WO2017051827A1 - ポリイミド前駆体、樹脂組成物および樹脂フィルムの製造方法 - Google Patents

ポリイミド前駆体、樹脂組成物および樹脂フィルムの製造方法 Download PDF

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WO2017051827A1
WO2017051827A1 PCT/JP2016/077878 JP2016077878W WO2017051827A1 WO 2017051827 A1 WO2017051827 A1 WO 2017051827A1 JP 2016077878 W JP2016077878 W JP 2016077878W WO 2017051827 A1 WO2017051827 A1 WO 2017051827A1
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Prior art keywords
polyimide
film
group
general formula
polyimide precursor
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PCT/JP2016/077878
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English (en)
French (fr)
Japanese (ja)
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昌樹 米谷
建樹 清水
隆行 金田
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旭化成株式会社
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Priority to KR1020187003697A priority Critical patent/KR102133559B1/ko
Priority to CN201680054473.7A priority patent/CN108026273B/zh
Priority to KR1020227037038A priority patent/KR102659377B1/ko
Priority to KR1020207019673A priority patent/KR102460768B1/ko
Priority to JP2017541568A priority patent/JP6444522B2/ja
Publication of WO2017051827A1 publication Critical patent/WO2017051827A1/ja

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1025—Preparatory processes from tetracarboxylic acids or derivatives and diamines polymerised by radiations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/16—Polyester-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a method for producing a polyimide precursor, a resin composition, and a resin film used for producing a substrate for a flexible device, for example.
  • a polyimide resin film is used as a resin film for applications requiring high heat resistance.
  • a general polyimide resin is prepared by preparing a polyimide precursor by solution polymerization of an aromatic carboxylic dianhydride and an aromatic diamine, and then thermally imidizing it at a high temperature or using a catalyst to form a chemical imide. It is a highly heat-resistant resin that is manufactured.
  • Polyimide resin is an insoluble and infusible super heat resistant resin, and has excellent characteristics such as heat oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. For this reason, polyimide resins are used in a wide range of fields including electronic materials. Examples of the application of polyimide resin in the field of electronic materials include, for example, insulating coating agents, insulating films, semiconductor protective films, and electrode protective films for TFT-LCDs. Recently, in place of a glass substrate conventionally used in the field of display materials, adoption as a colorless and transparent flexible substrate utilizing its lightness and flexibility has been studied.
  • a polyimide resin film is formed on a suitable support by applying a composition containing a polyimide precursor to form a coating film, followed by heat treatment and imidization. Get a film.
  • a suitable support for example, glass, silicon, silicon nitride, silicon oxide, metal or the like is used.
  • the heat processing in 250 degreeC or more are required for drying and imidation of a polyimide precursor. By this heat treatment, residual stress is generated in the laminate, and serious problems such as warpage and peeling occur. This is because the linear thermal expansion coefficient of polyimide is larger than that of the material constituting the support.
  • Non-patent Document 1 a polyimide formed from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and paraphenylenediamine is best known. Although depending on the film thickness and production conditions, it has been reported that this polyimide film exhibits a very low linear thermal expansion coefficient (Non-patent Document 1). Moreover, since the polyimide which has ester structure in a molecular chain has moderate linearity and rigidity, it is reported that a low linear thermal expansion coefficient is shown (patent document 1).
  • Non-Patent Document 1 obtained from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and paraphenylenediamine has a yellowness (YI value) of 40 or more at a film thickness of 10 ⁇ m. High and insufficient in terms of transparency. About the yellowness of a film, it is known that the polyimide using the monomer which has a fluorine atom shows very low yellowness, for example (patent document 2).
  • Japanese Patent No. 4627297 Special table 2010-538103 gazette Japanese Patent No. 3079867
  • the polyimide film described in Patent Document 2 shows a low yellowness in a temperature range of about 300 ° C., but the yellowness (YI value) is remarkably deteriorated in a high temperature range of 400 ° C. or higher. It was.
  • Patent Document 3 a polyimide composed of 4,4′-diaminodiphenyl ether and 4,4′-diaminodiphenyl ester is disclosed as a polyimide having a reduced linear expansion coefficient (Patent Document 3).
  • Patent Document 3 a polyimide having a reduced linear expansion coefficient
  • the present inventors have confirmed that the polyimide resin described in Patent Document 3 has a very brittle film for application as a flexible substrate, and there is room for improvement in yellowness at high temperatures.
  • an object of the present invention is to provide a polyimide resin film having a low residual stress, little warpage, a small yellowness (YI value), and a high elongation, and a method for producing the same.
  • the present invention is as follows. [1] (A1) The following general formula (1): ⁇ Wherein X 1 represents a tetravalent group having 4 to 32 carbon atoms. R 1 , R 2 and R 3 each independently represents a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1. A, b and c are integers from 0 to 4. ⁇ , A structural unit L represented by The following general formula (2): ⁇ Wherein X 2 represents a tetravalent group having 4 to 32 carbon atoms.
  • Y is at least one member selected from the group consisting of the following general formulas (3), (4) and (5) ⁇ 1/99 ⁇ (number of moles of structural unit L / number of moles of structural unit M) ⁇ 99/1
  • the polyimide precursor characterized by including by. ⁇ Wherein R 4 to R 11 each independently represents a monovalent organic group having 1 to 20 carbon atoms. d to k are integers of 0 to 4. ⁇ [2] The polyimide precursor according to [1], wherein n in the general formula (1) is 0. [3] The polyimide precursor according to [1] or [2], wherein Y in the general formula (2) is the general formula (3).
  • X 3 is 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic dianhydride (BPDA), and 4,4'-biphenylbis (trimellitic acid monoester anhydride) (TAHQ) represents a tetravalent group derived from at least one selected from the group consisting of: R 1 , R 2 and R 3 each independently represents a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1. A, b and c are integers from 0 to 4.
  • Polyimide precursor [10] A resin composition comprising the polyimide precursor according to any one of [1] to [9] and (b) an organic solvent. [11] The resin composition according to [10], further comprising at least one selected from the group consisting of (c) a surfactant and (d) an alkoxysilane compound. [12] The following general formula (11): ⁇ Wherein X 1 and X 2 represent a tetravalent group having 4 to 32 carbon atoms.
  • R 1 , R 2 and R 3 each independently represents a monovalent organic group having 1 to 20 carbon atoms.
  • n represents 0 or 1.
  • A, b and c are integers from 0 to 4.
  • Y is at least one selected from the group consisting of the following general formulas (3), (4) and (5).
  • l and m each independently represent an integer of 1 or more, and satisfy 0.01 ⁇ l / (l + m) ⁇ 0.99. ⁇ , The polyimide characterized by having a structural unit represented by these.
  • R 4 to R 11 each independently represents a monovalent organic group having 1 to 20 carbon atoms.
  • d to k are integers of 0 to 4.
  • [14] Forming a coating film on the surface of the support by applying the resin composition according to [10] or [11]; Heating the support and the coating to form a polyimide resin film by imidizing the polyimide precursor contained in the coating; and Peeling the polyimide resin film from the support;
  • a method for producing a resin film comprising: [15] The method for producing a resin film according to [14], wherein a step of irradiating a laser from the support side is performed prior to a step of peeling the polyimide resin film from the support.
  • [17] Forming a coating film on the surface of the support by applying the resin composition according to [10] or [11]; Heating the support and the coating to form a polyimide resin film by imidizing the polyimide precursor contained in the coating; and Forming an element or a circuit on the polyimide resin film; Peeling the polyimide resin film on which the element or circuit is formed from the support;
  • a method for manufacturing a display substrate comprising: [18] The following general formula (12): ⁇ Wherein X 3 is 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic dianhydride (BPDA), and 4,4'-biphenylbis (trimellitic acid monoester anhydride) It is at least one selected from the group consisting of (TAHQ), and R 1 , R 2 and R 3 each independently represents a monovalent organic group having 1 to 20 carbon atoms.
  • ODPA 4,4'-oxydiphthalic dianhydride
  • BPDA
  • n 0 or 1.
  • A, b and c are integers from 0 to 4.
  • the polyimide film for a display characterized by including the polyimide represented by these.
  • A, b and c are integers from 0 to 4.
  • the laminated body characterized by including the polyimide film layer containing the polyimide represented by, and a low-temperature polysilicon TFT layer. [20] Yellowness at a film thickness of 10 microns after heating at 400 ° C.
