WO2019065164A1 - Composition de résine de précurseur de polyimide, composition de résine de polyimide, film de résine de polyimide, procédé de production d'un produit stratifié, procédé de production d'un filtre couleur, procédé de production d'un élément cristal liquide, et procédé de production d'un élément el organique - Google Patents

Composition de résine de précurseur de polyimide, composition de résine de polyimide, film de résine de polyimide, procédé de production d'un produit stratifié, procédé de production d'un filtre couleur, procédé de production d'un élément cristal liquide, et procédé de production d'un élément el organique Download PDF

Info

Publication number
WO2019065164A1
WO2019065164A1 PCT/JP2018/033281 JP2018033281W WO2019065164A1 WO 2019065164 A1 WO2019065164 A1 WO 2019065164A1 JP 2018033281 W JP2018033281 W JP 2018033281W WO 2019065164 A1 WO2019065164 A1 WO 2019065164A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyimide precursor
group
film
polyimide
resin composition
Prior art date
Application number
PCT/JP2018/033281
Other languages
English (en)
Japanese (ja)
Inventor
昭典 佐伯
立花　康子
大地 宮崎
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to CN201880061722.4A priority Critical patent/CN111133054B/zh
Priority to KR1020207008170A priority patent/KR20200052303A/ko
Priority to JP2018548158A priority patent/JPWO2019065164A1/ja
Publication of WO2019065164A1 publication Critical patent/WO2019065164A1/fr

Links

Images

Classifications

    • 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
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • 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
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • 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
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • 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
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • 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
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices

Definitions

  • the present invention relates to a polyimide precursor resin composition, a polyimide resin composition, a polyimide resin film, a method of producing a laminate, a method of producing a color filter, a method of producing a liquid crystal element, and a method of producing an organic EL element.
  • Organic films are more flexible, less fragile, and lighter than glass. Recently, by replacing the substrate of the flat panel display with an organic film, the movement to make the display flexible has become active.
  • polyester As a resin used for an organic film, polyester, a polyamide, a polyimide, a polycarbonate, a polyether sulfone, an acryl, an epoxy etc. are mentioned. Among these, polyimide resin is suitable as a display substrate since it is a high heat resistant resin.
  • Patent Document 1 With respect to the problem of improving the transparency of such a polyimide resin, in Patent Document 1 below, the transmittance is obtained by using 2,2-bis (trifluoromethyl) benzidine (hereinafter also referred to as TFMB). And the method of improving the transparency of a color, and also reducing residual stress by introduce
  • TFMB 2,2-bis (trifluoromethyl) benzidine
  • Patent Document 2 discloses a polyimide precursor resin composition which is less in white turbidity and excellent in film productivity by using a non-amide solvent having a low boiling point as a main component.
  • Patent No. 5948545 gazette Patent No. 5862674
  • Patent Document 1 discloses a silicone-containing polyimide precursor resin composition using an NMP single solvent, but since the solubility of the silicone component in NMP is low, white turbidity tends to occur in the solution and the resulting cured film. , There was a problem.
  • Patent Document 2 discloses a silicone-containing polyimide precursor resin composition containing a solvent having a low boiling point as a main solvent, but when a solvent having a low boiling point is used as a main solvent, the coating liquid dries quickly. There is a problem that unevenness is likely to occur when coating is performed, and the coatability is apt to decrease.
  • the present invention has been made in view of the above problems, and a polyimide precursor resin composition having good slit coatability and suppressing white turbidity and residual stress of the obtained polyimide film, and polyimide using the same
  • a resin composition, a polyimide resin film, a method of manufacturing a laminate, a method of manufacturing a color filter, a method of manufacturing a liquid crystal element, and a method of manufacturing an organic EL element are used in view of the above problems, and a polyimide precursor resin composition having good slit coatability and suppressing white turbidity and residual stress of the obtained polyimide film, and polyimide using the same.
  • the polyimide precursor resin composition according to the present invention includes the structure represented by the general formula (1) and the structural unit represented by the general formula (2) It is a polyimide precursor resin composition containing a polyimide precursor (A) and a solvent (B), and as for the said polyimide precursor (A), the quantity of the whole polyimide precursor (A) was 100 mass%.
  • the solvent (B) contains 5 to 30% by mass of the structure represented by the general formula (1), the solvent (B) has an SP value of 7.7 or more and 9.0 or less, and an SP value of One or more solvents (B2) each of which is greater than 9.0 and not more than 12.5 are included.
  • R 1 and R 2 each independently represent a monovalent organic group having 1 to 20 carbon atoms.
  • M represents an integer of 3 to 200.
  • R 3 represents a divalent organic group
  • R 4 represents a tetravalent organic group
  • Y 1 and Y 2 each independently represent a hydrogen atom or a carbon number of 1 to 10. Indicates a monovalent organic group or a monovalent alkylsilyl group having 1 to 10 carbon atoms.
  • the solvent (B) when the solvent (B) is 100% by mass of the total amount of the solvent (B), 5 to 10 of the solvent (B1) It is characterized in that it contains 40% by mass and 60 to 95% by mass of the solvent (B2).
  • the solvent (B) has a vapor pressure of 10 Pa or more at 20 ° C., assuming that the total amount of the solvent (B) is 100 mass%. It is characterized in that it contains 70 to 100% by mass of a solvent having a pressure of 100 Pa or less.
  • the difference in vapor pressure between the solvent having the highest vapor pressure at 20 ° C. and the solvent having the lowest vapor pressure is 100 Pa or less It is characterized by
  • the polyimide precursor (A) is an acid anhydride residue having a fluorene skeleton, and 100 mol% of the polyimide precursor (A). It is characterized by containing 5 mol% or more and 55 mol% or less.
  • the polyimide precursor (A) contains a diamine residue having a diphenyl sulfone group in 100% by mole of the polyimide precursor (A) And 15 mol% or more and less than 60 mol% in total.
  • the polyimide precursor (A) comprises an acid anhydride residue having a diphenyl ether group and a diamine residue having a diphenyl ether group. 30% by mole or more in total in 100% by mole of the polyimide precursor (A).
  • the polyimide precursor resin composition according to the present invention is characterized in that, in the above invention, the polyimide precursor (A) contains a triamine skeleton.
  • the polyimide precursor resin composition according to the present invention is characterized in that, in the above invention, the polyimide precursor (A) contains a tetraamine skeleton.
  • the polyimide precursor resin composition according to the present invention further includes an imidation accelerator in the above invention, and the content of the imidation accelerator is 100 parts by mass of the polyimide precursor (A). And 0.1 to 3 parts by mass.
  • the polyimide resin composition which concerns on this invention is characterized by being obtained by imidating the polyimide precursor resin composition as described in any one of said invention.
  • the polyimide resin film according to the present invention is a polyimide resin film including a structure represented by the general formula (1) used for manufacturing a flexible display substrate, wherein the polyimide resin film is the entire polyimide resin film.
  • the amount is 100% by mass, it contains 5 to 30% by mass of the structure represented by the general formula (1), has a tensile modulus of 1.5 GPa to 3.5 GPa and a haze value of 1% or less It is characterized by
  • R 1 and R 2 each independently represent a monovalent organic group having 1 to 20 carbon atoms.
  • M represents an integer of 3 to 200.
  • the polyimide resin film according to the present invention is a polyimide resin film including a structure represented by the general formula (1) used for manufacturing a flexible display substrate, wherein the polyimide resin film is the entire polyimide resin film.
  • the amount is 100% by mass, it contains 5 to 30% by mass of the structure represented by the general formula (1), the haze value is 1% or less, and the glass transition point is 380 ° C. or more. I assume.
  • R 1 and R 2 each independently represent a monovalent organic group having 1 to 20 carbon atoms.
  • M represents an integer of 3 to 200.
  • the manufacturing method of the laminated body which concerns on this invention is the application process of apply
  • the said applied polyimide precursor The step of removing the solvent from the resin composition, the step of imidating the polyimide precursor resin composition from which the solvent has been removed, and the step of forming a polyimide resin film to obtain a film-like product of the polyimide resin composition And a step of forming an inorganic film on the film-like material of the polyimide resin composition.
  • a supporting electrode, an alignment film and a liquid crystal layer are formed on a laminate manufactured by the method of manufacturing a laminate according to the above invention, and the support And a peeling step of peeling the laminate from the substrate.
  • paintability in a slit is favorable and can provide the polyimide precursor resin composition which can suppress the cloudiness of the polyimide resin film obtained, and a residual stress.
  • the polyimide resin composition obtained from the polyimide precursor resin composition of the present invention can be suitably used as a support substrate for displays such as electronic devices, for example, touch panels, color filters, liquid crystal elements, organic EL elements and the like. By using such a support substrate, it is possible to produce a display with high definition and high reliability.
  • FIG. 1A is a plan view showing a configuration example of a touch panel including a polyimide resin film according to an embodiment of the present invention.
  • FIG. 1B is a cross-sectional view of the touch panel shown in FIG. 1A, taken along line I-I '.
  • FIG. 2 is a cross-sectional view showing a configuration example of a color filter including the laminate according to the embodiment of the present invention.
  • FIG. 3 is a cross-sectional view showing a configuration example of a liquid crystal element including the laminate according to the embodiment of the present invention.
  • FIG. 4: is sectional drawing which shows one structural example of the organic EL element containing the laminated body which concerns on embodiment of this invention.
  • FIG. 5 is a plan view for illustrating preparation of a polyimide resin film and evaluation of coating properties in Examples.
  • FIG. 6 is a schematic perspective view showing a state before bending when evaluating the bending resistance of the laminate.
  • FIG. 7 is a schematic perspective view showing a bent state when the bending resistance of the laminate is evaluated.
  • a polyimide precursor resin composition according to an embodiment of the present invention comprises a polyimide precursor (A) comprising a structure represented by the general formula (1) and a structural unit represented by the general formula (2); And B).
  • the polyimide precursor (A) contains 5 to 30% by mass of the structure represented by the general formula (1), where the total amount of the polyimide precursor (A) is 100% by mass.
  • the solvent (B) is a solvent (B1) having an SP value of not less than 7.7 and not more than 9.0, and a solvent (B2) having an SP value of not less than 9.0 and not more than 12.5. It includes the above.
  • R 1 and R 2 each independently represent a monovalent organic group having 1 to 20 carbon atoms.
  • m represents an integer of 3 to 200.
  • R 3 represents a divalent organic group
  • R 4 represents a tetravalent organic group
  • Y 1 and Y 2 each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbon atoms, or a monovalent alkylsilyl group having 1 to 10 carbon atoms.
  • C1 to C10 indicates “C1 or more and C10 or less”. Similar descriptions in the present invention indicate similar meanings.
  • the polyimide precursor resin composition of the present invention comprises the above-mentioned polyimide precursor (A) and a solvent (B) having an SP value in a preferred range, for example, two or more solvents (B1) having an SP value in each preferred range, By including (B2), the slit coatability is good. Furthermore, the polyimide resin composition obtained by imidization has a high glass transition temperature, less occurrence of warpage and cloudiness, and is excellent in mechanical strength.
  • the polyimide precursor (A) according to the embodiment of the present invention has a structure represented by the general formula (1) in at least one of an acid dianhydride residue and a diamine residue constituting the polyimide. Resin. Moreover, a polyimide precursor (A) has a structural unit represented by General formula (2). Since a part of the structural unit represented by the general formula (2) includes the flexible structure represented by the general formula (1), a rigid skeleton part (a part not having the structure represented by the general formula (1) ) Is considered to form a microstratified structure in which the flexible skeletal part becomes an island part. As a result, it is possible to efficiently absorb the stress generated in the film forming process at the flexible framework portion, to obtain a film in which the residual stress is small and the occurrence of warpage is suppressed.
  • Examples of the monovalent organic group having 1 to 20 carbon atoms as R 1 and R 2 include a hydrocarbon group, an amino group, an alkoxy group, an epoxy group and the like.
  • Examples of the hydrocarbon group in R 1 and R 2 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, and specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t- A butyl group, a pentyl group, a hexyl group etc. are mentioned.
  • the cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms, and specific examples thereof include a cyclopentyl group and a cyclohexyl group.
  • the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group and a naphthyl group.
  • Examples of the alkoxy group in R 1 and R 2 include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group and a cyclohexyloxy group.
  • R 1 and R 2 in the general formula (1) are preferably monovalent aliphatic hydrocarbon groups having 1 to 3 carbon atoms or aromatic groups having 6 to 10 carbon atoms.
  • the reason is that the resulting polyimide film has high heat resistance and low residual stress.
  • the monovalent aliphatic hydrocarbon having 1 to 3 carbon atoms is preferably a methyl group
  • the aromatic group having 6 to 10 carbon atoms is preferably a phenyl group.
  • At least one of R 1 and R 2 in the general formula (1) contains an aromatic group.
  • the island portion composed of a flexible skeletal portion is excellent in affinity with the sea portion composed of a rigid skeletal portion, and microlayer separation easily occurs at a size of about 1 nm to 1 ⁇ m.
  • the skeletal portion including the above-mentioned structural unit in the structure represented by the general formula (1) can be microlayer-separated and has a low residual stress and the like, a film excellent in transparency and difficult to be clouded You can get
  • the structure represented by the general formula (1) when the total amount of the polyimide precursor (A) is 100% by mass, the structure represented by the general formula (1) is 5 to 30% by mass included.
  • the structure represented by the general formula (1) is preferably contained in an amount of 6 to 23% by mass, more preferably 8 to 22% by mass, and still more preferably 10 to 21% by mass.
  • M (that is, the degree of polymerization m) in the general formula (1) is an integer of 3 to 200.
  • the degree of polymerization m is preferably an integer of 10 to 200, more preferably an integer of 20 to 150, still more preferably an integer of 30 to 100, and particularly preferably an integer of 30 to 60.
  • the polymerization degree m is in the above range, the residual stress of the polyimide can be reduced. Moreover, it can suppress that a polyimide film becomes cloudy and the mechanical strength of a polyimide film falls.
  • the polyimide precursor (A) containing the structure represented by General formula (1) is obtained by using the silicone compound represented by following General formula (3) as a monomer component.
