compound of the general formula (4) and the compound of the general formula (5).

14. A method for producing a resin composition, wherein: The resin composition comprises structural units represented by the following general formula (1) and general formula (2), In formula (1), P1 represents a divalent organic group, P2 represents a tetravalent organic group, and p represents a positive integer. In formula (2), P3 represents a divalent organic group, P4 represents a tetravalent organic group, q represents a positive integer, The method for producing the resin composition comprises the steps of, after synthesizing a resin 2 having a structural unit of the general formula (2), introducing a structural unit of the general formula (1) into the resin 2. The P1 or P3 comprises a structural unit derived from a compound represented by the following general formula (4), 15. A method for producing a polyimide resin film, comprising: A coating step of coating the resin composition according to claim 1 or 12 or the resin composition obtained by the method according to claim 13 or 14 on the surface of a support; a film forming step of heating the resin composition to form a polyimide resin film; a peeling step of peeling the polyimide resin film from the support; and an irradiation step of irradiating the resin composition with a laser beam from the support side before the peeling step.

16. A method for manufacturing a display, comprising: A coating step of coating the resin composition according to claim 1 or 12 or the resin composition obtained by the method according to claim 13 or 14 on the surface of a support; a film forming step of heating the resin composition to form a polyimide resin film; an element forming step of forming an element on the polyimide resin film; and A peeling step is to peel the polyimide resin film on which the element is formed from the support.

17. A method for manufacturing a laminate, comprising: A coating step of coating the resin composition according to claim 1 or 12 or the resin composition obtained by the method according to claim 13 or 14 on the surface of a support; a film forming step of heating the resin composition to form a polyimide resin film; and The device forming step is to form a device on the polyimide resin film.

18. A method for manufacturing a laminate, comprising: A coating step of coating the resin composition according to claim 1 or 12 or the resin composition obtained by the method according to claim 13 or 14 on the surface of a support; a film forming step of heating the resin composition to form a polyimide resin film; an element forming step of forming an element on the polyimide resin film; and a step of peeling the polyimide resin film on which the element is formed from the support.

19. A polyimide resin film, which satisfies all of the following characteristics: ·YI (yellowness index) is 15 or less (based on a film thickness of 10 μm) · Degassing start temperature (TDS evaluation) is 440℃ or above ·Residual stress is less than 35MPa (under nitrogen atmosphere) Rth (retardation in the thickness direction) is 100 nm or less (based on a film thickness of 10 μm).

20. A flexible display comprising the polyimide resin film according to claim 19 and LTPO (Low-temperature polycrystalline oxide).

21. A method for manufacturing a display, comprising: A step of heating a laminate including a polyimide resin film and an inorganic film at 420° C. or higher and then irradiating the laminate with an excimer laser. The polyimide resin film satisfies all of the following properties: ·YI (yellowness index) is 15 or less (based on a film thickness of 10 μm) The degassing start temperature (TDS evaluation) is 440°C or higher.

22. The method for manufacturing a display according to claim 20, wherein: The polyimide resin film satisfies all of the following characteristics: ·Residual stress is less than 35MPa (under nitrogen atmosphere) Rth (retardation in the thickness direction) is 100 nm or less (based on a film thickness of 10 μm).

23. A method for manufacturing a display, using a laminate comprising a polyimide resin film and an inorganic film, wherein the polyimide resin film satisfies all of the following characteristics: ·YI (yellowness index) is 15 or less (based on a film thickness of 10 μm) · Degassing start temperature (TDS evaluation) is 440℃ or above ·Residual stress is less than 35MPa (under nitrogen atmosphere) Rth (thickness direction retardation) is less than 100nm (converted to a film thickness of 10μm), The method for manufacturing the display includes a dehydrogenation treatment step, an excimer laser irradiation step, an ion implantation step, and a heating and annealing step at 400° C. or higher.

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