  • a polyimide film characterized by being: [21] (A) a polyimide precursor represented by the following general formula (1); (B) an organic solvent; (C) a surfactant and (d) at least one selected from the group consisting of alkoxysilane compounds; The resin composition characterized by including. ⁇ Wherein X 1 represents a tetravalent group having 4 to 32 carbon atoms. R 1 , R 2 and R 3 each independently represents a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1. A, b and c are integers from 0 to 4. ⁇
  • the polyimide film obtained from the polyimide precursor and resin composition according to the present invention has low residual stress, little warpage, low yellowness (YI value), and high elongation.
  • the resin composition provided by one embodiment of the present invention contains (a) a polyimide precursor and (b) an organic solvent.
  • a polyimide precursor contains (a) a polyimide precursor and (b) an organic solvent.
  • Polyimide precursor The polyimide precursor as the first embodiment of the present embodiment, (A1) The following general formula (1): ⁇ Wherein X 1 represents a tetravalent group having 4 to 32 carbon atoms. R 1 , R 2 and R 3 each independently represents a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1. A, b and c are integers from 0 to 4. ⁇ , A structural unit L represented by The following general formula (2): ⁇ Wherein X 2 represents a tetravalent group having 4 to 32 carbon atoms.
  • Y is at least one selected from the group consisting of the following general formulas (3), (4) and (5) ⁇ and 1/99 ⁇ (number of moles of structural unit L / structure) The number of moles of unit M) ⁇ 99/1.
  • R 4 to R 11 each independently represents a monovalent organic group having 1 to 20 carbon atoms.
  • d to k are integers of 0 to 4.
  • the polyimide precursor according to the first embodiment of the present invention has a low residual stress, a low warpage, a small yellowness (YI value), and a high elongation when formed as a polyimide film.
  • R 1 to R 3 are not limited as long as they are each independently a monovalent organic group having 1 to 20 carbon atoms.
  • examples of such an organic group include alkyl groups such as a methyl group, an ethyl group, and a propyl group, halogen-containing groups such as a trifluoromethyl group, and alkoxy groups such as a methoxy group and an ethoxy group.
  • a methyl group is preferable from the viewpoint of YI in a high temperature region.
  • a, b, c, and d are not limited as long as they are integers of 0 to 4.
  • an integer of 0 to 2 is preferable from the viewpoint of YI and residual stress, and 0 is particularly preferable from the viewpoint of YI in the high temperature region.
  • n is 0 or 1.
  • 0 is preferable from the viewpoint of YI in a high temperature region.
  • the lower limit of the molar ratio of the structural unit L to the structural unit M (the number of moles of the structural unit L / the number of moles of the structural unit M) may be 5/95, 10/90, 20/80, 30 / 70 or 40/60 may be used.
  • the upper limit of the molar ratio between the structural unit L and the structural unit M (number of moles of the structural unit L / number of moles of the structural unit M) may be 95/5, 90/10, 80/20, 70/30 However, it may be 60/40.
  • X 1 and X 2 are each independently a tetravalent group having 4 to 32 carbon atoms and may be the same or different.
  • the tetravalent organic group derived from the following tetracarboxylic dianhydride is illustrated.
  • Specific examples of the tetracarboxylic dianhydride include aromatic tetracarboxylic dianhydrides having 8 to 36 carbon atoms, aliphatic tetracarboxylic dianhydrides having 6 to 36 carbon atoms, and carbon numbers. Is a compound selected from among alicyclic tetracarboxylic dianhydrides having 6 to 36.
  • aromatic tetracarboxylic dianhydrides having 8 to 36 carbon atoms are preferable from the viewpoint of yellowness in a high temperature region.
  • the number of carbons herein includes the number of carbons contained in the carboxyl group.
  • examples of the aromatic tetracarboxylic dianhydride having 8 to 36 carbon atoms include 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (hereinafter also referred to as 6FDA), 5- ( 2,5-dioxotetrahydro-3-furanyl) -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride, pyromellitic dianhydride (hereinafter also referred to as PMDA), 1,2,3,4-benzene Tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4 4′-biphenyltetracarboxylic dianhydride (hereinafter also referred to as BPDA), 3,3 ′, 4,4′-diphenyl
  • Examples of the aliphatic tetracarboxylic dianhydride having 6 to 50 carbon atoms include ethylene tetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride; Examples of the alicyclic tetracarboxylic dianhydride having 6 to 36 carbon atoms include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2, 3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride (hereinafter referred to as CHDA), 3,3 ′, 4,4′-bicyclohexyltetracarboxylic acid Dianhydride, carbonyl-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4′
  • PMDA, BPDA, TAHQ, ODPA are preferred, and BPDA, TAHQ are more preferred from the viewpoint of CTE, chemical resistance, Tg and the balance of yellowness in the high temperature region.
  • the polyimide precursor in an embodiment is good also as a polyamidoimide precursor by using dicarboxylic acid in addition to the above-mentioned tetracarboxylic dianhydride.
  • dicarboxylic acids include dicarboxylic acids having an aromatic ring and alicyclic dicarboxylic acids.
  • it is preferably at least one compound selected from the group consisting of aromatic dicarboxylic acids having 8 to 36 carbon atoms and alicyclic dicarboxylic acids having 6 to 34 carbon atoms.
  • the number of carbons herein includes the number of carbons contained in the carboxyl group. Of these, dicarboxylic acids having an aromatic ring are preferred.
  • the weight average molecular weight (Mw) of the polyimide precursor in the present embodiment is preferably 10,000 to 300,000, particularly preferably 30,000 to 200,000.
  • Mw weight average molecular weight
  • the weight average molecular weight is greater than 10,000, mechanical properties such as elongation and breaking strength are excellent, residual stress is low, and YI is low.
  • the weight average molecular weight is less than 300,000, it becomes easy to control the weight average molecular weight during synthesis of the polyamic acid, a resin composition having an appropriate viscosity can be obtained, and the coating property of the resin composition is improved.
  • the weight average molecular weight is a value obtained as a standard polystyrene equivalent value using gel permeation chromatography (hereinafter also referred to as GPC).
  • the content of molecules having a molecular weight of less than 1,000 is preferably less than 5% by mass and more preferably less than 1% by mass with respect to the total amount of the polyimide precursor.
  • a polyimide film formed from a resin composition obtained using such a polyimide precursor has a low residual stress, which is preferable from the viewpoint that the inorganic film formed on the polyimide film has a low haze.
  • the content of molecules having a molecular weight of less than 1,000 relative to the total amount of the polyimide precursor can be calculated from the peak area obtained by performing GPC measurement using a solution in which the polyimide precursor is dissolved.
  • Examples of the diamine used in the structural unit represented by the general formula (1) in the present embodiment include the diamine represented by the following general formula (6).
  • R 1 , R 2 and R 3 each independently represents a monovalent organic group having 1 to 20 carbon atoms, n represents 0 or 1, and a, b and c are integers of 0 to 4) .
  • R 1 and R 2 include alkyl groups such as a methyl group, an ethyl group, and a propyl group, halogen-containing groups such as a trifluoromethyl group, and alkoxy groups such as a methoxy group and an ethoxy group.
  • a methyl group is preferable from the viewpoint of YI in a high temperature region.
  • a and b are not limited as long as they are integers of 0 to 4.
  • an integer of 0 to 2 is preferable from the viewpoint of YI and residual stress, and 0 is particularly preferable from the viewpoint of YI in the high temperature region.
  • n is 1, [4- (4-aminobenzoyl) oxyphenyl] 4-aminobenzoate and the like can be exemplified.
  • Examples of the diamine used in the structural unit represented by the general formula (3) in the present embodiment include the diamine represented by the following general formula (7).
  • R 4 and R 5 each independently represents a monovalent organic group having 1 to 20 carbon atoms .
  • D and e are integers of 0 to 4.
  • R 4 and R 5 are not limited as long as they are each independently a monovalent organic group having 1 to 20 carbon atoms.
  • Examples of such an organic group include alkyl groups such as a methyl group, an ethyl group, and a propyl group, halogen-containing groups such as a trifluoromethyl group, and alkoxy groups such as a methoxy group and an ethoxy group.
  • a methyl group is preferable from the viewpoint of YI in a high temperature region.
  • c and d are not limited as long as they are integers of 0 to 4.
  • an integer of 0 to 2 is preferable from the viewpoint of YI and residual stress, and 0 is particularly preferable from the viewpoint of YI in the high temperature region.