  • a plurality of R 5 s are each independently a single bond or a divalent organic group having 1 to 20 carbon atoms.
  • Each of R 6 , R 7 and R 8 is independently a monovalent organic group having 1 to 20 carbon atoms.
  • L 1 , L 2 and L 3 are each independently one group selected from the group consisting of an amino group, an acid anhydride group, a carboxyl group, a hydroxy group, an epoxy group, a mercapto group and R 9 .
  • R 9 is a monovalent organic group having 1 to 20 carbon atoms.
  • n is an integer of 3 to 200
  • o is an integer of 0 to 197.
  • examples of the divalent organic group having 1 to 20 carbon atoms for R 5 include an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. And the like.
  • the alkylene group having 1 to 20 carbon atoms is preferably an alkylene group having 1 to 10 carbon atoms, and examples thereof include methylene group, dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group and the like.
  • the cycloalkylene group having 3 to 20 carbon atoms is preferably a cycloalkylene group having 3 to 10 carbon atoms, and examples thereof include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group and a cycloheptylene group.
  • the arylene group having 6 to 20 carbon atoms is preferably an aromatic group having 3 to 20 carbon atoms, and examples thereof include a phenylene group and a naphthylene group.
  • divalent aliphatic hydrocarbons having 3 to 20 carbon atoms are preferable as the divalent organic groups having 1 to 20 carbon atoms in R 5 .
  • Preferred specific examples of each group in R 6 to R 8 include the same as those in R 1 and R 2 in the structure represented by the above general formula (1).
  • the amino group in L 1 , L 2 and L 3 includes not only the amino group itself but also its reactive derivative.
  • a reactive derivative of the amino group an isocyanate group, a bis (trialkylsilyl) amino group and the like can be mentioned.
  • the acid anhydride group in L 1 , L 2 and L 3 includes not only the acid anhydride group itself but also reactive derivatives thereof.
  • a reactive derivative of the acid anhydride group an acid ester of a carboxyl group, an acid chloride of the carboxyl group and the like can be mentioned.
  • Specific examples in which L 1 , L 2 and L 3 are acid anhydride groups include groups represented by the following formulae, and the like.
  • the degree of polymerization m can be calculated, for example, by the following equation. However, both ends is an amino propyl group, and, when all the general formula (3) in R 5 satisfies a condition that a compound has a methyl group or a phenyl group, this equation holds.
  • m (number average molecular weight-molecular weight of both terminal groups (aminopropyl group)) / (74.15 x mol% of methyl group x 0.01 + 198.29 x mol% of phenyl group x 0.01)
  • the molecular weight of the aminopropyl group is 116.2.
  • L 1, L 2 and L 3 is an acid anhydride group
  • specific examples of the compound represented by the general formula (3) X22-168AS (Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,000)
  • X22-168A (Shin-Etsu Chemical Co., Ltd., number average molecular weight 2,000)
  • X22-168 B (Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,200)
  • X22-168-P5-B Shin-Etsu Chemical Co., Ltd., number average Molecular weight: 4,200
  • Specific examples of the compound represented by the general formula (3) when L 1 , L 2 and L 3 are hydroxy groups include KF-6000 (Shin-Etsu Chemical, number average molecular weight 900), KF-6001 (Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,800), KF-6002 (Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,200), KF-6003 (Shin-Etsu Chemical Co., Ltd., number average molecular weight 5,000), etc.
  • Be The compound having a hydroxy group is considered to react with other tetracarboxylic acid dianhydride monomers.
  • a specific example of the compound represented by General Formula (3) when L 1 , L 2 and L 3 are epoxy groups is X22-163 (Shin-Etsu Chemical Co., Ltd., number average) which is an epoxy type having both ends Molecular weight 400), KF-105 (Shin-Etsu Chemical Co., number average molecular weight 980), X22-163A (Shin-Etsu Chemical Co., number average molecular weight 2,000), X22-163 B (Shin-Etsu Chemical Co., number average molecular weight 3, 500), X22-163C (Shin-Etsu Chemical Co., Ltd., number average molecular weight 5,400), both-end alicyclic epoxy type, X22-169AS (Shin-Etsu Chemical Co., number average molecular weight 1,000), X22-169 B (Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,400) and the like.
  • the compound having the epoxy group is considered to react with other
  • L 1 , L 2 and L 3 are mercapto groups
  • X22-167B Shin-Etsu Chemical, number average molecular weight 3,400
  • X22 And -167C Shin-Etsu Chemical Co., Ltd., number average molecular weight 4,600.
  • the compound having a mercapto group is considered to react with other tetracarboxylic acid dianhydride monomers.
  • L 1 , L 2 and L 3 each independently comprise an amino group, an acid anhydride group, and R 9 from the viewpoint of improving the molecular weight of the polyimide precursor (A) or the heat resistance of the resulting polyimide It is preferable that it is one group selected from the group. Furthermore, L 1 , L 2 and L 3 are each independently an amino group from the viewpoint of avoiding white turbidity of the varnish consisting of the polyimide precursor (A) and the solvent (B), or from the viewpoint of cost Is more preferred.
  • Examples of the monovalent organic group having 1 to 10 carbon atoms as Y 1 and Y 2 in the general formula (2) include monovalent hydrocarbon groups having 1 to 10 carbon atoms.
  • Examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkyl group having 1 to 10 carbon atoms.
  • alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group and hexyl group.
  • alkylsilyl group having 1 to 10 carbon atoms examples include monovalent silyl groups in which an alkyl group having 1 to 10 carbon atoms is bonded. Specific examples of the alkylsilyl group having 1 to 10 carbon atoms include a trimethylsilyl group and a triethylsilyl group.
  • the polyimide obtained from a polyimide precursor (A) has a rigid frame
  • part is a sea part
  • the flexible skeletal portion forms a microphase separation structure in which the island portion is formed. It is believed that the formation of this microphase-separated structure by polyimide results in a film with reduced residual stress.
  • microphase separation means that island portions consisting of a flexible skeletal portion are dispersed in a size of about 1 nm to 1 ⁇ m in a sea portion consisting of a rigid skeletal portion.
  • warping refers to the degree of rounding of the film which is judged visually.
  • residual stress refers to the stress remaining inside the film after the resin composition is applied onto a substrate such as a glass substrate to form a film, and is a measure of "warpage” that may occur in the film. . Specifically, it can be measured by the method described in the following examples.
  • a divalent organic group having 1 to 40 carbon atoms is preferable.
  • a divalent aromatic hydrocarbon group having 6 to 40 carbon atoms or an alicyclic hydrocarbon group is preferable, and from the viewpoint of heat resistance, an aromatic hydrocarbon group is preferable. More preferable.
  • the organic group contains two or more ring structures, it is a polycyclic structure in which the rings share one or more bonds, a spiro hydrocarbon structure, and a linking group such as a ring and a ring such as biphenyl as in biphenyl And the like.
  • the bonding group in addition to a single bond, an ether bond, a thioether group, a ketone group, an ester bond, a sulfonyl group, an alkylene group, an amide group, a siloxane group and the like can be mentioned.
  • the divalent organic group contains a hydrogen atom, any hydrogen atom may be substituted with a halogen atom.
  • Examples of the divalent organic group having 1 to 40 carbon atoms include aromatic diamine compounds, alicyclic diamine compounds, and aliphatic diamine compounds.
  • the aromatic diamine compound is not particularly limited, but 1,4-bis (4-aminophenoxy) benzene, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine Bis (4- (4-aminophenoxyphenyl)) sulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, bis ⁇ 4- (3-aminophenoxyphenyl) ⁇ sulfone, bis (4 -Aminophenoxy) biphenyl, bis ⁇ 4- (4-aminophenoxy) phenyl ⁇ ether, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropro , 3-amin
  • the alicyclic diamine compound is not particularly limited, and cyclobutanediamine, isophoronediamine, bicyclo [2.2.1] heptanebismethylamine, tricyclo [3.3.1.13,7] decane-1,3-, Diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, 4,4′-diaminodicyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 3, 3'-diethyl-4,4'-diaminodicyclohexylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 3,3', 5,5'-tetraethyl-4, 4'-Diaminodicyclohexylmethane, 3,5-diethy
  • the aliphatic diamine compound is not particularly limited, and ethylene diamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1 Alkylene diamines such as 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, etc.
  • Ethylene glycol diamines and 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, ⁇ , ⁇ -bis (3-aminopropyl) poly Examples include siloxane diamines such as dimethylsiloxane.
  • aromatic diamine compounds alicyclic diamine compounds, or aliphatic diamine compounds can be used alone or in combination of two or more.
  • the divalent organic group more preferably includes a group selected from the group of compounds represented by the following chemical formulas (4) to (6), and is represented by the following chemical formulas (4) to (6) More preferably, it is a group selected from the group of compounds.
  • the divalent organic group in R 3 is a group selected from the group of compounds represented by the following chemical formulas (4) to (6)
  • the sea part has a structure having a more rigid skeleton. Therefore, it is preferable because a film having a small residual stress and in which the occurrence of warpage is suppressed can be obtained.
  • each R 10 independently represents at least one bond selected from the group consisting of an ether bond, a sulfide bond, a ketone bond, an ester bond, a sulfonyl bond, an amide bond and a siloxane bond It is a containing group.
  • R 10 represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, a nitro group, a cyano group or a sulfonyl group. Any hydrogen atom of this alkyl group may be substituted by a halogen atom.
  • X 1 is a direct bond or an oxygen atom, a sulfur atom, a sulfonyl group, or a divalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom.
  • X 1 is a divalent cross-linked structure selected from the group consisting of an ester bond, an amide bond and a sulfide bond.
  • a 1 represents an integer of 1 to 3;
  • a 2 represents 1 or 2;
  • a 3 represents an integer of 0 to 4 independently.
  • e represents an integer of 0 to 3.
  • Examples of the group containing one or more bonds selected from the group consisting of ether bond, sulfide bond, ketone bond, ester bond, sulfonyl bond, amide bond and siloxane bond include, for example, ether bond, sulfide bond, ketone bond, ester bond And an organic group having 1 to 10 carbon atoms containing a sulfonyl bond, an amido group or a siloxane group.
  • R 10 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group, more preferably a methyl group or a trifluoromethyl group.
  • R 10 is a methyl group, it is possible to reduce the residual stress and to increase the elastic modulus of the resulting polyimide resin composition.
  • R 10 is a trifluoromethyl group, it is possible to increase the transparency of the resulting film.
  • X 1 is preferably a direct bond or a sulfonyl group.
  • X 1 is a direct bond or a sulfonyl group, it is possible to improve the glass transition point (Tg) of the resulting polyimide resin composition.
  • e is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
  • a 1 is preferably 1 or 3.
  • a 2 is preferably 2.
  • a 3 is preferably an integer of 0 to 2, more preferably 0 or 1.
  • the divalent organic group for R 3 is preferably a group selected from the group of compounds represented by the following chemical formulas (7) to (10).
  • R 10 is the above-mentioned formula (4) has the same meaning as R 10 in (5).
  • the divalent organic group for R 3 is more preferably a group selected from the group of compounds represented by the following chemical formulas (11) to (14).
  • the tetravalent organic group for R 4 is preferably a tetravalent organic group having 1 to 40 carbon atoms.
  • the tetravalent organic group having 1 to 40 carbon atoms is preferably a tetravalent alicyclic hydrocarbon group having 3 to 40 carbon atoms or a tetravalent aromatic hydrocarbon group having 6 to 40 carbon atoms.
  • the organic group contains two or more ring structures, it is a polycyclic structure in which the rings share one or more bonds, a spiro hydrocarbon structure, and a bond such as a single bond between a ring and a ring like biphenyl. It includes a group-bonded structure and the like.
  • an ether bond, a thioether group, a ketone group, an ester bond, a sulfonyl group, an alkylene group, an amide group, a siloxane group etc. are mentioned other than the said single bond.
  • aromatic acid dianhydride, alicyclic acid dianhydride, or aliphatic acid dianhydride is mentioned.
  • the aromatic acid dianhydride is not particularly limited, and is, for example, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) propane dianhydride, 2,2-bis (3- (3 2,4-dicarboxyphenoxy) phenyl) propane dianhydride, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2,2-bis (3- (3 (3) 2,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4 ′ -Biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-terphenyltetracar
  • 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4- Cyclopentanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cycloheptane tetracarboxylic acid dianhydride, 2,3 1,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 2,3,5-tricarboxycycl
  • aliphatic acid dianhydrides include, but are not limited to, 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-pentanetetracarboxylic acid dianhydride and derivatives thereof Can be mentioned.
  • these other acid dianhydrides can be used individually or in combination of 2 or more types.
  • R 4 in the above general formula (2) a group selected from the group of compounds represented by the following chemical formulas (15) to (21) is more preferable.
  • each R 11 independently represents one or more bonds selected from the group consisting of ether bonds, sulfide bonds, ketone bonds, ester bonds, sulfonyl bonds, amide bonds and siloxane bonds. It is a containing group.
  • R 11 represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, a nitro group, a cyano group or a sulfonyl group, and any hydrogen atom of the alkyl group may be a halogenated alkyl group substituted by a halogen atom.
  • X 1 is a direct bond or an oxygen atom, a sulfur atom, a sulfonyl group, or a divalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom.
  • X 1 is a divalent cross-linked structure selected from the group consisting of an ester bond, an amide bond and a sulfide bond.
  • each b independently represents 1 or 2;
  • c each independently represents an integer of 1 to 3;
  • f represents an integer of 0 to 3;
  • Examples of the group containing one or more bonds selected from the group consisting of ether bond, sulfide bond, ketone bond, ester bond, sulfonyl bond, amide bond and siloxane bond include, for example, ether bond, sulfide bond, ketone bond, ester bond And an organic group having 1 to 10 carbon atoms containing a sulfonyl bond, an amido group or a siloxane group.
  • examples of the halogenated alkyl group for R 11 include a methyl group substituted by a halogen atom and an alkyl group having 2 to 20 carbon atoms.
  • the halogenated alkyl group having 2 to 20 carbon atoms is preferably an alkyl group having 2 to 10 carbon atoms which is substituted by a halogen atom.
  • any hydrogen atom of ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group and hexyl group is a fluorine atom, chlorine atom, bromine
  • Examples thereof include an atom or a group substituted with an iodine atom.
  • the halogenated alkyl group for R 11 is preferably an alkyl group having 1 to 2 carbon atoms substituted with a halogen atom, and specifically, a methyl group or an ethyl group And groups in which any hydrogen atom is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • the halogen atom in R 11 and the halogen atom contained in the halogenated alkyl group are fluorine atoms because they can obtain a film having excellent mechanical strength and good transparency. Is preferred.
  • R 11 not containing a halogen atom a hydrogen atom, an alkyl group, a fluorene group, a hydroxy group, a nitro group, a cyano group or a sulfo group is preferable, and a hydrogen atom or an alkyl group is preferable.
  • the alkyl group for R 11 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms.
  • examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group and a hexyl group.
  • the group selected from the group of compounds represented by the chemical formulas (15) to (21) is preferably a group selected from the group of compounds represented by the following chemical formulas (22) to (25).
  • the group represented by the chemical formula (22) is contained, it is possible to reduce the cloudiness of the obtained polyimide resin, to improve the transparency, and to reduce the residual stress.
  • the group represented by the chemical formula (23) is contained, the resulting polyimide resin has a rigid skeleton, so that mechanical strength can be improved (elastic modulus can be improved) and Tg can be improved.
  • the group represented by the chemical formula (24) is included, it is possible to reduce the cloudiness of the polyimide resin and to reduce the in-plane / out-plane birefringence.
  • the Tg can be improved.
  • the group represented by the chemical formula (24) it is particularly preferable because the characteristics of high Tg, low birefringence, and high transparency can be exhibited thereby.
  • a group exemplified in the structure of the chemical formula (24), that is, an acid anhydride residue having a fluorene skeleton is a polyimide precursor It is preferable to contain 5 mol% or more and 55 mol% or less in 100 mol% of a body (A), and it is still more preferable to contain 10 mol% or more and 35 mol% or less.
  • R 3 is a group selected from the group of compounds represented by chemical formulas (4) to (6), in particular, selected from the group of compounds represented by chemical formulas (7) to (10)
  • R 4 is a group selected from the group of compounds represented by chemical formulas (15) to (21), particularly a group selected from the group of compounds represented by chemical formulas (22) to (25)
  • m in the general formula (1) is 3 or more, the polyimide obtained from the polyimide precursor (A) is more likely to have a microphase separation structure, so that the residual stress of the obtained film can be reduced. Particularly preferred is
  • the polyimide precursor (A) preferably contains a triamine skeleton.
  • Triamine has three amino groups, and forms a branched molecular chain by combining with three tetracarboxylic acid dianhydride components.
  • the triamine skeleton introduces a branched structure into the molecular chain of polyamic acid to form a branched polyamic acid.
  • the molecular weight of the polyimide resin obtained from the polyimide precursor (A) having a branched structure is larger than that of the polyimide resin without the branched structure, the cluster effect improves the interaction with the inorganic film formed on the polyimide resin. It is possible to
  • triamine compounds those having no aliphatic group include 2,4,4'-triaminodiphenyl ether (TAPE), 1,3,5-tris (4-aminophenoxy) benzene (1,3,3, 5-TAPOB), 1,2,3-tris (4-aminophenoxy) benzene (1,2,3-TAPOB), tris (4-aminophenyl) amine, 1,3,5-tris (4-aminophenyl) ) Benzene, 3,4,4'-triaminodiphenyl ether, etc. can be mentioned, and as those having aliphatic groups, tris (2-aminoethyl) amine (TAEA), tris (3-aminopropyl) amine Etc. can be mentioned.
  • TAEA 2,4,4'-triaminodiphenyl ether
  • TAEA 2,4,4'-triaminoethyl) amine
  • TAEA tris (3-aminopropyl) amine Etc.
  • triamines constitute branches of the cross-linked structure in the molecular chains of the polyimide resin.
  • the triamine component it is preferable to use a component which does not have an aliphatic group and is difficult to be thermally decomposed. That is, 2,4,4'-triaminodiphenyl ether (TAPE), 1,3,5-tris (4-aminophenoxy) benzene (1,3,5-TAPOB), 1,2,3-tris (4- It is preferable to use aminophenoxy) benzene (1,2,3-TAPOB) or the like.
  • TAPE 2,4,4'-triaminodiphenyl ether
  • 1,3,5-tris (4-aminophenoxy) benzene 1,3,5-TAPOB
  • 1,2,3-tris 4,2,3-tris (4- It is preferable to use aminophenoxy) benzene (1,2,3-TAPOB) or the like.
  • the polyimide precursor (A) preferably contains a tetraamine skeleton.
  • Tetraamine has four amino groups, and forms a branched molecular chain by combining with four tetracarboxylic acid dianhydride components.
  • the tetraamine skeleton introduces a branched structure into the molecular chain of polyamic acid to form a branched polyamic acid.
  • the molecular weight of the polyimide resin obtained from the polyimide precursor (A) having a branched structure is larger than that of the polyimide resin without the branched structure, the cluster effect improves the interaction with the inorganic film formed on the polyimide resin. It is possible to Furthermore, Tg of a polyimide resin composition can be improved by using tetraamine. It is known that highly heat-resistant benzimidazole can be obtained by reacting dicarboxylic acid and tetraamine, but some benzimidazole is formed also when tetracarboxylic acid dianhydride and tetraamine are reacted. It is considered to be
  • tetraamine compounds include 1,2,4,5-tetraaminobenzene, 3,3 ', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl sulfone, 3, 3 ', 4,4'-tetraaminodiphenyl ether, 3,3', 4,4'-tetraaminodiphenyl sulfide, 2,3,6,7-tetraaminonaphthalene, 1,2,5,6-tetraaminonaphthalene And the like.
  • tetraamine compound a compound in which a part of hydrogen bonded to an aromatic ring contained in these polyhydric amine compounds or diamine compounds is substituted with a hydrocarbon or a halogen can be mentioned.
  • the tetraamine component like the above triamine, it is preferable to use a component which does not have an aliphatic group and is difficult to be thermally decomposed, and further, to improve transparency, it has an electron withdrawing group preferable. That is, it is preferable to use 3,3 ', 4,4'-tetraaminodiphenyl sulfone or the like.
  • the electron withdrawing group has a Hammett's substituent constant (para position, ⁇ p) of usually greater than 0, preferably 0.01 or more, and more preferably 0.1 or more. It is particularly preferable to be 0.5 or more.
  • the Hammett's substituent constant is described, for example, in "Chemical Handbook", Rev. 5th Edition, Volume II, Maruzen Co., Ltd., February 2004, p. 380, edited by The Chemical Society of Japan.
  • Examples of the electron withdrawing group include a halogen atom, a cyano group, a hydrogen atom or a substituted carbonyl group, a nitro group, a perfluoroalkyl group such as a trifluoromethyl group, a sulfonyl group, and the like.
  • the halogen atom includes a fluorine atom, a bromine atom, a chlorine atom and an iodine atom.
  • the polyimide precursor (A) preferably has a diphenyl ether group. As a result, it is possible to suppress the deterioration of the haze of the cured film due to the layer separation.
  • the polyimide precursor (A) has a total of 30 acid anhydride residues having a diphenyl ether group and diamine residues or triamine residues having a diphenyl ether group in 100 mol% of the polyimide precursor (A). It is preferable to contain mol% or more, and it is more preferable to contain 40 mol% or more.
  • anhydride containing a diphenyl ether group for example, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) propane dianhydride, 2,2-bis (3- (3,4-diethyl) Carboxyphenoxy) phenyl) propane dianhydride, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2,2-bis (3- (3,4-di) Carboxyphenoxy) phenyl) hexafluoropropane dianhydride, 4,4′-oxydiphthalic dianhydride, 3,4′-oxydiphthalic dianhydride, 3,3′-oxydiphthalic dianhydride.
  • diamine containing a diphenyl ether group for example, 1,4-bis (4-aminophenoxy) benzene, bis ⁇ 4- (4-aminophenoxyphenyl) ⁇ sulfone, bis ⁇ 4- (3-aminophenoxyphenyl) ⁇ sulfone Bis (4-aminophenoxy) biphenyl, bis ⁇ 4- (4-aminophenoxy) phenyl ⁇ ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3 ' -Diamino diphenyl ether is mentioned.
  • triamines containing a diphenyl ether group examples include 2,4,4′-triaminodiphenyl ether (TAPE), 1,3,5-tris (4-aminophenoxy) benzene (1,3,5-TAPOB), Examples include 2,3-tris (4-aminophenoxy) benzene (1,2,3-TAPOB), 3,4,4'-triaminodiphenyl ether.
  • TAPE 2,4,4′-triaminodiphenyl ether
  • 1,3,5-tris (4-aminophenoxy) benzene 1,3,5-tris (4-aminophenoxy) benzene
  • 2,3-tris (4-aminophenoxy) benzene 1,2,3-TAPOB
  • 3,4,4'-triaminodiphenyl ether examples include 2,3-tris (4-aminophenoxy) benzene (1,2,3-TAPOB), 3,4,4'-triaminodiphenyl ether.
  • the polyimide precursor (A) preferably has a diphenyl sulfone group. Thereby, the Tg of the polyimide resin can be improved, and the birefringence can be further reduced.
  • the polyimide precursor (A) comprises an acid anhydride residue having a diphenyl sulfone group, a diamine residue having a diphenyl sulfone group, a triamine residue or a tetraamine residue, and 100 moles of the polyimide precursor (A). In%, the total content is preferably 15% by mole to 60% by mole, and more preferably 20% by mole to 50% by mole.
  • the polyimide precursor (A) can improve the Tg of the cured film, reduce the haze value, and further reduce the birefringence and increase the elastic modulus of the cured film. Can improve flexibility.
  • diphenyl sulfone-3,3 ′, 4,4′-tetracarboxylic acid dianhydride DSDA
  • diphenyl sulfone-2,3,3 ′, 4′-tetra Carboxylic acid dianhydride diphenyl sulfone-2,2 ′, 3 ′, 3′-tetracarboxylic acid dianhydride
  • Examples of the diamine containing a diphenyl sulfone group include bis ⁇ 4- (4-aminophenoxyphenyl) ⁇ sulfone, bis ⁇ 4- (3-aminophenoxyphenyl) ⁇ sulfone, 4,4'-diaminodiphenyl sulfone, and 3, And 3'-diaminodiphenyl sulfone.
  • Examples of tetraamines containing a diphenyl sulfone group include 3,3 ', 4,4'-tetraaminodiphenyl sulfone.
  • part of the structural unit represented by the general formula (2) may be imidized.
  • the viscosity stability of the resin solution when stored at room temperature can be improved.
  • the range of the imidation ratio of the polyimide precursor (A) is preferably 1% to 50% from the viewpoint of solubility in solution and viscosity stability.
  • polyimide precursor (A) for example, a resin having a repeating unit represented by the general formula (26), the general formula (27) and the general formula (28) can be mentioned.
  • R 12 represents a divalent organic group
  • R 13 represents a tetravalent organic group
  • W 1 and W 2 each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbon atoms, or a monovalent alkylsilyl group having 1 to 10 carbon atoms.
  • the number of repeating units represented by the general formula (26), the general formula (27) and the general formula (28) in the polyimide precursor (A) is p, q, r, respectively.
  • p represents an integer of 1 or more.
  • Each of q and r independently represents an integer of 0 or 1 or more.
  • p, q and r preferably satisfy the relationship of 1% ⁇ (2r + q) ⁇ 100 / (2p + 2q + 2r) ⁇ 50%.
  • p, q and r satisfy the relationship of 1% ⁇ (2r + q) ⁇ 100 / (2p + 2q + 2r) ⁇ 50%, but the relationship of 2% ⁇ (2r + q) ⁇ 100 / (2p + 2q + 2r) ⁇ 30% is more preferable desirable.
  • (2r + q) x 100 / (2p + 2q + 2r) is the number of the bond part which is imide ring closed (2r + q) in the bond part of the specific polyimide precursor (the reaction part of tetracarboxylic acid dianhydride and diamine compound).
  • the ratio to the total number of coupled parts (2p + 2q + 2r) is shown. That is, “(2r + q) ⁇ 100 / (2p + 2q + 2r)” indicates the imidation ratio of the specific polyimide precursor.
  • the polyimide precursor (A) is prepared by setting the imidization ratio (value of “(2r + q) ⁇ 100 / (2p + 2q + 2r)”) of the polyimide precursor (A) to 1 to 50%, more preferably 2 to 30%.
  • the viscosity stability can be improved without deteriorating the solubility of the solution in the solution).
  • the imidation ratio (value of “(2r + q) ⁇ 100 / (2p + 2q + 2r)”) of the polyimide precursor (A) is measured by the following method.
  • a sample of the polyimide precursor (A) is produced. Specifically, in the first step, the composition of the polyimide precursor (A) to be measured is applied on a silicon wafer in a film thickness of 1 ⁇ m to 10 ⁇ m to prepare a coating film sample.
  • the coating sample is immersed in tetrahydrofuran (THF) for 20 minutes to replace the solvent in the coating sample with tetrahydrofuran (THF).
  • the solvent to be immersed is not limited to THF, and can be selected from solvents which do not dissolve the polyimide precursor (A) and which are miscible with solvent components contained in the composition of the polyimide precursor (A). Specifically, alcohol solvents such as methanol and ethanol, and ether compounds such as dioxane can be used.
  • the coating film sample is taken out of THF, and the THF adhering to the surface of the coating film sample is sprayed with N 2 gas and removed.
  • the coated film sample is dried under a reduced pressure of 10 mmHg or less at a temperature of 5 ° C. to 25 ° C. for 12 hours or more, and a sample of the polyimide precursor (A) (hereinafter abbreviated as a polyimide precursor sample as appropriate) Make.
  • a 100% imidized standard sample is prepared.
  • the composition of the polyimide precursor (A) to be measured is applied onto a silicon wafer, as in the first step. Make a coating sample.
  • the coating film sample is heated at 380 ° C. for 60 minutes to carry out imidation reaction to prepare a 100% imidation standard sample.