  • 4,4′-diaminodiphenyl sulfone and 3,3′-diaminodiphenyl sulfone can be exemplified.
  • Examples of the diamine used in the structural unit represented by the general formula (4) in the present embodiment include the diamine represented by the following general formula (8).
  • R 6 and R 7 are not limited as long as they are each independently a monovalent organic group having 1 to 20 carbon atoms.
  • examples of such an organic group include alkyl groups such as methyl group, ethyl group, and propyl group; halogen-containing groups such as trifluoromethyl group; alkoxy groups such as methoxy group and ethoxy group; Among these, a methyl group is preferable from the viewpoint of YI in a high temperature region.
  • R 8 and R 9 are not limited as long as they are each independently a monovalent organic group having 1 to 20 carbon atoms, a hydroxyl group, or a halogen atom.
  • Examples of the organic group include alkyl groups such as methyl group, ethyl group, and propyl group; halogen-containing groups such as trifluoromethyl group; alkoxy groups such as methoxy group and ethoxy group;
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
  • f, g, h, and i are not limited as long as they are each independently an integer of 0 to 4.
  • an integer of 0 to 2 is preferable from the viewpoint of YI and residual stress, and 0 is particularly preferable from the viewpoint of YI in the high temperature region.
  • Z examples include a single bond, a methylene group, an ethylene group, ether, and ketone.
  • a single bond is more preferable from the viewpoint of YI in a high temperature region. More specifically, 9,9-bis (aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, 9,9-bis (4-amino-3-fluorophenyl) fluorene , 9,9-bis (4-hydroxy-3-aminophenyl) fluorene, 9,9-bis [4- (4-aminophenoxy) phenyl] fluorene, and the like. It is preferable to use one or more.
  • Examples of the diamine used in the structural unit represented by the general formula (5) in the present embodiment include the diamine represented by the following general formula (9).
  • R 10 and R 11 are not limited as long as they are each independently a monovalent organic group having 1 to 20 carbon atoms.
  • Examples of such an organic group include alkyl groups such as methyl group, ethyl group, and propyl group; halogen-containing groups such as trifluoromethyl group; alkoxy groups such as methoxy group and ethoxy group; Among these, a methyl group is preferable from the viewpoint of YI in a high temperature region.
  • j and k are not limited as long as they are each independently an integer of 0 to 4.
  • the polyimide film formed from the polyimide precursor of the first embodiment of the present invention has low residual stress, little warpage, low yellowness (YI value) in a high temperature region, and high elongation.
  • (A2) The following general formula (10): And a polyimide precursor having a weight average molecular weight of 30,000 or more and 300,000 or less.
  • X 3 is 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic dianhydride (BPDA), and 4,4'-biphenylbis (trimellitic acid monoester anhydride) (TAHQ) represents a tetravalent group derived from at least one selected from: R 1 , R 2 and R 3 each independently represents a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1. A, b and c are integers from 0 to 4.
  • ⁇ X 3 is not limited as long as it is a tetravalent organic group derived from at least one selected from ODPA, BPDA, and TAHQ, but BPDA and TAHQ are preferable from the viewpoint of CTE and Tg.
  • R 1 to R 3 are not limited as long as they are each independently a monovalent organic group having 1 to 20 carbon atoms. Examples of such an organic group include alkyl groups such as a methyl group, an ethyl group, and a propyl group, halogen-containing groups such as a trifluoromethyl group, and alkoxy groups such as a methoxy group and an ethoxy group.
  • a methyl group is preferable from the viewpoint of YI in a high temperature region.
  • a, b, c, and d are not limited as long as they are integers of 0 to 4.
  • an integer of 0 to 2 is preferable from the viewpoint of YI and residual stress, and 0 is particularly preferable from the viewpoint of YI in the high temperature region.
  • n is 0 or 1.
  • 0 is preferable from the viewpoint of YI in a high temperature region.
  • the weight average molecular weight (Mw) of the polyimide precursor in the second embodiment is 30,000 to 300,000.
  • Mw weight average molecular weight
  • mechanical properties such as elongation and breaking strength are excellent, residual stress is low, and YI is low.
  • the weight average molecular weight is less than 300,000, it becomes easy to control the weight average molecular weight during synthesis of the polyamic acid, a resin composition having an appropriate viscosity can be obtained, and the coating property of the resin composition is improved.
  • the weight average molecular weight (Mw) is more preferably 35000 to 250,000, and particularly preferably 40000 to 230,000.
  • the content of molecules having a molecular weight of less than 1,000 is preferably less than 5% by mass and less than 1% by mass with respect to the total amount of the polyimide precursor. More preferably.
  • a polyimide film formed from a resin composition obtained using such a polyimide precursor has a low residual stress, which is preferable from the viewpoint that the inorganic film formed on the polyimide film has a low haze.
  • the content of molecules having a molecular weight of less than 1,000 relative to the total amount of the polyimide precursor can be calculated from the peak area obtained by performing GPC measurement using a solution in which the polyimide precursor is dissolved.
  • the polyimide precursor of the second embodiment of the present embodiment is excellent in storage stability and excellent in coatability. Moreover, the polyimide film formed from the polyimide precursor of the second aspect of the present embodiment has low residual stress, low warpage, low yellowness (YI value), high elongation, and high breaking strength.
  • the diamines represented by the general formulas (6) to (9) described above within a range not impairing the elongation, strength, stress, and yellowness can be used.
  • other diamines include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfide, and 4,4′-.
  • the polyimide precursor (polyamic acid) of the present invention includes a tetracarboxylic dianhydride, a diamine (for example, APAB) used in the structural unit represented by the general formula (1), and the general formula (2). It can be synthesized by polycondensation reaction with a diamine (for example, 4,4′-DAS) used in the structural unit represented by This reaction is preferably carried out in a suitable solvent. Specifically, for example, a predetermined amount of APAB and 4,4′-DAS are dissolved in a solvent, and then a predetermined amount of tetracarboxylic dianhydride is added to the obtained diamine solution, followed by stirring. It is done.
  • the molar ratio of the diamine used in the structural unit represented by the general formula (1) and the diamine used in the structural unit represented by the general formula (2) may be 99/1 to 1/99.
  • the diamine used in the structural unit represented by the general formula (2) in the diamine component is 1 mol% or more, the yellowness tends to be good, and the structural unit represented by the general formula (1) is used. If the diamine to be obtained is 1 mol% or more, the warp after forming an inorganic film on the resulting polyimide film tends to be good.
  • the molar ratio of the diamine used in the structural unit represented by the general formula (1) and the diamine used in the structural unit represented by the general formula (2) is preferably 95/5 to 50/50, and 90/10 More preferable is 50/50.
  • the molar ratio of the diamine used in the structural unit represented by the general formula (1) and the diamine used in the structural unit represented by the general formula (2) may be 80/20 to 50/50, It may be 30-50 / 50. It is preferable that the molar ratio of the diamine used in the structural unit represented by the general formula (1) is equal to or higher than the molar ratio of the diamine used in the structural unit represented by the general formula (2).
  • the polyimide precursor of the second embodiment of the present invention includes a tetracarboxylic dianhydride (for example, TAHQ) and a diamine (for example, APAB) used for the structural unit represented by the general formula (6).
  • TAHQ tetracarboxylic dianhydride
  • APAB diamine
  • the ratio (molar ratio) of the tetracarboxylic dianhydride component to the diamine component is determined by the thermal linear expansion coefficient, residual stress, elongation, and yellowness (hereinafter referred to as YI) of the obtained resin film.
  • diamine 100: 90 to 100: 110 (diamine 0.90 to 1.1.0 mol per 1 mol of tetracarboxylic dianhydride). 10 mol parts), preferably 100: 95 to 100: 105 (0.95 to 1.05 mol parts of diamine with respect to 1 mol part of acid dianhydride).
  • the molecular weight is controlled by adjusting the ratio of the tetracarboxylic dianhydride component and the diamine component and adding a terminal blocking agent. It is possible.
  • the molecular weight of the polyamic acid can be increased as the ratio of the acid dianhydride component to the diamine component is closer to 1: 1 and as the amount of the end-capping agent used is smaller. It is recommended to use high-purity products as the tetracarboxylic dianhydride component and the diamine component.
  • the purity is preferably 98% by mass or more, more preferably 99% by mass or more, and still more preferably 99.5% by mass or more.
  • the acid dianhydride component or diamine component has the above purity as a whole, but all types of acid dianhydrides used It is preferable that the component and the diamine component each have the above-described purity.
  • the solvent for the reaction is not particularly limited as long as it is a solvent that can dissolve the tetracarboxylic dianhydride component and the diamine component, and the resulting polyamic acid, and obtain a high molecular weight polymer.
  • solvents include aprotic solvents, phenol solvents, ethers and glycol solvents. Specific examples of these are: Examples of the aprotic solvent include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, 1,3-dimethyl.
  • Imidazolidinone, tetramethylurea the following general formula (13):
  • R 12 Ecamide M100 represented by methyl group (trade name: manufactured by Idemitsu Kosan Co., Ltd.)
  • R 12 Ecamide B100 represented by n-butyl group (trade name: manufactured by Idemitsu Kosan Co., Ltd.), etc.
  • amide solvent An amide solvent
  • Lactone solvents such as ⁇ -butyrolactone and ⁇ -valerolactone
  • Phosphorus-containing amide solvents such as hexamethylphosphoric amide and hexamethylphosphine triamide
  • Sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide, sulfolane
  • Ketone solvents such as cyclohexanone and methylcyclohexanone
  • Tertiary amine solvents such as picoline and pyridine
  • Ester solvents such as acetic acid (2-methoxy-1-methylethyl) include:
  • the phenol solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2, 5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xyleno
  • the boiling point at normal pressure of the solvent used for synthesizing the polyamic acid is preferably 60 to 300 ° C, more preferably 140 to 280 ° C, and particularly preferably 170 to 270 ° C.
  • the boiling point of the solvent is higher than 300 ° C.
  • a drying process is required for a long time.
  • the boiling point of the solvent is lower than 60 ° C., the surface of the resin film may be roughened during the drying process, bubbles may be mixed into the resin film, and a uniform film may not be obtained.
  • the solvent is preferably 3000 ppm by mass or less. These solvents may be used alone or in combination of two or more.
  • the polyimide precursor (a) in this embodiment preferably has a molecular content of less than 1,000 molecular weight of less than 5% by mass.
  • the water content of this solvent is preferably 3,000 mass ppm or less, more preferably 1,000 mass ppm or less.
  • the water content of the solvent includes the grade of solvent used (dehydration grade, general-purpose grade, etc.), solvent container (bottle, 18L can, canister can, etc.), solvent storage status (whether or not rare gas is sealed, etc.), from opening to use (Such as use immediately after opening or use after lapse of time after opening) and the like.
  • solvent container bottle, 18L can, canister can, etc.
  • solvent storage status whether or not rare gas is sealed, etc.
  • the rare gas replacement in the reactor before the synthesis the presence or absence of a rare gas flow during the synthesis, and the like are also involved. Therefore, when synthesizing (a) a polyimide precursor, a high-purity product is used as a raw material, a solvent with a small amount of water is used, and measures are taken to prevent moisture from the environment from entering the system before and during the reaction. It is recommended.
  • the reaction temperature during the synthesis of the polyimide precursor is preferably 0 ° C. to 120 ° C., more preferably 40 ° C. to 100 ° C., and still more preferably 60 to 100 ° C. By performing the polymerization reaction at this temperature, a polyimide precursor having a high degree of polymerization can be obtained.
  • the polymerization time is preferably 1 to 100 hours, more preferably 2 to 10 hours. By setting the polymerization time to 1 hour or more, a polyimide precursor having a uniform polymerization degree can be obtained, and by setting the polymerization time to 100 hours or less, a polyimide precursor having a high polymerization degree can be obtained.
  • (a1) polyimide precursor and (a2) polyimide precursor have the following characteristics.
  • a nitrogen atmosphere for example, having an oxygen concentration of 2,000 ppm or less.
  • a resin obtained by imidizing the polyimide precursor by heating for example, 1 hour
  • the yellowness in a 10 ⁇ m film thickness is 30 or less.
  • the polyimide precursor according to the present embodiment is, as necessary, the following general formula (14) as long as the desired performance of the present invention is not impaired.
  • a plurality of R 13 are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon having 1 to 20 carbon atoms, or a monovalent aromatic group
  • X 4 is a tetravalent organic group having 4 to 32 carbon atoms
  • Y is a divalent organic group having 4 to 32 carbon atoms.
  • the structural unit corresponding to the general formula (1) and the general formula (6) is excluded.
  • ⁇ May further contain a polyimide precursor having a structure represented by:
  • R 13 is preferably a hydrogen atom.
  • X 3 is preferably a tetravalent aromatic group from the viewpoints of heat resistance, YI value reduction, and total light transmittance.
  • Y is preferably a divalent aromatic group or an alicyclic group from the viewpoints of heat resistance, YI value reduction, and total light transmittance.
  • the mass proportion of the polyimide precursor having the structural unit represented by the general formula (14) in (a) the polyimide precursor according to the present embodiment is 80% by mass or less based on the total of the (a) polyimide precursor. It is preferable that it is 70 mass% or less from a viewpoint of the oxygen-dependent fall of YI value and a total light transmittance.
  • the polyimide precursor and (a2) the polyimide precursor may be partially imidized.
  • the imidization rate is preferably 80% or less, and more preferably 50% or less.
  • This partial imidization can be obtained by heating the above polyimide precursor (a) and dehydrating and closing the ring. This heating is preferably 120 to 200 ° C., more preferably 150 to 180 ° C., preferably 15 minutes to 20 hours, more preferably 30 minutes to 10 hours.
  • N, N-dimethylformamide dimethyl acetal or N, N-dimethylformamide diethyl acetal is added to the polyamic acid obtained by the above reaction and heated to esterify part or all of the carboxylic acid.
  • the (a) polyimide precursor in the present embodiment, a resin composition having improved viscosity stability during storage at room temperature can be obtained.
  • the above acid dianhydride component is sequentially reacted with one equivalent of a monohydric alcohol with respect to the acid anhydride group and a dehydration condensing agent such as thionyl chloride or dicyclohexylcarbodiimide. Thereafter, it can also be obtained by a condensation reaction with a diamine component.
  • the proportion of the (a) polyimide precursor (preferably polyamic acid) in the resin composition of the present embodiment is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, from the viewpoint of coating film formation. 30% by mass is particularly preferred.
  • ⁇ Resin composition> Another aspect of the present invention provides a resin composition containing the aforementioned (a) polyimide precursor and (b) an organic solvent. This resin composition is typically a varnish.
  • the (b) organic solvent in the present embodiment is not particularly limited as long as it can dissolve the aforementioned (a) polyimide precursor and other optional components.
  • organic solvent those described above as the solvent that can be used in the synthesis of (a) the polyimide precursor can be used. Preferred organic solvents are also the same as described above.
  • the (b) organic solvent in the resin composition of the present embodiment may be the same as or different from the solvent used for the synthesis of (a) the polyimide precursor.
  • the organic solvent is preferably in an amount such that the solid content concentration of the resin composition is 3 to 50% by mass. Further, it is preferable to add (b) after adjusting the constitution and amount of the organic solvent so that the viscosity (25 ° C.) of the resin composition is 500 mPa ⁇ s to 100,000 mPa ⁇ s.
  • the resin composition of the present embodiment may further contain (c) a surfactant, (d) an alkoxysilane compound and the like in addition to the components (a) and (b).
  • the resin composition according to this embodiment includes (a) a polyimide precursor, (b) an organic solvent, (c) a surfactant, and (d) at least one selected from the group consisting of alkoxysilane compounds, including.
  • the skeleton of the polyimide precursor is not limited to the skeleton described above in the first aspect and the second aspect. That is, the skeleton of the polyimide precursor is not particularly limited as long as it is a skeleton represented by the following general formula (1).
  • X 1 represents a tetravalent group having 4 to 32 carbon atoms.
  • R 1 , R 2 and R 3 each independently represents a monovalent organic group having 1 to 20 carbon atoms.
  • n represents 0 or 1.
  • A, b and c are integers from 0 to 4. ⁇
  • (C) surfactant By adding a surfactant to the resin composition of the present embodiment, the applicability of the resin composition can be improved. Specifically, the generation of streaks in the coating film can be prevented.
  • surfactants include silicone surfactants, fluorosurfactants, and other nonionic surfactants. Examples of these are: Examples of silicone-based surfactants include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, X-70-093 (above, trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), SH-28PA.
  • silicone-based surfactants and fluorine-based surfactants are preferable, and the YI value and total light transmission depending on the oxygen concentration during the curing process. From the viewpoint of influence on the rate, a silicone-based surfactant is preferable.