  • the aromatic ring derived absorption peak near 1500cm -1 (Ab (1500cm -1) ), 1780cm -
  • the ratio I (x) of absorbance peaks (Ab (1780 cm ⁇ 1 )) derived from imide bond in the vicinity of 1 is determined.
  • the imidation ratio of the polyimide precursor (A) is calculated based on the following first to third formulas.
  • Imidation ratio of polyimide precursor (%) I (x) ⁇ 100 / I ′ (100)
  • Second equation: I '(100) (Ab' (1780 cm- 1 )) / (Ab '(1500 cm- 1 ))
  • Third equation: I (x) (Ab (1780 cm -1 )) / (Ab (1500 cm -1 ))
  • the weight average molecular weight (Mw) of the polyimide precursor (A) is preferably 10,000 to 1,000,000, more preferably 10,000 to 500,000, and still more preferably 20,000 to 400. , 000.
  • the number average molecular weight (Mn) of the polyimide precursor (A) is 5,000 to 1,000,000, preferably 5,000 to 500,000, and particularly preferably 15,000 to 300,000. is there.
  • the weight average molecular weight and the number average molecular weight of the polyimide precursor (A) are in the above ranges, it is possible to increase the strength of the film obtained after curing without deteriorating the flatness of the obtained film.
  • weight average molecular weight, number average molecular weight and molecular weight distribution DP-8020 GPC apparatus made by TOSOH (guard column: TSK guard colomn ALPHA column: TSK-GEL ⁇ -M, developing solvent: N, N'-dimethylacetamide ( It is the value measured using DMAc), 0.05 M LiCl, 0.05% phosphoric acid addition).
  • the polyimide precursor (A) may be end-capped with an end-capping agent in order to adjust the molecular weight to a preferred range.
  • the end capping agent that reacts with the acid dianhydride in the polyimide precursor (A) include monoamines and monohydric alcohols.
  • an acid anhydride, a monocarboxylic acid, a mono-acid chloride compound, a monoactive ester compound, a carbonic acid ester, vinyl ether etc. are mentioned.
  • various organic groups can be introduced as end groups by reacting an end capping agent.
  • 5-amino-8-hydroxyquinoline As a monoamine used for the blocking agent of an acid anhydride group terminal, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-amino naphthalene, 1-hydroxy-7-amino Examples include, but are not limited to, naphthalene, 1-hydroxy-6-aminonaphthalene and the like.
  • the monohydric alcohol used as a capping agent for the terminal of the acid anhydride group is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3 -Pentanol, 1-hexanol, 2-hexanol, 3-hexanol and the like, but not limited thereto.
  • Examples of acid anhydrides, monocarboxylic acids, monoacid chloride compounds and monoactive ester compounds used as capping agents at the end of amino group include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic acid anhydride, 2--2- Monocarboxylic acids such as carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, and monoacid chloride compounds in which the carboxyl group is acid-chlorided, and terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid Acid, a monoacid chloride compound in which only a monocarboxyl group of a dicarboxylic acid such as 3-hydroxyphthalic acid is acid chlorided, a monoacid chloride compound and N-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3 Active ester compounds obtained by reaction of a dicarboxylate imide
  • Examples of the carbonic acid ester compound used as a capping agent at the end of the amino group include di-tert-butyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate and diethyl bicarbonate.
  • Examples of vinyl ether compounds used as capping agents at the end of the amino group include tert-butyl chloroformate, n-butyl chloroformate, isobutyl chloroformate, chloroformates such as benzyl chloroformate, butyl isocyanate, isocyanate 1 And isocyanate compounds such as naphthyl, butyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether and the like.
  • benzyl chloroformate benzoyl chloride, fluorenylmethyl chloroformate, 2,2,2-trichloroethyl chloroformate, allyl chloroformate, methanesulfonic acid chloride, p-toluenesulfonic acid chloride, phenyl isocyanate and the like can be mentioned.
  • the proportion of the end-capping agent at the end of the acid anhydride group is preferably 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, relative to the acid dianhydride component.
  • the introduction ratio of the blocking agent at the end of the amino group is preferably in the range of 0.1 to 100 mol%, more preferably 0.5 to 80 mol%, and particularly preferably 1 to 100 mol% with respect to the diamine component. 60 mol%.
  • Multiple different end groups may be introduced by reacting multiple end capping agents.
  • the end capping agent introduced into the polyimide precursor (A) can be easily detected by the following method. For example, a polymer into which an end capping agent has been introduced is dissolved in an acidic solution and decomposed into an amine component which is a constituent unit of the polymer and an acid anhydride component, and this is measured by gas chromatography (GC) or NMR measurement. And end capping agents can be easily detected. In addition, it is also easily detectable by directly measuring a polymer into which an end capping agent is introduced by pyrolysis gas chromatography (PGC) or infrared spectrum and 13 C NMR spectrum.
  • PPC pyrolysis gas chromatography
  • the polyimide precursor resin composition which concerns on embodiment of this invention contains the polyimide precursor (A) mentioned above and a solvent (B).
  • the solvent (B) is a solvent (B1) having an SP value of not less than 7.7 and not more than 9.0, and a solvent (B2) having an SP value of not less than 9.0 and not more than 12.5. Including the above.
  • the SP value is a parameter serving as an indicator of solubility and compatibility, which is also called a solubility parameter.
  • a solubility parameter there are a method of calculating the value of solubility parameter from physical properties such as heat of evaporation and a method of estimating the value of solubility parameter from molecular structure.
  • Polym. Eng. Sci. , 14 (2), 147-154 (1974) the value calculated from the molecular structure is used based on the method of Fedors, and the unit thereof is (cal / cm 3 ) 1/2 .
  • a polyimide precursor (A) has a structural unit represented by General formula (2), The one part contains the structure represented by General formula (1).
  • the SP value of the structural unit of the polyimide precursor (A) including the structure of the general formula (1) is approximately 8.0, and the SP value of the polyimide precursor structural unit not including the general formula (1) is approximately 11.2. It will be 0. From this, when the solvent (B) contains at least one or more of each of the above solvents (B1) and (B2), the polyimide precursor resin composition is dissolved in the solvent (B) without causing turbidity. be able to.
  • solvent (B1) for example, 3-methoxy-3-methyl-1-butyl acetate (MMBAc, SP value: 8.85), dipropylene glycol methyl ether acetate (DPMA, SP value: 8.99), di- Propylene glycol dimethyl ether (DMM, SP value: 7.88), N, N-dimethylisobutyramide (DMIB, SP value: 8.81) and the like can be mentioned.
  • MMBAc 3-methoxy-3-methyl-1-butyl acetate
  • DPMA dipropylene glycol methyl ether acetate
  • DM di- Propylene glycol dimethyl ether
  • DMIB N-dimethylisobutyramide
  • solvent (B2) for example, ⁇ -butyrolactone (GBL, SP value: 10.52), N-methyl-2-pyrrolidone (NMP, SP value: 10.05), cyclohexanone (SP value: 9.80), Propylene glycol monomethyl ether (PGME, SP value: 11.27), propylene glycol monomethyl ether acetate (PGMEA, SP value: 9.11), dimethylacetamide (DMAc, SP value: 9.13), 1,3-dimethyl- Examples thereof include 2-imidazolidinone (DMI, SP value: 9.70), diethylene glycol monobutyl ether acetate (BDGAc, SP value: 9.19) and the like.
  • the polyimide precursor resin composition contains one or more of each of the solvents (B1) and (B2) as the solvent (B), the coatability at the slit is good, and the clouding of the obtained polyimide film, The residual stress can be suppressed.
  • the SP value is 7.7 or more, 9 when the amount of the whole solvent (B) is 100% by mass. It is preferable to contain 5 to 40% by mass of the solvent (B1) which is not more than 0, and 60 to 95% by mass of the solvent (B2) whose SP value is more than 9.0 and not more than 12.5. From the viewpoint of reducing the haze of the cured film, the solvent (B) preferably contains 15 to 35% by mass of the solvent (B1) and more preferably 65 to 85% by mass of the solvent (B2).
  • the polyimide precursor resin composition according to the embodiment of the present invention is a solvent having a vapor pressure of 10 Pa or more and 100 Pa or less at 20 ° C. when the total amount of the solvent (B) is 100 mass%. Is preferably contained in an amount of 70 to 100% by mass, and more preferably 80 to 100% by mass. By including 70 to 100% by mass of a solvent having a vapor pressure of 100 Pa or less at 20 ° C. in all the solvents (B), the evaporation of the solvent (B) can be suppressed. It is possible to suppress the solidification of the varnish generated in the above, and to suppress the application unevenness such as the streak unevenness etc. generated in the coating film.
  • the solvent (B) is uniformly removed from the entire coated film in the drying process of the coated film by containing 70 to 100% by mass of a solvent having a vapor pressure of 10 Pa or more at 20 ° C. in all the solvents (B). it can. Therefore, the film thickness uniformity of the film obtained after drying can be improved, and the haze of the film obtained can be suppressed.
  • Examples of the solvent having a vapor pressure of 10 Pa to 100 Pa at 20 ° C. include, for example, NMP (39 Pa), DMI (100 Pa), MMBAc (53 Pa), DMM (80 Pa), MMB (66 Pa), diethylene glycol monomethyl ether (20 Pa) Diethylene glycol monoethyl ether (60 Pa), dipropylene glycol dimethyl ether (70 Pa) and the like.
  • the difference in vapor pressure between the solvent having the highest vapor pressure and the solvent having the lowest vapor pressure at 20 ° C. is 100 Pa or less Is preferable, and 50 Pa or less is more preferable.
  • the polyimide precursor resin composition which concerns on embodiment of this invention may also contain the solvent except the above in the range which does not prevent the effect of this invention.
  • the viscosity of the polyimide precursor resin composition according to the embodiment of the present invention is usually 500 to 10,000 mPa ⁇ s, preferably 1,000, although it depends on the molecular weight and concentration of the polyimide precursor (A). ⁇ 6,000 mPa ⁇ s.
  • the viscosity of the polyimide precursor resin composition is in the above range, it is possible to obtain a coated film which is excellent in retention of the polyimide precursor resin composition during film formation and excellent in film thickness uniformity.
  • the viscosity of the polyimide precursor resin composition is a value measured at 25 ° C. in air using an E-type viscometer (viscometer Model RE 100 manufactured by Toki Sangyo Co., Ltd.).
  • the concentration of the polyimide precursor (A) in the polyimide precursor resin composition according to the embodiment of the present invention is preferably adjusted so that the viscosity of the polyimide precursor resin composition is in the above range, and the polyimide precursor although it depends on the molecular weight of (A), it is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and particularly preferably 10 to 20% by mass.
  • concentration of the polyimide precursor (A) in the polyimide precursor resin composition is in the above range, both thin film formation and thick film formation are possible, pinholes are not easily generated, and a film excellent in surface smoothness is obtained. It can be formed.
  • the polyimide precursor resin composition according to the embodiment of the present invention preferably contains an imidization accelerator.
  • an imidization accelerator for example, when the polyimide precursor (A) is polymerized, the imidation ratio of the polyimide precursor (A) can be increased by adding an imidation promoter.
  • the thermal imidization reaction during curing can be catalyzed to increase the breaking elongation of the polyimide resin composition obtained after curing.
  • the imidization accelerator referred to herein is a compound having a function of enhancing nucleophilicity and electrophilicity, and specifically, tertiary amine compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine and the like, 4- 4- Carboxylic acid compounds such as hydroxyphenylacetic acid and 3-hydroxybenzoic acid, Polyphenol compounds such as 3,5-dihydroxyacetophenone and methyl 3,5-dihydroxybenzoate, pyridine, quinoline, isoquinoline, imidazole, benzimidazole, 2- Heterocyclic compounds such as ethyl-4-methylimidazole and 1,2,4-triazole can be mentioned.
  • tertiary amine compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine and the like
  • 4- 4- Carboxylic acid compounds such as hydroxyphenylacetic acid and 3-hydroxybenzoic acid
  • Polyphenol compounds such as 3,5-
  • the imidization accelerator is preferably contained in an amount of 0.1 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight, with respect to 100 parts by weight of the polyimide precursor (A). It is particularly preferable to contain 3 parts by weight.
  • the polyimide precursor resin composition according to the embodiment of the present invention may contain a surfactant.
  • the surfactant may, for example, be a fluorine-based surfactant such as Florard (trade name, manufactured by Sumitomo 3M), Megafac (trade name, manufactured by DIC), sulfuron (trade name, manufactured by Asahi Glass).
  • organic siloxane interfaces such as KP 341 (trade name, Shin-Etsu Chemical Co., Ltd.), DBE (trade name, Chisso), Polyflow, Granol (trade name, Kyoeisha Chemical), BYK (Bic Chemie), etc. Activators are mentioned.
  • Examples thereof include polyoxyalkylene laurates such as Emulmin (manufactured by Sanyo Chemical Industries, Ltd.), polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene cetyl ether surfactants. Further, acrylic polymer surfactants such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be mentioned. Such surfactant is preferably contained in an amount of 0.001 to 1 part by weight with respect to 100 parts by weight of the polyimide precursor resin composition.
  • the polyimide precursor resin composition according to the embodiment of the present invention may contain an internal mold release agent.
  • the internal mold release agent include long chain fatty acids such as stearic acid and lauric acid.
  • the polyimide precursor resin composition according to the embodiment of the present invention may contain a thermal crosslinking agent.
  • a thermal crosslinking agent an epoxy compound and a compound having at least two alkoxymethyl groups or methylol groups are preferable. By having at least two of these groups, a condensation reaction occurs with the resin and the same molecule to form a crosslinked structure, and the mechanical strength and chemical resistance of the cured film after heat treatment can be improved.
  • the epoxy compound include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidyloxypropyl), epoxy group-containing silicone such as siloxane, etc.
  • the present invention is not limited to these.
  • Epiclon 850-S Epiclon HP-4032, Epiclon HP-7200, Epiclon HP-820, Epiclon HP-4700, Epiclon EXA-4710, Epiclon HP-4770, Epiclon EXA-859 CRP, Epiclon EXA-1514, Epiclon EXA-4880, Epiclon EXA-4850-150, Epiclon EXA-4850-1000, Epiclon EXA-4816, Epiclon EXA-4822 (trade names of Dainippon Ink and Chemicals, Inc.), Rica Resin BEO-60E, Jamaica Resin BPO- 20E, Guatemala Resin HBE-100, Jamaica Resin DME-100 (trade name, made by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000 S (trade name, made by Adeka), PG-100, CG-5 0, EG-200 (trade name, manufactured by Osaka Gas Chemical Co., Ltd.), NC-3000, NC-6000 (trade name, manufactured
  • Examples of compounds having at least two alkoxymethyl groups or methylol groups include DML-PC, DML-PEP, DML-OC, DMLOEP, DML-34X, DML-PTBP, DML-PCHP, DMLOCHP, DML-PFP, and DML.
  • the thermal crosslinking agent is preferably contained in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of the polyimide precursor (A).
  • the polyimide precursor resin composition according to the embodiment of the present invention may contain a colorant. By adding a coloring agent, the color tone of the heat-treated film of the polyimide precursor resin composition can be adjusted.
  • a coloring agent although a dye, an organic pigment, an inorganic pigment, etc. can be used, an organic pigment is preferable from heat resistance and the surface of transparency. Among them, those having high transparency and excellent in light resistance, heat resistance and chemical resistance are preferable.
  • color index (CI) numbers the following are preferably used, but all are not limited thereto.
  • yellow pigments examples include pigment yellow (hereinafter abbreviated as PY) 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 129, 137, 138, 139, 147. , 148, 150, 153, 154, 166, 168, 185, etc. are used.
  • PY pigment yellow
  • orange orange
  • pigment red (it abbreviates as PR hereafter) 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209, 215, 216, 217 220, 223, 224, 226, 227, 228, 240, 254, etc. are used.
  • pigment violet (it abbreviates as PV hereafter) 19, 23, 29, 30, 32, 37, 40, 50 etc. are used.
  • blue pigment pigment blue (it abbreviates as PB hereafter) 15, 15: 3, 15: 4, 15: 6, 22, 60, 64 etc. are used.
  • pigment green (it abbreviates to PG hereafter) 7, 10, 36, 58 etc. are used. These pigments may be subjected to surface treatment such as rosin treatment, acid group treatment, basic treatment and the like, if necessary.
  • the polyimide precursor resin composition according to the embodiment of the present invention may contain an inorganic filler.
  • the inorganic filler include silica particles, alumina particles, titania particles, and zirconia particles.
  • the shape of the inorganic filler is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, a flat shape, a lot shape, and a fibrous shape.
  • the contained inorganic filler preferably has a small particle size to prevent light scattering.
  • the average particle size of the inorganic filler is in the range of 0.5 to 100 nm, and preferably in the range of 0.5 to 30 nm.
  • the content of the inorganic filler is preferably 1 to 50% by weight, more preferably 10 to 30% by weight, based on 100% by weight of the total amount of the polyimide precursor (A).
  • a method of making a polyimide precursor resin composition contain an inorganic filler.
  • mixing the organo-inorganic filler sol with the polyimide precursor (A) may be mentioned.
  • the organo-inorganic filler sol is obtained by dispersing an inorganic filler in an organic solvent at a rate of about 30% by mass.
  • organic solvent methanol, isopropanol, normal butanol, ethylene glycol, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl acetate, propylene glycol monomethyl ether, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2 Pyrrolidone, 1,3-dimethylimidazolidinone, gamma butyl lactone and the like.
  • the organo-inorganic filler sol may be treated with a silane coupling agent.
  • the terminal functional group of the silane coupling agent has an epoxy group or an amino group
  • the carboxylic acid of the polyimide precursor (A) and the silane coupling agent are combined to form the polyimide precursor (A) and the inorganic substance.
  • the affinity with the filler is enhanced, and more effective dispersion can be performed.
  • silane coupling agent having an epoxy group 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidone And xylpropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and the like.
  • silane coupling agent having an amino group N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrile.
  • Methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane and the like can be mentioned.
  • the method of treating the organo-inorganic filler sol with the silane coupling agent can be treated by adding a silane coupling agent to an organo-inorganic filler sol having adjusted concentration and stirring at room temperature to 80 ° C. for 0.5 to 2 hours.
  • the polyimide precursor resin composition which concerns on embodiment of this invention can add coupling agents, such as a silane coupling agent and a titanium coupling agent, in order to improve adhesiveness with a base material.
  • the content of the coupling agent in the polyimide precursor resin composition is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the polyimide precursor (A).
  • the polyimide precursor resin composition which concerns on embodiment of this invention can add an ultraviolet absorber in order to improve light resistance (resistance to light, especially ultraviolet light).
  • the content of the ultraviolet light agent in the polyimide precursor resin composition is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the polyimide precursor (A).
  • the polyimide resin composition according to the embodiment of the present invention is obtained by imidizing the above-mentioned polyimide precursor resin composition.
  • the method of imidation is not particularly limited, imidation by heating and chemical imidation may be mentioned. Among them, imidization by heating is preferable from the viewpoint of the heat resistance of the resulting polyimide resin composition and the transparency in the visible light region.
  • the polyimide precursor resin composition film is heated in the range of 180 ° C. or more and 650 ° C. or less to convert it into a polyimide resin composition. This is called a thermal imidization process.
  • the thermal imidization process may be performed after some process after the process of evaporating the solvent from the coating film.
  • the step of evaporating the solvent from the coating may be carried out by vacuum drying or heating the coating, but in view of the transparency of the film after imidization, the solvent is evaporated without white turbidity.
  • drying use a hot plate, an oven, an infrared, a vacuum chamber or the like.
  • vacuum drying is preferably performed using a vacuum chamber, and heating for drying is further performed after vacuum drying, or heating for drying while vacuum drying is more preferably performed. Thereby, the drying processing time can be shortened, and furthermore, a uniform coated film can be obtained.
  • the heating temperature for drying varies depending on the type and purpose of the body to be heated, and is preferably in the range from room temperature to 170 ° C. for 1 minute to several hours.
  • the room temperature is usually 20 to 30 ° C., preferably 25 ° C.
  • the drying step may be performed multiple times under the same condition or different conditions.
  • the atmosphere of the thermal imidization step is not particularly limited, and may be air or an inert gas such as nitrogen or argon.
  • an atmosphere having an oxygen concentration of 3% or less it is preferable to perform thermal imidization by heating in an atmosphere having an oxygen concentration of 3% or less.
  • the polyimide resin composition according to the embodiment of the present invention is preferable because it can maintain higher transparency if the oxygen concentration at the time of heat curing is 3% or less.
  • the time required to reach the heating temperature for thermal imidization is not particularly limited, and a temperature rising method can be selected according to the heating system of the production line.
  • a temperature rising method can be selected according to the heating system of the production line.
  • the temperature of the polyimide precursor resin composition formed on the substrate may be raised from room temperature to the heating temperature for thermal imidization in 5 to 120 minutes, or 200 ° C. in advance.
  • the polyimide precursor resin composition formed on the base material may be charged as it is into an oven heated to a temperature not lower than 650 ° C. and subjected to heat treatment. Moreover, you may heat under pressure reduction as needed.
  • the film-like substance of the polyimide resin composition according to the embodiment of the present invention is a film containing polyimide formed by imidizing the polyimide precursor (A), that is, a polyimide resin film.
  • the film-like product of the polyimide resin composition (hereinafter, appropriately abbreviated as a polyimide resin film) can be obtained, for example, by the following method.
  • a coating film forming step of applying the above-mentioned polyimide precursor resin composition on a substrate to form a coating film, a solvent (for example, the above-mentioned solvent (B)) from the coating film includes a drying step of evaporation, an imidization step of imidizing the polyimide precursor (A), and the like.
  • the substrate to which the polyimide precursor resin composition is applied may be appropriately referred to as a support substrate, and may be distinguished from other substrates (for example, a flexible substrate with a polyimide resin film, etc.).
  • a coating film of a polyimide precursor resin composition is formed by applying the polyimide precursor resin composition on a supporting substrate in a coating film forming step.
  • a method of applying the polyimide precursor resin composition on a support substrate to form a coating film methods such as roll coating, spin coating, slit die coating, and coating using a doctor blade, a coater, etc. It can be mentioned.
  • the thickness and surface smoothness of the coating film may be controlled by repeating the application. Among them, the slit die coating method is preferable from the viewpoint of the surface smoothness of the coating film and the film thickness uniformity.
  • the thickness of the coating film is appropriately selected depending on the desired application, and is not particularly limited, but is, for example, 1 to 500 ⁇ m, preferably 2 to 250 ⁇ m, and particularly preferably 5 to 125 ⁇ m.
  • a support substrate polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, polybutylene terephthalate (PBT) film, silicon wafer, glass wafer, oxide wafer, glass substrate (including alkali-free glass substrate), Cu substrate And SUS plates.
  • alkali-free glass substrates are preferred from the viewpoint of surface smoothness and dimensional stability at the time of heating.
  • the coating film is dried by evaporating the solvent from the coating film on the supporting substrate.
  • the coating film may be dried by vacuum drying or heating, but in consideration of the transparency of the film after imidization, it is preferable to evaporate the solvent without causing white turbidity.
  • For drying use a hot plate, an oven, an infrared, a vacuum chamber or the like.
  • the drying process time of the coating film can be shortened, and furthermore, a uniform coating film can be obtained.
  • the temperature of the heating for drying varies depending on the type and purpose of the object to be heated such as a coating film, and is preferably performed in the range from room temperature to 170 ° C. for one minute to several hours.
  • the room temperature is usually 20 to 30 ° C., preferably 25 ° C.
  • the drying step may be performed multiple times under the same condition or different conditions.
  • the polyimide precursor (A) in the coating film on the support substrate is imidized, whereby a polyimide resin film is formed on the support substrate.
  • the polyimide resin film formed on the support substrate through the above steps can be peeled off from the support substrate, or can be used as it is without peeling off.
  • a peeling method of a polyimide resin film As an example of a peeling method of a polyimide resin film, a method of immersing in water, a method of immersing in a chemical solution such as hydrochloric acid or hydrofluoric acid, laser light in a wavelength range of ultraviolet light to infrared light to the polyimide resin film and the supporting substrate A method of irradiating the interface and the like can be mentioned.
  • peeling after forming a device on a polyimide resin film it is necessary to peel without damaging the device, so peeling using a laser of ultraviolet light is preferable.
  • a mold release agent silicone type, fluorine type, aromatic polymer type, alkoxysilane type etc. are mentioned.
  • the sacrificial layer may, for example, be a metal film, a metal oxide film, or an amorphous silicon film.
  • the thickness of the resulting polyimide resin film is appropriately selected depending on the desired application, but is preferably 1 to 100 ⁇ m, more preferably 5 to 30 ⁇ m, and particularly preferably 7 to 20 ⁇ m.
  • the polyimide resin film according to the embodiment of the present invention includes the structure represented by the general formula (1) described above, and is preferably used for applications such as the production of a flexible display substrate. Further, such a polyimide resin film preferably contains 5 to 30% by mass of the structure represented by the general formula (1), when the amount of the entire polyimide resin film is 100% by mass.
  • the tensile modulus of elasticity of the polyimide resin film obtained from the polyimide precursor resin composition of the present invention is preferably 1.5 GPa or more, more preferably 2.0 GPa or more, and particularly preferably 2.5 GPa or more .
  • the tensile modulus of elasticity of the polyimide resin film is 1.5 GPa or more, preferably 2.0 GPa or more, breakage when peeling the film from the substrate can be suppressed, and a polyimide resin film having sufficient flexibility You can get
  • the upper limit of the tensile modulus of elasticity of the polyimide resin film is preferably 3.5 GPa or less.
  • the breaking elongation of the polyimide resin film obtained from the polyimide precursor resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and particularly preferably 50% or more.
  • the breaking elongation of the polyimide resin film is 30% or more, it is preferable because it is excellent in bending resistance.
  • the glass transition temperature of the polyimide resin film according to the present embodiment is 250 ° C. or more, preferably 350 ° C. or more, more preferably 380 ° C. or more, and particularly preferably 400 ° C. or more.
  • the polyimide resin film is heated to 250 ° C. or more, preferably 350 ° C. or more at the time of device fabrication, and therefore, when the polyimide resin film has a glass transition temperature of less than 350 ° C., the polyimide resin film is used for such applications.
  • the polyimide resin film may be deformed.
  • the glass transition temperature of the polyimide resin film is 380 ° C. or more, the deterioration of the surface roughness after forming the gas barrier film on the polyimide resin film can be significantly suppressed.
  • the haze value of the polyimide resin film according to the present embodiment is 1% or less, preferably 0.8% or less, and particularly preferably 0.5% or less.
  • the polyimide precursor resin composition of the present invention contains two or more solvents (for example, the above-mentioned solvents (B1) and (B2)) each having an SP value in a preferable range, so that the haze value increases due to phase separation. Can be suppressed.
  • the laminate according to the embodiment of the present invention has a film-like product (polyimide resin film) of the above polyimide resin composition and an inorganic film.
  • the inorganic film is a gas barrier layer.
  • the gas barrier layer plays a role of preventing permeation of water vapor, oxygen and the like.
  • Examples of the material constituting the gas barrier layer include metal oxides, metal nitrides, metal oxynitrides and metal carbonitrides.
  • metal elements contained in these for example, aluminum (Al), silicon (Si), titanium (Ti), tin (Sn), zinc (Zn), zirconium (Zr), indium (In), niobium (Nb) And molybdenum (Mo), tantalum (Ta), calcium (Ca) and the like.
  • the gas barrier layer preferably contains at least one or more of silicon oxide, silicon nitride, silicon oxynitride and silicon carbonitride.
  • a uniform and dense film can be easily obtained, and the oxygen barrier property of the gas barrier layer can be further improved.
  • a gas barrier layer contains the component represented by SiOxNy from a viewpoint that oxygen barrier property improves more.
  • x and y are values that satisfy 0 ⁇ x ⁇ 1, 0.55 ⁇ y ⁇ 1, 0 ⁇ x / y ⁇ 1.
  • the layer which touches a polyimide resin film among these inorganic films is a value which satisfy
  • the method for manufacturing a laminate according to the embodiment of the present invention includes, for example, the following application process, removal process, polyimide resin film formation process, inorganic film formation process and process.