  • the blending amount is preferably 0.001 to 5 parts by mass, and 0.01 to 3 parts by mass with respect to 100 parts by mass of (a) polyimide precursor in the resin composition. Is more preferable.
  • the resin composition The product may contain 0.01 to 20% by mass of an alkoxysilane compound with respect to (a) 100% by mass of the polyimide precursor.
  • the content of the alkoxysilane compound with respect to 100% by mass of the polyimide precursor is 0.01% by mass or more, good adhesion to the support can be obtained.
  • the content of the alkoxysilane compound is more preferably 0.02 to 15% by mass, further preferably 0.05 to 10% by mass, more preferably 0.1 to 0.1% by mass with respect to 100 parts by mass of the polyimide precursor. It is especially preferable that it is 8 mass%.
  • alkoxysilane compound examples include 3-ureidopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltripropoxysilane, ⁇ -aminopropyltributoxysilane, ⁇ -aminoethyltriethoxysilane, ⁇ -aminoethyltripropoxysilane, ⁇ -aminoethyltributoxysilane, ⁇ -aminobutyltriethoxysilane, ⁇ - Aminobutyltrimethoxysilane, ⁇ -aminobutyltripropoxysilane, ⁇ -aminobutyltributoxysilane, phenylsilanetriol, trimethoxyphenylsilane
  • the method for producing the resin composition in the present embodiment is not particularly limited.
  • the following method can be used.
  • the synthesized polyimide precursor solution can be used as it is as the resin composition.
  • at least one of (b) an organic solvent and other components is added to the polyimide precursor at room temperature (25 ° C.) to 80 ° C., and the mixture is stirred and mixed. You may use as a thing.
  • an appropriate device such as a three-one motor (manufactured by Shinto Chemical Co., Ltd.) equipped with a stirring blade, a rotation and revolution mixer, or the like can be used. If necessary, heat of 40 to 100 ° C. may be applied.
  • the solvent used when synthesizing the polyimide precursor when (a) the solvent used when synthesizing the polyimide precursor is different from (b) the organic solvent, the solvent in the synthesized polyimide precursor solution may be reprecipitated, e.g. After removing by a suitable method (a) isolating the polyimide precursor, (b) adding an organic solvent and other components as necessary in a temperature range of room temperature to 80 ° C., and stirring and mixing. Thus, a resin composition may be prepared.
  • a part of the polyimide precursor is dehydrated to such an extent that the polymer does not precipitate by heating the composition solution at 130 to 200 ° C., for example, for 5 minutes to 2 hours. It may be imidized.
  • the imidization rate can be controlled by controlling the heating temperature and the heating time.
  • the imidation ratio is preferably 5% to 70% from the viewpoint of balancing the solubility of the polyimide precursor in the resin composition solution and the storage stability of the solution.
  • the resin composition according to the present embodiment preferably has a water content of 3,000 mass ppm or less.
  • the water content of the resin composition is more preferably 1,000 ppm by mass or less, and still more preferably 500 ppm by mass or less, from the viewpoint of viscosity stability when the resin composition is stored.
  • the solution viscosity of the resin composition according to the present embodiment is preferably 500 to 200,000 mPa ⁇ s, more preferably 2,000 to 100,000 mPa ⁇ s at 25 ° C., and 3,000 to 30,000 mPa ⁇ s. Is particularly preferred.
  • This solution viscosity can be measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., VISCONICEHD).
  • E-type viscometer manufactured by Toki Sangyo Co., Ltd., VISCONICEHD
  • A When a polyimide precursor is synthesized, even if the solution becomes highly viscous, it is possible to obtain a resin composition having a good handleability by adding a solvent after the reaction and stirring.
  • the resin composition of the present embodiment has the following characteristics in a preferred embodiment. After the resin composition is applied to the surface of the support to form a coating film, the coating film is heated at 300 ° C. to 550 ° C. in a nitrogen atmosphere (for example, in nitrogen having an oxygen concentration of 2,000 ppm or less).
  • the resin film obtained by imidizing the polyimide precursor contained in the coating film has a yellowness YI of 30 or less at a film thickness of 10 ⁇ m.
  • the coating film is heated at 300 ° C. to 550 ° C. in a nitrogen atmosphere (for example, in nitrogen having an oxygen concentration of 2,000 ppm or less).
  • the resin film obtained by imidizing the polyimide precursor contained in the coating film has a residual stress of 25 MPa or less.
  • the resin composition according to the present embodiment can be suitably used for forming a transparent substrate of a display device such as a liquid crystal display, an organic electroluminescence display, a field emission display, or electronic paper. Specifically, it can be used for forming a thin film transistor (TFT) substrate, a color filter substrate, a transparent conductive film (ITO, Indium Thin Oxide) substrate, and the like. Since the resin precursor of this embodiment can form a polyimide film having a residual stress of 25 MPa or less, it can be easily applied to a display manufacturing process including a TFT element device on a colorless transparent polyimide substrate.
  • TFT thin film transistor
  • ITO Indium Thin Oxide
  • ⁇ Resin film> Another aspect of the present invention provides a resin film formed from the aforementioned resin precursor. Moreover, another aspect of this invention provides the method of manufacturing a resin film from the above-mentioned resin composition.
  • the resin film in the present embodiment is Forming a coating film by applying the resin composition described above on the surface of the support (application process); Heating the support and the coating film to imidize the polyimide precursor contained in the coating film to form a polyimide resin film (heating process); A step of peeling the polyimide resin film from the support (peeling step); It is characterized by including.
  • the support is not particularly limited as long as it has heat resistance at the heating temperature in the subsequent step and has good peelability.
  • a glass (eg, alkali-free glass) substrate e.g, alkali-free glass) substrate; Silicon wafers; Resin substrates such as PET (polyethylene terephthalate), OPP (stretched polypropylene), polyethylene glycol terephthalate, polyethylene glycol naphthalate, polycarbonate, polyimide, polyamideimide, polyetherimide, polyetheretherketone, polyethersulfone, polyphenylenesulfone, polyphenylenesulfide ;
  • a metal substrate such as stainless steel, alumina, copper, or nickel is used.
  • a film-like polyimide molded body for example, a glass substrate, a silicon wafer or the like is preferable.
  • a film-like or sheet-like polyimide molded body for example, PET (polyethylene terephthalate), OPP A support made of (stretched polypropylene) or the like is preferable.
  • coating methods include doctor blade knife coaters, air knife coaters, roll coaters, rotary coaters, flow coaters, die coaters, bar coaters, and other coating methods, spin coating, spray coating, dip coating and the like; screen printing and Printing techniques such as gravure printing can be applied.
  • 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, but is preferably about 1 to 1,000 ⁇ m.
  • the application step is sufficient at room temperature, but the resin composition may be heated in the range of 40 to 80 ° C. for the purpose of reducing viscosity and improving workability.
  • the drying process may be performed following the coating process, or the drying process may be omitted and the process may proceed directly to the next heating process.
  • This drying step is performed for the purpose of removing the organic solvent.
  • suitable apparatuses such as a hot plate, a box-type dryer, and a conveyor type dryer, can be utilized, for example.
  • the drying step is preferably performed at 80 to 200 ° C., more preferably 100 to 150 ° C.
  • the duration of the drying step is preferably 1 minute to 10 hours, more preferably 3 minutes to 1 hour.
  • a coating film containing a polyimide precursor is formed on the support.
  • a heating process is performed.
  • the heating step is a step of removing the organic solvent remaining in the coating film in the above-described drying process and advancing the imidization reaction of the polyimide precursor in the coating film to obtain a film made of polyimide.
  • This heating process can be performed using apparatuses, such as an inert gas oven, a hot plate, a box-type dryer, and a conveyor type dryer, for example. This step may be performed simultaneously with the drying step, or both steps may be performed sequentially.
  • the heating step may be performed in an air atmosphere, but it is recommended that the heating step be performed in an inert gas atmosphere from the viewpoints of safety, transparency of the obtained polyimide film, and YI value.
  • the inert gas include nitrogen and argon.
  • the heating temperature may be appropriately set according to the type of (b) organic solvent, but is preferably 250 ° C. to 550 ° C., more preferably 300 to 450 ° C. When it is 250 ° C. or higher, imidization is sufficient, and when it is 550 ° C. or lower, there are no inconveniences such as a decrease in transparency and deterioration of heat resistance of the obtained polyimide film.