  • the applying step is a step of applying a polyimide precursor resin composition on a support substrate.
  • the removing step is a step of removing the solvent from the applied polyimide precursor resin composition.
  • the polyimide resin film forming step is a step of imidizing the polyimide precursor resin composition from which the solvent has been removed to obtain a film-like product of the polyimide resin composition.
  • the inorganic film forming step is a step of forming an inorganic film on the film-like material of the obtained polyimide resin composition.
  • the coating step, the removing step and the polyimide resin film forming step can be carried out according to the method for producing a film-like product of the polyimide resin composition described above. That is, the application process in the method of manufacturing a laminate is the same as the process of forming a coating film in the method of manufacturing a polyimide resin film.
  • the removal process in the manufacturing method of a laminated body is the same as the drying process in the manufacturing method of a polyimide resin film.
  • the polyimide resin film formation process in the manufacturing method of a laminated body is the same as the imidization process in the manufacturing method of a polyimide resin film.
  • the inorganic film forming step in the method for manufacturing a laminate for example, the inorganic film is formed as follows.
  • the inorganic film can be produced, for example, by a vapor deposition method such as sputtering, vacuum evaporation, ion plating, plasma CVD or the like, in which a material is deposited from the vapor phase to form a film.
  • a vapor deposition method such as sputtering, vacuum evaporation, ion plating, plasma CVD or the like, in which a material is deposited from the vapor phase to form a film.
  • a vapor deposition method such as sputtering, vacuum evaporation, ion plating, plasma CVD or the like, in which a material is deposited from the vapor phase to form a film.
  • a sputtering method or a plasma CVD method because a film more uniform and having high oxygen barrier properties can be obtained.
  • the number of layers of the inorganic film is not particularly limited, and may be only one layer or a multilayer of two or more layers, but it is a multilayer of two or more layers from the viewpoint of achieving both flex resistance and gas barrier properties. preferable.
  • the multilayer inorganic film include a gas barrier layer in which the first layer is made of SiN and the second layer is made of SiO, and a gas barrier layer in which the first layer is made of SiON and the second layer is made of SiO.
  • the total thickness of the inorganic film is preferably 10 nm or more, and more preferably 50 nm or more, from the viewpoint of improving the oxygen barrier property.
  • the total thickness of the inorganic film is preferably 1 ⁇ m or less, and more preferably 200 nm or less.
  • the laminate formed on the substrate through the above-described steps can be peeled off from the substrate, or can be used as it is without peeling off.
  • the peeling method of a laminated body the method similar to the method of peeling the above-mentioned polyimide resin film from a board
  • substrate can be used.
  • the polyimide precursor resin composition which concerns on embodiment of this invention, the polyimide resin composition obtained using this, a polyimide resin film, and a laminated body can be used for an electronic device. More specifically, it can be used for display devices such as liquid crystal displays, organic EL displays, touch panels, electronic paper, color filters, micro LED displays, solar cells, light receiving devices such as CMOS, and the like. These electronic devices are preferably flexible devices.
  • the above-mentioned polyimide resin film is preferably used as a substrate in these electronic devices, particularly as a flexible substrate (for example, a flexible display substrate etc.).
  • the manufacturing process of a flexible device includes a process of forming a circuit necessary for a display device or a light receiving device on a laminate formed on a substrate.
  • a circuit necessary for a display device or a light receiving device can be formed over a flexible substrate.
  • TFTs thin film transistors
  • the structure necessary for the device can be formed thereon by a known method.
  • the laminate having the circuit or the like formed on the surface can be peeled off from the substrate using a known method such as laser irradiation to obtain a flexible device.
  • the touch panel according to the embodiment of the present invention includes the above-described laminate.
  • An example of the configuration of a touch panel according to an embodiment of the present invention will be described with reference to the drawings.
  • FIG. 1A is a plan view showing a configuration example of a touch panel including a polyimide resin film according to an embodiment of the present invention.
  • FIG. 1B is a cross-sectional view of the touch panel shown in FIG. 1A, taken along line I-I '.
  • the touch panel 7 includes a polyimide resin film 1, a gas barrier layer 2, a first wiring layer 3, a first insulating layer 4, a second wiring layer 5, and a second wiring layer 5.
  • Two insulating layers 6 are provided in this order. That is, the touch panel 7 includes the polyimide resin film 1 as a flexible substrate, and includes the gas barrier layer 2 on the polyimide resin film 1.
  • the touch panel 7 includes the first wiring layer 3 on the gas barrier layer 2, the first insulating layer 4 on the first wiring layer 3, and the second on the first insulating layer 4. And the second insulating layer 6 on the second wiring layer 5.
  • the first wiring layer 3 and the second wiring layer 5 can be formed using a conductive composition.
  • a conductive composition for example, conductive particles, alkali soluble resins, organic tin compounds, metal chelate compounds, dispersants, photopolymerization initiators, monomers, photoacid generators, thermal acid generators, solvents And at least one of a sensitizer, a pigment and a dye having absorption to visible light, an adhesion improver, a surfactant or a polymerization inhibitor, and the like.
  • the conductive particles contained in the conductive composition preferably have a coating layer on at least a part of the surface.
  • the surface activity of the conductive particles can be reduced, and at least one of the reaction between the conductive particles and the reaction between the conductive particles and the organic component can be suppressed to improve the dispersibility of the conductive particles.
  • the coating layer can be easily removed by heating at a high temperature of about 150 to 350 ° C. in the presence of oxygen, and sufficient conductivity as a wiring can be expressed.
  • the covering layer preferably contains at least one of carbon and a carbon compound.
  • the coating layer contains at least one of carbon and a carbon compound, the dispersibility of the conductive particles in the conductive composition can be further improved.
  • a reactive gas containing carbon such as methane gas and conductive particles are formed by a thermal plasma method.
  • a method of contacting for example, see JP-A-2007-138287.
  • the first insulating layer 4 and the second insulating layer 6 can be formed using a photosensitive insulating composition containing an alkali-soluble resin.
  • the content of the alkali-soluble resin contained in the insulating composition can be optionally selected according to the desired film thickness and application, but 10 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the solid content It is common to
  • the insulating composition may contain a hindered amine light stabilizer. By containing the hindered amine light stabilizer, coloring of the first insulating layer 4 and the second insulating layer 6 can be further reduced, and the weather resistance can be improved.
  • the insulating composition further comprises, if necessary, a polyfunctional monomer, a curing agent, an ultraviolet absorber, a polymerization inhibitor, an adhesion improver, a solvent, a surfactant, a dissolution inhibitor, a stabilizer, an antifoamer, etc. It can also contain an agent.
  • the manufacturing method of the touch panel using the layered product concerning an embodiment of the invention includes the following layer formation processes and the exfoliation process, for example.
  • the layer forming step is a step of forming a wiring layer and an insulating layer on the laminate.
  • a peeling process is a process of peeling the said laminated body from the said support substrate.
  • the peeling process in the manufacturing method of a touch panel can be performed according to the manufacturing method of the above-mentioned laminated body.
  • the layer forming step in the method of manufacturing the touch panel for example, the wiring layers (the first wiring layer 3 and the second wiring layer 5 in FIGS. 1A and 1B) and the insulating layer (FIGS. 1A and 1B)
  • the first insulating layer 4 and the second insulating layer 6) are formed on a laminate (a laminate comprising the polyimide resin film 1 and the gas barrier layer 2 in FIGS. 1A and 1B).
  • the method of forming the first wiring layer includes a coating step of coating the conductive composition on the gas barrier layer 2, a prebaking step of drying the coating film, It is preferable to include a step of exposing and developing the pre-baked film to form a mesh pattern (exposure step and developing step), and a curing step of curing the pattern.
  • the first wiring layer using a conductive composition containing conductive particles having a covering layer on at least a part of the surface.
  • the conductive particles having the covering layer on at least a part of the surface can suppress scattering of the exposure light in the exposure step, and the wiring can be patterned with high accuracy.
  • a light source used in the exposure process for example, j-line, i-line, h-line, and g-line of a mercury lamp are preferable.
  • a well-known developer can be used as a developer used at the image development process.
  • an alkaline aqueous solution in which an alkaline substance such as sodium hydroxide, potassium hydroxide, tetramethyl ammonium hydroxide (TMAH) or the like is dissolved in water can be mentioned.
  • the atmosphere, temperature, and time for curing may be determined as appropriate depending on the composition of the conductive composition and the thickness of the coating film.
  • the coating film is preferably heated in air at a temperature range of 100 to 300 ° C. for 5 to 120 minutes.
  • an atmosphere having an oxygen concentration of 15% or more in order to reliably remove the coating layer and to develop sufficient conductivity is heated at a temperature of 100 ° C. or more and 300 ° C. or less.
  • the temperature is 300.degree. C. or more and 450.degree.
  • the method includes the steps of heating to form a polyimide resin film, and heating at a temperature of 100 ° C. to 300 ° C. in an atmosphere with an oxygen concentration of 15% or more to form a first wiring layer.
  • the method of forming the first insulating layer (for example, the first insulating layer 4 shown in FIGS. 1A and 1B) on the first wiring layer includes applying an insulating composition on the first wiring layer, It is preferable to include a pre-baking step of drying the coated film, a step of exposing and developing the pre-baked film to form a pattern (exposure step, developing step), and a curing step of curing the pattern.
  • the respective steps can be performed in the same manner as in the case of forming the first wiring layer.
  • a second wiring layer (for example, the second wiring layer 5 shown in FIGS. 1A and 1B) is formed on the first insulating layer.
  • the second wiring layer can be formed by the same method as the first wiring layer.
  • a second insulating layer may be formed on the second wiring layer, as exemplified by the second insulating layer 6 in FIGS. 1A and 1B, for example. By forming the second insulating layer, moisture in the air can be prevented from reaching the second wiring layer, and the moisture and heat resistance of the touch panel can be improved.
  • the second insulating layer can be formed by the same method as the first insulating layer.
  • a color filter according to an embodiment of the present invention includes the above-described laminate.
  • An example of the configuration of a color filter according to an embodiment of the present invention will be described with reference to the drawings.
  • FIG. 2 is a view showing a configuration example of a color filter including a laminate according to the embodiment of the present invention.
  • the color filter 8 includes a polyimide resin film 1 and a gas barrier layer 2 in this order. That is, in the color filter 8, the laminate is formed of the polyimide resin film 1 and the gas barrier layer 2 formed (laminated) thereon.
  • the color filter 8 further includes a black matrix 9, a red pixel 10 R, a green pixel 10 G, a blue pixel 10 B, and an overcoat layer 11 on the gas barrier layer 2.
  • the red pixel 10R is a red colored pixel.
  • the green pixel 10G is a green colored pixel.
  • the blue pixel 10B is a blue colored pixel.
  • the overcoat layer 11 is formed to cover the black matrix 9, the red pixel 10R, the green pixel 10G, and the blue pixel 10B.
  • the black matrix 9 is preferably a resin black matrix in which a black pigment is dispersed in a resin.
  • black pigments include carbon black, titanium black, titanium oxide, titanium oxynitride or titanium nitride. In particular, carbon black and titanium black are preferable. Red pigments, green pigments and blue pigments can also be mixed and used as black pigments.
  • a polyimide resin is preferable because a thin pattern is easily formed.
  • the polyimide resin is preferably a polyimide resin obtained by thermally curing a polyamic acid synthesized from an acid anhydride and a diamine after pattern processing.
  • an acid anhydride, diamine, and a solvent what was mentioned by the above-mentioned polyimide precursor (A) can be used.
  • the resin black matrix using this contains an alkali-soluble acrylic resin in which a black pigment is dispersed, a photopolymerizable monomer, a polymer dispersant, and an additive.
  • alkali-soluble acrylic resins include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds.
  • the colored pixels are generally made up of three colored pixels of red, green and blue (i.e., red pixel 10R, green pixel 10G and blue pixel 10B).
  • the brightness of the white display of the display device can also be improved by forming a colorless and transparent pixel or a very thin and light-colored fourth color pixel.
  • resins used for the red pixel 10R, the green pixel 10G, and the blue pixel 10B include acrylic resins, epoxy resins, and polyimide resins.
  • the photosensitivity Acrylic resins are preferred.
  • the photosensitive acrylic resin generally contains an alkali soluble resin, a photopolymerizable monomer and a photopolymerization initiator. Examples of alkali-soluble resins include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds.
  • the method for producing a color filter using the laminate according to the embodiment of the present invention includes, for example, the following forming step and peeling step.
  • the forming step is a step of forming a black matrix and colored pixels on the laminate.
  • a peeling process is a process of peeling the said laminated body from the said support substrate.
  • the peeling process in the manufacturing method of a color filter can be performed according to the manufacturing method of the above-mentioned laminated body.
  • a black matrix black matrix 9 in FIG. 2 is formed as follows.
  • a black resin composition for resin black matrix comprising a polyamic acid in which a black pigment is dispersed on the laminate (for example, on the gas barrier layer 2 shown in FIG. 2).
  • the solution is applied by a method such as spin coater or die coater so that the film thickness after curing becomes 1 ⁇ m. It is dried under reduced pressure at 60 Pa or less and then semi-cured in a hot air oven or hot plate at 110 to 140.degree.
  • a positive resist is applied by a method such as spin coater or die coater so that the film thickness after prebaking becomes 1.2 ⁇ m. This is dried under reduced pressure at 80 Pa and then prebaked in a hot air oven or hot plate at 80 to 110 ° C. to form a resist film. Thereafter, exposure is selectively performed with ultraviolet light through a photomask using a proximity exposure device or a projection exposure device. Then, the exposed portion is removed by immersion in an alkaline developer such as 1.5 to 3.0% by weight of potassium hydroxide or tetramethyl ammonium hydroxide for 20 to 300 seconds.
  • an alkaline developer such as 1.5 to 3.0% by weight of potassium hydroxide or tetramethyl ammonium hydroxide for 20 to 300 seconds.
  • exposure and development can be performed without apply
  • colored pixels are formed on the laminate after the resin black matrix is formed, for example, by the following method.
  • a red pixel 10R, a green pixel 10G, and a blue pixel 10B shown in FIG. 2 are formed as colored pixels.