  • the heating time is preferably about 0.5 to 3 hours.
  • the oxygen concentration in the ambient atmosphere in the heating step is preferably 2,000 ppm by mass or less, more preferably 100 ppm by mass or less, from the viewpoint of the transparency and YI value of the obtained polyimide film. More preferred is mass ppm or less.
  • the YI value of the resulting polyimide film can be made 30 or less.
  • a peeling step for peeling the resin film from the support is required after the heating step.
  • This peeling step is preferably performed after cooling the resin film on the support to room temperature to about 50 ° C.
  • Examples of the peeling step include the following aspects (1) to (4).
  • a laser is irradiated from the support side of the structure to ablate the interface between the support and the polyimide resin film.
  • a method of peeling polyimide resin examples include a solid (YAG) laser and a gas (UV excimer) laser. It is preferable to use a spectrum having a wavelength of 308 nm or the like (refer to JP-T2007-512568, JP-T2012-511173, etc.).
  • release layer A method in which a release layer is formed on a support before applying the resin composition to the support, and then a polyimide resin film / release layer / a structure including the support is obtained to release the polyimide resin film.
  • the release layer include a method using parylene (registered trademark, manufactured by Japan Parylene Godo Kaisha), tungsten oxide; a method using a release agent such as vegetable oil, silicone, fluorine, alkyd and the like. (See JP 2010-67957 A, JP 2013-179306 A, etc.). You may use together this method (2) and the laser irradiation of said (1).
  • the metal for example, copper (as an example, electrolytic copper foil “DFF” manufactured by Mitsui Mining & Smelting Co., Ltd.), aluminum, or the like can be used.
  • the etchant ferric chloride or the like can be used for copper, and dilute hydrochloric acid or the like can be used for aluminum.
  • an adhesive film is attached to the surface of the polyimide resin film to separate the adhesive film / polyimide resin film from the support, and then the adhesive film Of separating the polyimide resin film from the substrate.
  • the method (1) or (2) is appropriate from the viewpoint of the refractive index difference between the front and back of the polyimide resin film to be obtained, the YI value, and the elongation.
  • the method (1) is more appropriate from the viewpoint of the refractive index difference.
  • the method (3) when using copper as a support body, the YI value of the polyimide resin film obtained becomes large, and the tendency for elongation to become small is seen. This is considered to be an influence of copper ions.
  • the thickness of the resin film obtained by the above method is not particularly limited, but is preferably in the range of 1 to 200 ⁇ m, more preferably 5 to 100 ⁇ m.
  • the resin film according to the present embodiment can have a yellowness YI of 30 ⁇ m or less at a film thickness of 10 ⁇ m. Further, the residual stress can be 25 MPa or less. In particular, the yellowness YI at 10 ⁇ m thickness can be 30 or less and the residual stress can be 25 MPa or less.
  • Such characteristics include, for example, that the resin precursor of the present disclosure is imide in a nitrogen atmosphere (for example, in nitrogen having an oxygen concentration of 2,000 ppm or less), preferably at 300 ° C. to 550 ° C., more preferably at 350 ° C. to 450 ° C. By realizing, it is realized well.
  • the resin film according to the present embodiment can further have a tensile elongation of 15% or more.
  • the tensile elongation of the resin film can be further 20% or more, particularly 30% or more.
  • the tensile elongation can be measured using a commercially available tensile tester using a 10 ⁇ m-thick resin film as a sample.
  • the resin film according to the present embodiment is a film made of polyimide obtained by thermal imidization of the (a1) polyimide precursor contained in the above resin composition. Therefore, the following general formula (11): ⁇ Wherein X 1 and X 2 represent a tetravalent group having 4 to 32 carbon atoms. R 1 , R 2 and R 3 each independently represents a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1. A, b and c are integers from 0 to 4. Y is at least one selected from the group consisting of the general formulas (3), (4) and (5). l and m each independently represent an integer of 1 or more, and satisfy 0.01 ⁇ l / (l + m) ⁇ 0.99.
  • the lower limit of l / (l + m) may be 0.05, 0.10, 0.20, 0.30, or 0.40.
  • the upper limit of l / (l + m) may be 0.95, 0.90, 0.80, 0.70, or 0.60.
  • the residual stress is 25 MPa or less
  • the YI is 30 or less
  • the glass transition temperature is 400 ° C. or more
  • the elongation is 15% or more
  • the breaking strength is 250 MPa or more. .
  • X 3 is 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic dianhydride (BPDA), and 4,4'-biphenylbis (trimellitic acid monoester anhydride) (TAHQ) represents a tetravalent group derived from at least one selected from: R 1 , R 2 and R 3 each independently represents a monovalent organic group having 1 to 20 carbon atoms. n represents 0 or 1.
  • ODPA 4,4'-oxydiphthalic dianhydride
  • BPDA biphenyltetracarboxylic dianhydride
  • TAHQ 4,4'-biphenylbis (trimellitic acid monoester anhydride)
  • A, b and c are integers from 0 to 4.
  • ⁇ Laminate> Another aspect of the present invention provides a laminate comprising a support and a polyimide resin film formed from the above resin composition on the surface of the support. Still another embodiment of the present invention provides a method for producing the laminate.
  • the laminate in the present embodiment is On the surface of the support, a step of forming a coating film by applying the resin composition described above (application step), Heating the support and the coating film to imidize the polyimide precursor contained in the coating film to form a polyimide resin film (heating process); It can obtain by the manufacturing method of a laminated body containing.
  • the manufacturing method of said laminated body can be implemented like the manufacturing method of the above-mentioned resin film except not performing a peeling process, for example.
  • This laminated body can be used suitably for manufacture of a flexible device, for example. This will be described in detail below.
  • a glass substrate is used as a support, a flexible substrate is formed thereon, and a TFT or the like is further formed thereon.
  • the process of forming a TFT or the like on a flexible substrate is typically performed at a wide temperature range of 150 to 650 ° C.
  • an inorganic material is used at a high temperature around 250 ° C. to 450 ° C., and the TFT-IGZO (InGaZnO) oxide semiconductor or TFT (a-Si-TFT, poly) is used.
  • a-Si-TFT TFT-Si-TFT
  • the polyimide film obtained from the polyimide precursor according to the present invention is extremely low in yellowness and elongation even in a high temperature region of 400 ° C. or higher, and can be used favorably in that region.
  • the laminated body containing the polyimide film layer containing the polyimide represented by following General formula (13), and a LTPS (low temperature polysilicon TFT) layer can be provided.
  • X 1 represents a tetravalent group having 4 to 32 carbon atoms.
  • R 1 , R 2 and R 3 each independently represents a monovalent organic group having 1 to 20 carbon atoms.
  • n represents 0 or 1.
  • A, b and c are integers from 0 to 4.
  • an amorphous Si layer is formed after producing a laminate comprising the above-mentioned support and a polyimide resin film formed from the above-mentioned resin composition on the surface of the support.
  • the LTPS layer can be formed by crystallization with an excimer laser or the like. Then, the said laminated body can be obtained by peeling glass and a polyimide film by laser peeling etc.
  • a laminate including a polyimide film layer containing polyimide represented by the general formula (13) and an LTPS (low-temperature polysilicon TFT) layer has little peeling and swelling after the heat cycle test and little substrate warpage. Also, if the residual stress generated in the flexible substrate and the polyimide resin film is high, when the laminate composed of both expands in the high-temperature TFT process and then contracts during cooling at room temperature, the glass substrate warps and breaks, and the flexible substrate glass Problems such as peeling from the substrate may occur. In general, since the thermal expansion coefficient of a glass substrate is smaller than that of a resin, a residual stress is generated between the glass substrate and the flexible substrate. Since the resin film concerning this embodiment can make the residual stress produced between glass substrates into 25 Mpa or less as mentioned above, it can be used conveniently for formation of a flexible display.
  • LTPS low-temperature polysilicon TFT
  • the polyimide film according to the present embodiment can have a yellowness YI at a film thickness of 10 ⁇ m of 30 or less and a tensile elongation of 15% or more.
  • the resin film according to the present embodiment is excellent in breaking strength when handling a flexible substrate, and thus can improve the yield when manufacturing a flexible display.
  • the yellowness at a film thickness of 10 microns after heating at 400 ° C. or higher is 20 or less
  • the absorbance at 308 nm when the film thickness is 0.1 microns is from 0.6 to 2.0
  • a polyimide film having an elongation of 15% or more can be provided.
  • a polyimide film can be easily peeled off from a glass substrate with a laser.
  • 0.6 or more and 1.5 or less and an elongation of 20% or more are preferable.
  • the upper limit of the elongation is not particularly limited, but may be 80% or less, 70% or less, 60% or less, 50% or less, or 40% or less.
  • a polyimide film may burn with a laser beam at the time of laser peeling, and the unburned residue is ash.
  • another aspect of the present invention provides a display substrate.
  • Still another aspect of the present invention provides a method for manufacturing the display substrate.
  • the manufacturing method of the display substrate in the present embodiment is as follows: Forming a coating film by applying the resin composition described above on the surface of the support (application process); Heating the support and the coating film to imidize the polyimide precursor contained in the coating film to form a polyimide resin film (heating process); A step of forming an element or a circuit on the polyimide resin film (element / circuit formation step); A step (peeling step) of peeling the polyimide resin film on which the element or circuit is formed from the support.
  • coating process, a heating process, and a peeling process can respectively be performed like the manufacturing method of the resin film mentioned above.
  • the element / circuit formation step can be performed by a method known to those skilled in the art.
  • the resin film according to the present embodiment satisfying the above physical properties is suitably used for uses such as colorless transparent substrates for flexible displays, protective films for color filters, etc., where use is restricted by the yellow color of existing polyimide films.
  • protective films, diffuser sheets and coating films for TFT-LCDs eg TFT-LCD interlayers, gate insulating films, liquid crystal alignment films, etc.
  • touch panel ITO substrates eg. TFT-LCD interlayers, gate insulating films, liquid crystal alignment films, etc.
  • smartphone cover glass substitute resin substrates It can also be used in fields where colorless transparency and low birefringence are required.
  • the polyimide according to the present embodiment is applied as the liquid crystal alignment film, a TFT-LCD having a high aperture ratio and a high contrast ratio can be manufactured.
  • the polyimide precursor and the resin film and laminate produced using the resin precursor according to this embodiment can be applied as, for example, a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, etc. In production, it can be suitably used particularly as a substrate.
  • the flexible device to which the resin film and the laminate according to this embodiment can be applied include a flexible display, a flexible solar cell, a flexible touch panel electrode substrate, flexible lighting, and a flexible battery.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) under the following conditions.
  • GPC gel permeation chromatography
  • N, N-dimethylformamide manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph
  • 24.8 mmol / L lithium bromide monohydrate manufactured by Wako Pure Chemical Industries, Ltd., purity 99.75
  • 63.2 mmol / L phosphoric acid manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph
  • a calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).
  • the content of molecules having a molecular weight of less than 1,000 in the resin is determined by the ratio (percentage) of the peak area occupied by the component having a molecular weight of less than 1,000 to the peak area of the entire molecular weight distribution, using the GPC measurement results obtained above. ).
  • Viscosity measurement at 23 ° C. is performed using a sample that has been allowed to stand at room temperature for 3 days after preparation as a sample after preparation; Thereafter, the sample was further allowed to stand at room temperature for 2 weeks, and the viscosity at 23 ° C. was measured again as a sample after 2 weeks.
  • These viscosities were measured using a temperature controller viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.). Using the above measured values, the viscosity change rate at room temperature for 2 weeks was calculated according to the following formula.
  • Viscosity change rate (%) at room temperature for 2 weeks [(viscosity of sample after 2 weeks) ⁇ (viscosity of sample after preparation)] / (viscosity of sample after preparation) ⁇ 100
  • the viscosity change rate at room temperature for 2 weeks was evaluated according to the following criteria.
  • Each resin composition was applied by a spin coater onto a 6-inch silicon wafer having a thickness of 625 ⁇ m ⁇ 25 ⁇ m, for which the “warping amount” had been measured in advance, and prebaked at 100 ° C. for 7 minutes. Thereafter, using a vertical curing furnace (manufactured by Koyo Lindberg Co., Ltd., model name: VF-2000B), the oxygen concentration in the chamber was adjusted to 10 ppm by mass or less, and heat curing treatment at 430 ° C. for 1 hour ( A silicon wafer with a polyimide resin film having a thickness of 10 ⁇ m after curing was prepared.
  • the amount of warpage of the wafer was measured using a residual stress measuring device (manufactured by Tencor, model name FLX-2320) to evaluate the residual stress generated between the silicon wafer and the resin film.
  • X Residual stress exceeds 25 MPa (residual stress evaluation “bad”)
  • the resin composition prepared in each of the examples and comparative examples was spin-coated on a 6-inch silicon wafer substrate provided with an aluminum vapor deposition layer on the surface so that the film thickness after curing was 10 ⁇ m, and then at 100 ° C. for 7 minutes. Pre-baked. Then, using a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B), the oxygen concentration in the chamber is adjusted to 10 ppm by mass or less, and a heat curing treatment at 430 ° C. for 1 hour is performed. And a wafer having a polyimide resin film formed thereon was produced.
  • SiNx silicon nitride
  • the laminate wafer obtained above was immersed in a dilute hydrochloric acid aqueous solution, and the two layers of the inorganic film and the polyimide film were integrally peeled from the wafer to obtain a polyimide film sample having an inorganic film formed on the surface.
  • the warpage of the polyimide resin film was evaluated using this sample.
  • ⁇ The film is curled due to warping (warping “defective”)
  • YI value yellowness (YI value)>
  • a wafer (no inorganic film formed) was prepared in the same manner as described above ⁇ Evaluation of warpage of polyimide resin film with inorganic film formed>.
  • the wafer was immersed in a dilute hydrochloric acid aqueous solution, and the polyimide resin film was peeled off to obtain a resin film.
  • YI value film thickness conversion of 10 micrometers
  • a wafer (no inorganic film formed) was prepared in the same manner as described above ⁇ Evaluation of warpage of polyimide resin film with inorganic film formed>.
  • a dicing saw (DAD 3350, manufactured by DISCO Corporation)
  • DAD 3350 a 3 mm wide cut was made in the polyimide resin film of the wafer, and then immersed in a dilute hydrochloric acid solution overnight to peel off the resin film piece and dried. This was cut into a length of 50 mm to obtain a sample.
  • Example 1 In a 500-ml separable flask purged with nitrogen, 96 g of N-methyl-2-pyrrolidone (NMP) was added, 17.71 g (77.6 mmol) of 4-aminophenyl-4-aminobenzoate (APAB) and 4,4′- Diaminodiphenyl sulfone (DAS) (4.82 g, 19.4 mmol) was added and stirred to dissolve APAB and DAS. Thereafter, 29.42 g (100 mmol) of biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride (BPDA) was added, and a polymerization reaction was performed with stirring at 80 ° C.
  • NMP N-methyl-2-pyrrolidone
  • APAB 4-aminophenyl-4-aminobenzoate
  • DAS 4,4′- Diaminodiphenyl sulfone
  • BPDA 4,4′-tetracarbox
  • the obtained polyamic acid had a weight average molecular weight (Mw) of 65,000.
  • Examples 2 to 21 and Comparative Examples 1 to 5 In the said Example 1, the preparation amount (molar ratio) of a raw material, the kind of use solvent, superposition
  • the polyimide films obtained in Comparative Examples 1 and 2 containing only the structural unit represented by the general formula (1) are brittle and can be evaluated for physical properties such as elongation. There wasn't. Also, the residual stress was high. Moreover, the polyimide film obtained in Comparative Example 3 containing only the structural unit represented by the general formula (2) had high residual stress, warped after formation of the inorganic film, and low in elongation. On the other hand, the polyimide film obtained from Examples 1 to 21 containing the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) at a molar ratio of 99/1 to 1/99.
  • the polyimide resin film obtained from the resin composition according to the present invention is a resin film having small yellowness, low residual stress, and excellent mechanical properties. Specifically, in the present invention, a resin film having a residual stress of 25 MPa or less, a yellowness YI of 30 or less, and an elongation of 15% or more is obtained.
  • Example 22 In a 500-ml separable flask purged with nitrogen, N-methyl-2-pyrrolidone (NMP) (water content 250 mass ppm) immediately after opening the 18-L can was placed in an amount corresponding to a solid content of 17 wt%. 5.71 g (25.0 mmol) of -4-aminobenzoate (APAB, purity 99.5%, manufactured by Nippon Pure Chemicals Co., Ltd.) was added and stirred to dissolve APAB.