  • Colored pixels of the color filter are manufactured using a colorant and a resin.
  • a pigment is used as the colorant, the pigment is mixed with a polymer dispersant and a solvent and subjected to dispersion treatment, and then an alkali-soluble resin, a monomer, a photopolymerization initiator and the like are added.
  • a dye is used as the colorant, a solvent, an alkali-soluble resin, a monomer, a photopolymerization initiator and the like are added to the dye.
  • the total solid content in this case is the sum of the polymer dispersant as the resin component, the alkali-soluble resin and the monomer, and the colorant.
  • the colorant composition obtained is subjected to a heat treatment of 0.8 to 3.0 ⁇ m in thickness by a method such as spin coater or die coater. Apply to a film thickness. This is dried under reduced pressure at 80 Pa and then prebaked in a hot air oven or hot plate at 80 to 110 ° C. to form a coating film of a colorant.
  • the patterning step as described above can be carried out by using red colored pixels (eg red pixel 10R), green colored pixels (eg green pixel 10G) and blue colored
  • red colored pixels eg red pixel 10R
  • green colored pixels eg green pixel 10G
  • blue colored The process is sequentially performed on pixels (for example, blue pixels 10B).
  • the order of patterning of colored pixels is not particularly limited.
  • the color filter may be provided with a planarizing layer.
  • resin used for formation of a planarization layer an epoxy resin, an acrylic epoxy resin, an acrylic resin, a siloxane resin, or a polyimide resin is mentioned.
  • the thickness of the planarizing layer is preferably such that the surface becomes flat, specifically 0.5 to 5.0 ⁇ m is more preferable, and 1.0 to 3.0 ⁇ m is more preferable.
  • a liquid crystal element according to an embodiment of the present invention includes the above-described laminate. An example of the configuration of a liquid crystal element according to an embodiment of the present invention will be described with reference to the drawings.
  • FIG. 3 is a view showing a configuration example of a liquid crystal element including the laminate according to the embodiment of the present invention.
  • the liquid crystal element 12 is opposed to the polyimide resin films 1-1 and 1-2, the gas barrier layer 2, the pixel electrode 13, the first alignment film 14, and the second alignment film 15.
  • An electrode 16, a liquid crystal layer 17, and a polarizing plate 18 are provided.
  • the polyimide resin film 1-1 as the first base material is disposed opposite to the polyimide resin film 1-2 as the second base material with a gap.
  • a liquid crystal layer 17 is provided between them.
  • a gas barrier layer 2 which is an inorganic film is provided on the polyimide resin film 1-1, and a transparent electrode formed of a transparent conductive film such as ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide) is formed thereon.
  • a pixel electrode 13 and a first alignment film 14 are provided.
  • the gas barrier layer 2 which is an inorganic film is provided on the opposite surface (surface facing the polyimide resin film 1-1) of the polyimide resin film 1-2.
  • a counter electrode 16 which is a transparent electrode is provided on the surface of the gas barrier layer 2 on the liquid crystal layer 17 side so as to face the pixel electrode 13.
  • a second alignment film 15 is provided on the surface of the counter electrode 16 on the liquid crystal layer 17 side.
  • the manufacturing method of the liquid crystal element using the laminated body which concerns on embodiment of this invention includes the following formation process and a peeling process, for example.
  • the forming step is a step of forming a transparent electrode, an alignment film, and a liquid crystal layer on the laminate.
  • a peeling process is a process of peeling the said laminated body from the said support substrate.
  • the peeling step in the method for manufacturing a liquid crystal element can be performed according to the above-described method for manufacturing a laminate.
  • the formation process in the method of manufacturing a liquid crystal element can be performed, for example, as follows.
  • the pixel electrode for example, the pixel electrode 13 shown in FIG. 3 is laminated on the laminate to be the first support substrate, and the laminate to be the second support substrate.
  • the counter electrode for example, the counter electrode 16 shown in FIG. 3 is formed on the top.
  • the laminate to be the first support base is composed of the polyimide resin film 1-1 and the gas barrier layer 2 shown in FIG.
  • the laminate to be the second supporting base is composed of the polyimide resin film 1-2 and the gas barrier layer 2 shown in FIG.
  • the method of forming the pixel electrode and the counter electrode may be any method capable of forming a target thin film or pattern, and for example, vapor phase such as sputtering, vacuum evaporation, ion plating, plasma CVD, etc.
  • a vapor deposition method of depositing a metal oxide from the inside to form a film is suitable.
  • the film thickness of each of the pixel electrode and the counter electrode is preferably 20 to 500 nm, and more preferably 50 to 300 nm.
  • a first alignment film for example, the first alignment film 14 shown in FIG. 3 is formed on the pixel electrode, and a second alignment film (for example, the second alignment film 15 shown in FIG. 3) is formed on the counter electrode.
  • a second alignment film for example, the second alignment film 15 shown in FIG. 3 is formed on the counter electrode.
  • known ones can be used. For example, it can be formed by applying an alignment film made of a polyimide resin by a printing method, heating at 250 ° C. for 10 minutes using a hot plate, and rubbing the obtained film.
  • the thickness of the first alignment film and the second alignment film may be any thickness as long as the liquid crystal of the liquid crystal layer (the liquid crystal layer 17 in FIG. 3) can be aligned, and is preferably 20 nm to 150 nm.
  • a liquid crystal layer is formed.
  • a publicly known method can be used to form a liquid crystal layer, for example, a liquid crystal layer can be formed by the following method.
  • the sealing agent is applied onto the second alignment film by a dispensing method, and heated at 90 ° C. for 10 minutes using a hot plate.
  • a spherical spacer having a diameter of 5.5 ⁇ m is dispersed on the first alignment film. This is superposed on a substrate (second alignment film) coated with a sealing agent, and heated in an oven at 160 ° C. for 90 minutes while being pressurized to cure the sealing agent, to obtain a cell. Subsequently, the cell is left to stand at a temperature of 120 ° C.
  • the liquid crystal compound is charged again under vacuum.
  • the liquid crystal compound is filled by placing the cell in a chamber and reducing the pressure to 13.3 Pa at room temperature, then immersing the liquid crystal inlet in liquid crystal, and returning to normal pressure using nitrogen. After filling the liquid crystal, the liquid crystal inlet is sealed with an ultraviolet curing resin.
  • the liquid crystal layer (for example, the liquid crystal layer 17 shown in FIG. 3) is formed between the first alignment film and the second alignment film.
  • the polyimide resin film (the polyimide resin films 1-1 and 1-2 in FIG. 3) is peeled off from the support substrate, and the first substrate (polyimide resin film 1-1) and the second substrate (the The polarizing plate 18 is attached to each of the polyimide resin films 1-2). Thereby, a liquid crystal element (for example, the liquid crystal element 12 shown in FIG. 3) can be obtained.
  • An organic EL element according to an embodiment of the present invention includes the above-described laminate. An example of the configuration of the organic EL element according to the embodiment of the present invention will be described with reference to the drawings.
  • FIG. 4 is a view showing one configuration example of the organic EL element including the laminate according to the embodiment of the present invention.
  • the organic EL element 19 includes a polyimide resin film 1, a gas barrier layer 2, a TFT layer 20, a flattening layer 21, a first electrode 22, an insulating layer 23, and a red organic EL.
  • a light emitting layer 24R, a green organic EL light emitting layer 24G, a blue organic EL light emitting layer 24B, and a second electrode 25 are provided.
  • a gas barrier layer 2 which is an inorganic film is formed on the polyimide resin film 1.
  • the polyimide resin film 1 and the gas barrier layer 2 constitute a laminate included in the organic EL element 19.
  • a TFT layer 20 made of amorphous, silicon, low temperature polysilicon, an oxide semiconductor or the like, and a planarization layer 21 are provided on the gas barrier layer 2.
  • a first electrode 22 made of Al / ITO or the like and an insulating layer 23 covering the end of the first electrode 22 are provided.
  • a red organic EL light emitting layer 24R, a green organic EL light emitting layer 24G, and a blue organic EL light emitting layer 24B are provided on the first electrode 22 .
  • Each of the red organic EL light emitting layer 24R, the green organic EL light emitting layer 24G, and the blue organic EL light emitting layer 24B includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
  • a second electrode 25 made of ITO or the like is formed on the insulating layer 23, the red organic EL light emitting layer 24R, the green organic EL light emitting layer 24G, and the blue organic EL light emitting layer 24B. The second electrode 25 is sealed by the gas barrier layer 2 as shown in FIG.
  • the gas barrier layer 2 as a sealing film comprises the organic EL light emission circuit on a laminated body.
  • the manufacturing method of the organic EL element using the laminated body which concerns on embodiment of this invention includes the following formation process and the peeling process, for example.
  • the forming step is a step of forming an organic EL light emitting circuit on the laminate.
  • a peeling process is a process of peeling the said laminated body from the said support substrate.
  • the peeling process in the manufacturing method of an organic EL element can be performed according to the manufacturing method of the above-mentioned laminated body.
  • the formation process in the manufacturing method of an organic EL element can be performed as follows, for example.
  • a TFT layer is formed on the above-described laminate.
  • the semiconductor layer for forming the TFT layer include amorphous silicon semiconductors, polycrystalline silicon semiconductors, oxide semiconductors represented by InGaZnO, and organic semiconductors represented by pentacene and polythiophene.
  • the specific method of forming the TFT layer is as follows. For example, a gas barrier film, a gate electrode, a gate insulating film, a polycrystalline silicon semiconductor layer, an etching stopper film, and a source / drain electrode are sequentially formed by a known method using the laminate according to the embodiment of the present invention as a base material.
  • a TFT layer such as a bottom gate type TFT (for example, the TFT layer 20 shown in FIG. 4) can be manufactured.
  • a planarization layer (for example, the planarization layer 21 shown in FIG. 4) is formed on the TFT layer.
  • resin used for formation of a planarization layer an epoxy resin, an acrylic epoxy resin, an acrylic resin, a polysiloxane resin, or a polyimide resin is mentioned.
  • an electrode and an organic layer are formed on this planarizing layer.
  • a first electrode for example, the first electrode 22 shown in FIG. 4 made of Al / ITO or the like is formed.
  • an insulating layer (for example, the insulating layer 23 shown in FIG.
  • the white organic EL light emitting layer is configured by the red organic EL light emitting layer 24R, the green organic EL light emitting layer 24G, and the blue organic EL light emitting layer 24B.
  • a second electrode for example, the second electrode 25 shown in FIG. 4 made of ITO or the like is formed on the white organic EL light emitting layer, and then a sealing film (FIG. Then, the gas barrier layer 2) on the second electrode 25 is formed.
  • an organic EL element for example, the organic EL element 19 shown in FIG. 4) can be obtained.
  • BSAA 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) propane dianhydride
  • ODPA 3,3 ', 4,4'-diphenylethertetracarboxylic acid dianhydride
  • PMDA 1,2, 4,5-benzenetetracarboxylic acid dianhydride
  • PMDA-HS 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride
  • BPAF 4,4'- (fluorenyl) diphthalic anhydride
  • X-22- 168-P5-B Both terminal carboxylic acid anhydride modified methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • CHDA trans-1,4-diaminocyclohexane
  • TFMB 2,2'-bis (trifluoromethyl) benzidine
  • m-TB 2,2'-dimethyl-4,4'-diaminobiphenyl
  • 4,4'-DDS 4,4'-Diaminodiphenyl sulfone
  • X22-1660B-3 Amine-modified amine-modified methylphenyl silicone oil (Shin-Etsu Chemical Co., Ltd.)
  • 1,3,5-TAPOB 1,3,5-tris (4-aminophenoxy) benzene
  • tetraamine compound those shown below are appropriately used.
  • TAB-S 3,3 ', 4,4'-tetraaminodiphenyl sulfone
  • NMP N-methyl-2-pyrrolidone (SP value: 10.05, vapor pressure (20 ° C.): 39 Pa)
  • GBL ⁇ -butyrolactone (SP value: 10.52, vapor pressure (20 ° C.): 150 Pa)
  • MMBAc 3-methoxy-3-methyl-1-butyl acetate (SP value: 8.85, vapor pressure (20 ° C.): 53 Pa)
  • DPMA Dipropylene glycol methyl ether acetate (SP value: 8.99, vapor pressure (20 ° C): 6.8 Pa)
  • PGME Propylene glycol monomethyl ether (SP value: 11.27, vapor pressure (20 ° C.): 1150 Pa)
  • DMIB N, N-dimethylisobutyramide (SP value: 8.81, vapor pressure (20 ° C.): 167 Pa)
  • BDG Ac butyl diglycol
  • Alkali-soluble resin (AR): 0.4 equivalent of glycidyl methacrylate added to the carboxyl group of a copolymer of methacrylic acid / methyl methacrylate / styrene 54/23/23 (mol%) (Weight average molecular weight (Mw): 29,000)
  • Conductive particles (A-1) Silver particles having an average thickness of 1 nm on the surface carbon coating layer and a primary particle diameter of 40 nm (manufactured by Nisshin Engineering Co., Ltd.)
  • Conductive particles (A-2) Silver particles having a primary particle diameter of 0.7 ⁇ m (manufactured by Mitsui Metals Co., Ltd.)
  • haze refers to the layer separation phenomenon that occurs due to the insufficient affinity between the silicone component and the solvent.
  • White turbidity refers to a phenomenon in which a polyimide precursor (A) obtained by polymerization does not completely dissolve in a solvent (B) and precipitates.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyimide precursor (A) in the polyimide precursor resin composition obtained in Examples and Comparative Examples are the HLC-8220 GPC apparatus (guard column) manufactured by TOSOH : TSK guard colomn ALPHA column: measured using TSK gel ALPHA-M, developing solvent: NMP).
  • the calibration curve for calculating a weight average molecular weight was created using standard polystyrene (made by Tosoh Corporation).
  • FIG. 5 is a figure for demonstrating preparation of a polyimide resin film in an Example, and evaluation of coating property.