  • NMP N-methyl-2-pyrrolidone
  • Example 23 to 33 and Comparative Examples 6 to 11 In Example 22 above, except that the type of raw material, the amount of raw material charged, the type of solvent used, the polymerization temperature, and the polymerization time were changed as shown in Table 3, respectively, as in Synthesis Example 1, Varnishes P-28 to P-44 were obtained. Table 3 shows the weight average molecular weight (Mw) of the polyamic acid contained in each varnish.
  • Comparative Example 6 P-39
  • Comparative Example 7 P-40
  • Comparative Example 8 P in which the weight average molecular weight of the polyimide precursor (varnish) was 3,0000 or less.
  • Comparative Example 10 P-43)
  • Comparative Example 11 P-44) had large residual stress and large warpage.
  • yellowness was large and elongation and breaking strength were also small.
  • Comparative Examples 10 and 11 having a large amount of water the film was very fragile.
  • Comparative Example 9 in which the weight average molecular weight of the polyimide precursor was 30,000 or more, the residual stress and warpage were small, the yellowness was low, the elongation and the breaking strength were large, but the coatability was high. It got worse.
  • Examples 22 to 33 using polyimide precursors P-27 to P-38 having a weight average molecular weight of 30,000 or more and 300,000 or less the residual stress is low, the warp is small, and the yellow Excellent results were obtained with any of the properties of low degree, high elongation and high breaking strength.
  • the polyimide resin film obtained from the resin composition according to the present invention is a resin film having a small yellowness, a low residual stress, and excellent mechanical properties.
  • the residual stress is 25 MPa or less
  • the yellowness YI is 20 or less
  • the glass transition temperature is 400 ° C. or more
  • the elongation is 15% or more
  • the breaking strength is 250 MPa.
  • Example 34 In Examples 34 to 45 shown below, experiments were conducted on the effects of adding at least one selected from the group consisting of a surfactant and an alkoxysilane compound to the resin composition.
  • varnish P-27 obtained in Example 22 was used as a resin composition as it was, and coating stripes were evaluated by the following procedure.
  • Coating was performed three times using the same resin composition, the number of coating stripes was examined for each coating film, and evaluation was performed according to the following criteria using the average value.
  • the evaluation results are shown in Table 5.
  • Examples 35 to 45 By adding a surfactant or alkoxysilane compound of the type and amount shown in Table 5 as an additional additive to varnish P-27 obtained in Example 22 above, the mixture was filtered through a 0.1 ⁇ m filter. A resin composition was prepared. Using the resin composition, coating streaks were evaluated in the same manner as in Example 34. The results are shown in Table 5.
  • Varnish P-27 was applied onto an alkali-free glass substrate (size 37 ⁇ 47 mm, thickness 0.7 mm) using a bar coater so as to have a film thickness of 10 ⁇ m after curing, and then prebaked at 140 ° C. for 60 minutes. Subsequently, using a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B), the oxygen concentration in the chamber was adjusted to 10 ppm by mass or less, and a heat curing treatment at 430 ° C. for 1 hour was performed. And a glass substrate on which a polyimide resin film was formed.
  • An amorphous silicon layer was formed on the polyimide film, subjected to dehydrogenation annealing at 430 ° C. for 1 hour, and then irradiated with an excimer laser to form an LTPS layer.
  • the glass substrate was peeled off with an excimer laser (wavelength 308 nm, repetition frequency 300 Hz) to obtain a laminate including a polyimide film and an LTPS layer. This laminate had no warpage and the yellowness was 20 or less.
  • Example 47 A laminate was obtained in the same manner as in Example 46 except that varnish P-1 was used. This laminate had no warpage and the yellowness was 20 or less.
  • Example 12 A laminate was obtained in the same manner as in Example 46 except that varnish P-24 was used. This laminate was greatly warped, and a part of the polyimide film was cracked.
  • Examples 48 to 53, Comparative Example 13 An organic EL substrate as shown in FIG. 1 was produced.
  • a polyimide precursor varnish (P-1, P-11, P-20, P-22, P-27, P-33, P-45) was placed on a mother glass substrate (thickness 0.7 mm) using a bar coater. After curing, the film was applied so as to have a film thickness of 10 ⁇ m, and then prebaked at 140 ° C. for 60 minutes. Subsequently, using a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B), the oxygen concentration in the chamber was adjusted to 10 ppm by mass or less, and a heat curing treatment at 430 ° C. for 1 hour was performed. And a glass substrate on which a polyimide resin film was formed. Subsequently, a SiN layer was formed to a thickness of 100 nm by a CVD (Chemical Vapor Deposition) method.
  • CVD Chemical Vapor
  • a titanium film was formed by a sputtering method, and then patterning was performed by a photolithography method to form a scanning signal line.
  • a SiN layer having a thickness of 100 nm was formed on the entire glass substrate on which the scanning signal lines were formed by a CVD method. (This is the lower substrate 2a.)
  • an amorphous silicon layer 256 was formed on the lower substrate 2a, dehydrogenation annealing was performed at 430 ° C. for 1 hour, and then an excimer laser was irradiated to form an LTPS layer.
  • a photosensitive acrylic resin was coated on the entire surface of the lower substrate 2a by spin coating, and exposure and development were performed by photolithography to form 258 having a plurality of contact holes 257. Through this contact hole 257, a part of each LTPS 256 was exposed. Next, an ITO film is formed on the entire surface of the lower substrate 2a on which the interlayer insulating film 258 is formed by a sputtering method, exposed and developed by a photolithography method, patterned by an etching method, and paired with each LTPS. Thus, the lower electrode 259 was formed. In each contact hole 257, the lower electrode 252 penetrating the interlayer insulating film 258 and the LTPS 256 were electrically connected.
  • the hole transport layer 253 and the light emitting layer 254 were formed in each space partitioned by the partition 251.
  • an upper electrode 255 was formed so as to cover the light emitting layer 254 and the partition 251.
  • the organic EL substrate 25 was produced by the above process.
  • a UV curable resin is coated around the sealing substrate 2b on which the glass substrate, the polyimide film of the present embodiment, and the SiN layer are formed in this order, and the sealing substrate 2b and the organic EL substrate are bonded in an argon gas atmosphere. By adhering, the organic EL element was enclosed. Thereby, the hollow part 261 was formed between each organic EL element and the sealing substrate 2b.
  • Excimer laser (wavelength: 308 nm, repetition frequency: 300 Hz) was irradiated from the lower substrate 2a side and the sealing substrate 2b side of the laminate thus formed, and peeling was performed with the minimum energy necessary for peeling the entire surface. .
  • substrate curvature after peeling, a lighting test, and the cloudiness evaluation of a laminated body was evaluated.
  • a heat cycle test was also conducted. The results are shown in Table 6.
  • Examples 59 to 63, Comparative Example 15 A polyimide precursor varnish (P-1, P-11, Pb, P-11, which gives an absorbance at 308 nm of 0.6 or more and 2.0 or less when the YI is 20 or less and a film thickness of 0.1 microns is 0.6 or more and 2.0 or less.
  • P-20, P-27, P-33, and P-45 the minimum energy required for laser stripping during the laser stripping described above, and the ash when irradiated with the minimum energy plus 10 mJ / cm 2 ( Ashes) were evaluated. The case where no ash was generated was indicated by ⁇ , the case where ash was slightly observed on the ridge was indicated by ⁇ , and the case where ash was entirely observed was indicated by ⁇ .
  • Table 8 The results are shown in Table 8.
  • the resin film formed from the polyimide precursor of the present invention can be applied to, for example, a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, etc.
  • a semiconductor insulating film for example, a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, etc.
  • an electrode protective film for example, a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, etc.
  • touch panel ITO electrode substrates, etc. Can be suitably used.

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KR20230007328A (ko) 2020-04-16 2023-01-12 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 이미드-아미드산 공중합체 및 그의 제조방법, 바니시, 그리고 폴리이미드 필름
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WO2023190749A1 (ja) * 2022-03-29 2023-10-05 Ｕｂｅ株式会社 フレキシブル配線基板用ポリイミド前駆体組成物、ポリイミドフィルムおよびポリイミド金属積層体
KR20230170677A (ko) 2021-04-16 2023-12-19 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 이미드-아미드산 공중합체 및 그의 제조방법, 바니시, 그리고 폴리이미드 필름
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JP7483480B2 (ja) 2020-04-24 2024-05-15 旭化成株式会社 ポリイミド前駆体、ポリイミド樹脂組成物、並びにポリイミド樹脂フィルム及びその製造方法
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