  • the preparation of the polyimide resin film in the third item after curing the varnish on a glass substrate 26 (AN-100 manufactured by Asahi Glass Co., Ltd.) and a slit coater (manufactured by Toray Engineering Co., Ltd.) using a 300 mm ⁇ 350 mm ⁇ 0.5 mm thick glass substrate 26
  • the film was applied in the direction indicated by the arrow 29 so that the film thickness of the film became 10 ⁇ 0.5 ⁇ m, and then prebaking was performed using a heating vacuum dryer and a hot plate.
  • the heating type vacuum dryer heated the upper plate to 60 ° C. and the lower plate to 40 ° C., and performed drying under the condition that the internal pressure was lowered to 60 Pa in 150 seconds.
  • the hot plate was dried for 6 minutes using one which had been heated to 120 ° C. in advance.
  • the pre-bake film thus obtained is heated to 400 ° C. in 80 minutes under nitrogen stream (oxygen concentration 100 ppm or less) using an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) for 30 minutes. Hold and cool to 50 ° C. at 5-8 ° C./min. Thereby, as shown in FIG. 5, the polyimide resin film 27 was produced on the glass substrate 26 (first glass substrate).
  • In-plane uniformity of film thickness In the in-plane uniformity evaluation of the film thickness, the film thickness in the nozzle direction at a position of 50 mm from the application start portion except for the application end (a portion 10 mm from the outer periphery of the polyimide resin film 27) The in-plane uniformity of the film thickness was determined according to the following calculation formula.
  • the maximum film thickness and the minimum film thickness in the formula means the largest one and the smallest one of the ten measured points.
  • An average film thickness means the average value of the film thickness of ten measured.
  • the nozzle direction herein refers to a direction perpendicular to the application direction.
  • In-plane uniformity (%) ((maximum film thickness) ⁇ (minimum film thickness)) / (2 ⁇ (average film thickness)) ⁇ 100
  • the resulting pre-baked film is heated to 400 ° C. at 4 ° C./min under nitrogen stream (oxygen concentration 100 ppm or less) using an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) and held for 30 minutes, 5 It cooled to 50 ° C. at ⁇ 8 ° C./min.
  • an inert oven IH-21CD manufactured by Koyo Thermo Systems Co., Ltd.
  • the seventh item describes a method for producing a polyimide resin film (on a second silicon substrate).
  • a varnish is applied to a 4-inch silicon substrate (second silicon substrate) cut into quarters, and cured using a spin coater MS-A200 manufactured by Mikasa Corporation. Spin coating was carried out so that the film thickness after this would be 5 ⁇ 0.5 ⁇ m.
  • prebaking was performed at 120 ° C. for 6 minutes using a hot plate D-SPIN manufactured by Dainippon Screen. The resulting pre-baked film is heated to 400 ° C.
  • the eighth item describes the measurement of the light transmittance (T) of the polyimide resin film.
  • the light transmittance of the polyimide resin film at a wavelength of 450 nm was measured using a UV-visible spectrophotometer (MultiSpec 1500 manufactured by Shimadzu Corporation).
  • the polyimide resin film shown by the said 6th item was used for this measurement.
  • the ninth item describes measurement of the haze value of the polyimide resin film.
  • the haze value (%) of the polyimide resin film on the second glass substrate shown in the sixth item using the direct reading haze computer (HGM2DP manufactured by Suga Test Instruments Co., Ltd., C light source) was measured.
  • the average value of three measurements was used as each value.
  • the tenth item describes measurement of in-plane / out-plane birefringence of a polyimide resin film.
  • the tenth item describes measurement of in-plane / out-plane birefringence of a polyimide resin film.
  • n (TE) TE refractive index
  • TM refractive index n (TM )
  • n (TE) and TM) are refractive indexes in the parallel direction and the vertical direction, respectively, with respect to the polyimide resin film surface.
  • the in-plane / out-of-plane birefringence was calculated as the difference between n (TE) and n (TM) (n (TE) -n (TM)).
  • the polyimide resin film shown by the said 7th item was used for this measurement.
  • the eleventh item describes the measurement of the glass transition temperature of the polyimide resin film.
  • measurement was performed under a nitrogen stream using a thermomechanical analyzer (EXSTAR6000TMA / SS6000 manufactured by SII Nano Technology Inc.).
  • the temperature raising method was performed under the following conditions. In the first stage, the sample was heated to 150 ° C. at a temperature rising rate of 5 ° C./min to remove the adsorbed water of the sample, and in the second stage, it was air cooled to room temperature at a temperature lowering rate of 5 ° C./min.
  • the main measurement was performed at a temperature elevation rate of 5 ° C./min to determine the glass transition temperature.
  • membrane shown by the said 5th item was peeled and used for this measurement from the silicon wafer (1st silicon substrate).
  • the twelfth item describes the measurement of the 1% weight loss temperature of the polyimide resin film.
  • the measurement was performed under a nitrogen stream using a thermogravimetric measurement apparatus (TGA-50 manufactured by Shimadzu Corporation).
  • TGA-50 thermogravimetric measurement apparatus manufactured by Shimadzu Corporation.
  • the temperature raising method was performed under the following conditions. In the first stage, the sample was heated to 150 ° C. at a temperature rising rate of 3.5 ° C./min to remove the adsorbed water of the sample, and cooled in the second stage to a temperature lowering rate of 10 ° C./min.
  • the main measurement was performed at a temperature rising rate of 10 ° C./min to determine the 1% thermal weight loss temperature.
  • membrane shown by the said 5th item was peeled and used for this measurement from the silicon wafer (1st silicon substrate).
  • the thirteenth item describes the measurement of the breaking elongation and the elastic modulus of the polyimide resin film.
  • the measurement of elongation at break and elastic modulus in the 13th item was performed using Tensilon (RTM-100 manufactured by Orientec Co., Ltd.). Ten or more samples were measured for each sample, and the JIS average value was calculated using JIS number average (JIS K-6301).
  • membrane shown by the said 5th item was peeled and used for this measurement from the silicon wafer (1st silicon substrate).
  • the fourteenth item describes the measurement of the residual stress of the polyimide resin film.
  • the measurement was performed using a thin film stress measurement apparatus FLX-3300-T manufactured by KLA-Tencor Corporation.
  • the polyimide resin film shown in the above fifth item was used. At that time, the polyimide resin film was allowed to stand in a room at a room temperature of 23 ° C. and a humidity of 55% for 24 hours before measurement.
  • Item 15 Evaluation of Arithmetic Average Roughness (Ra)
  • Item 15 describes the evaluation of arithmetic mean roughness (Ra).
  • Arithmetic mean roughness (Ra) was measured on the surface of the inorganic film of System: NanoScope III / MMAFM (made by Digital Instruments)
  • Scanning mode Tapping mode Scanning range: 10 ⁇ m ⁇ 10 ⁇ m Scanning speed: 0.5 Hz
  • Measurement environment Temperature 23 ° C, relative humidity 65%, in the atmosphere
  • the sixteenth item describes the evaluation of the bending resistance of the laminate.
  • the bending resistance of the laminate having the inorganic film on the polyimide resin film was measured by the following method. First, the laminate peeled off from the glass substrate is sampled to a size of 100 mm ⁇ 140 mm, a metal cylinder of 30 mm in diameter is fixed at the center on the surface, and the holding angle of the metal cylinder is 0 ° along this metal cylinder. The sample was placed in a flat state) (see the laminate 30 and the metal cylinder 31 shown in FIG. 6).
  • the bending operation is performed 100 times to this laminated body in a range where the holding angle to the metal cylindrical column is 180 ° (a state in which the metal cylindrical column is folded back) (see the laminated body 30 and the metal cylindrical column 31 shown in FIG. 7). went.
  • the bending resistance was visually observed using a light microscope (OPTIPHOT 300, manufactured by Nikon Corporation) after the test, using the presence or absence of cracks in the inorganic film before and after the bending operation as an index.
  • the seventeenth item describes the preparation of the touch panel and the moist heat resistance evaluation.
  • the preparation of the touch panel is performed using the conductive composition and the insulating composition prepared in advance by the following method, and subsequently, the heat and moisture resistance test of the touch panel Did.
  • Production Example 1 Preparation of Conductive Composition
  • a conductive composition (AE-1) was prepared. Specifically, 80 g of conductive particles (A-1), 4.06 g of surfactant ("DISPERBYK” (registered trademark) 21116: manufactured by DIC Corporation), 98.07 g of PGMEA, 98.07 g of DPM, and mixed The resulting product was treated with a homogenizer at 1200 rpm for 30 minutes. Furthermore, the mixture was dispersed using a high pressure wet medialess atomization device Nanomizer (manufactured by Nanomizer Co., Ltd.) to obtain a silver dispersion having a silver content of 40% by mass.
  • DISPERBYK registered trademark 21116: manufactured by DIC Corporation
  • an insulating composition (OA-1) was prepared. Specifically, 50.0 g of a cardo resin (V-259ME: manufactured by Nippon Steel Sumitomo Chemical Co., Ltd.), 18.0 g of a crosslinkable monomer (TAIC: manufactured by Nippon Kasei Co., Ltd.), and a crosslinkable monomer (M-315) in a clean bottle : Add 10.0 g of Toagosei Co., Ltd., 20.0 g of an epoxy compound (PG-100: manufactured by Osaka Gas Chemical Co., Ltd.), and add 0.2 g of a photopolymerization initiator (OXE-01: manufactured by BASF) The mixture was stirred for 1 hour to obtain an insulating composition (OA-1).
  • V-259ME manufactured by Nippon Steel Sumitomo Chemical Co., Ltd.
  • TAIC manufactured by Nippon Kasei Co., Ltd.
  • M-315 crosslinkable monomer
  • the first wiring layer of the touch panel was formed by the following method.
  • a spin coater (“1H-360S (trade name)” manufactured by Mikasa Co., Ltd.) on a polyimide resin film or a laminate containing the polyimide resin film
  • the conductive composition (AE-1) is used.
  • the spin coating was performed at 300 rpm for 10 seconds and at 500 rpm for 2 seconds. Then, it was prebaked at 100 ° C. for 2 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a prebaked film.
  • SCW-636 (trade name) manufactured by Dainippon Screen Mfg. Co., Ltd.
  • a parallel light mask aligner (“PLA-501F (trade name)” manufactured by Canon Inc.)
  • PPA-501F (trade name)
  • a super high pressure mercury lamp as a light source.
  • AD-2000 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.
  • shower development is carried out for 60 seconds with a 0.045% by mass potassium hydroxide aqueous solution, followed by rinsing for 30 seconds with water.
  • Pattern processing The patterned substrate was cured at 250 ° C. for 30 minutes in air (21% oxygen concentration) using an oven to form a first wiring layer.
  • the first insulating layer of the touch panel was formed by the following method.
  • the insulating composition (OA-1) was spin-coated for 5 seconds at 650 rpm using a spin coater on the substrate on which the first wiring layer was formed. Then, it prebaked for 2 minutes at 100 degreeC using the hotplate, and produced the prebaking film
  • a parallel light mask aligner an ultra-high pressure mercury lamp was used as a light source, and the prebake film was exposed through a desired mask. Thereafter, using an automatic developing apparatus, shower development was performed for 60 seconds with a 0.045% by mass aqueous potassium hydroxide solution, followed by rinsing for 30 seconds with water, and pattern processing was performed. The patterned substrate was cured at 250 ° C. for 60 minutes in air (21% oxygen concentration) using an oven to form a first insulating layer.
  • a second wiring layer was formed on the substrate on which the first insulating layer was formed, in the same manner as the first wiring layer.
  • a second insulating layer was formed on the substrate on which the second wiring layer was formed, in the same manner as the first insulating layer.
  • the periphery of the region in which the first wiring layer and the second wiring layer were formed was cut with a single blade from the upper surface, and mechanically peeled from the cut end surface to obtain a touch panel.
  • a voltage was applied between the electrodes of the first wiring layer and the second wiring layer, and the change with time of the insulation resistance was measured.
  • a voltage of 10 V was applied to the first wiring layer as a positive electrode and the second wiring layer as a negative electrode, and the resistance value for 500 hours was measured at 5-minute intervals.
  • the measured resistance value reaches 10 5 or less, it is judged as a short circuit because of insulation failure, and the printing pressure is stopped, and the test time until that time is taken as the short circuit time. Thereafter, the moist heat resistance was evaluated according to the following evaluation criteria, and the case where the evaluation level was 2 or more was regarded as a pass.
  • Example 1 In Example 1, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), and m-TB (4. 5 g (2.24 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen. 64 g (21.9 mmol)), X-22-1 660 B-3 (2.26 g (0.51 mmol)), NMP (75 g) and MMBAc (25 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 70,000 and 33,000, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 2 In Example 2, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), and m-TB (4. 5 g (2.24 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen. 64 g (21.9 mmol)), X-22-1 660 B-3 (2.26 g (0.51 mmol)), NMP (75 g) and DPMA (25 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 72,000 and 32,500, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 3 In Example 3, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), and m-TB (4. 5 g (2.24 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen. 64 g (21.9 mmol)), X-22-1 660 B-3 (2.26 g (0.51 mmol)), NMP (75 g) and DMM (25 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 72,000 and 33,000, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 4 In Example 4, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), and m-TB (4. 5 g (2.24 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen. 64 g (21.9 mmol)), X-22-1 660 B-3 (2.26 g (0.51 mmol)), NMP (75 g) and DMIB (25 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 69,000 and 33,000, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 5 In Example 5, ODPA (6.31 g (20.3 mmol)), PMDA (0.49 g (2.26 mmol)), and m-TB (4. 6 g) in a 200 mL four-necked flask under a stream of dry nitrogen. 55 g (21.4 mmol)), X-22-1 660 B-3 (2.29 g (0.52 mmol)), 1,3,5-TAPOB (0.181 g (0.45 mmol)), NMP (75 g) ) And MMBAc (25 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 202,000 and 54,000, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 6 In Example 6, ODPA (6.24 g (20.1 mmol)), PMDA (0.49 g (2.23 mmol)), and m-TB (4. 5 g (2.23 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen. 56 g (21.5 mmol)), X-22-1 660 B-3 (2.26 g (0.51 mmol)), 1,3,5-TAPOB (0.089 g (0.25 mmol)), NMP (75 g) ) And MMBAc (25 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 152,000 and 48,000, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 7 In Example 7, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), and m-TB (4. 5 g (2.24 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen. 64 g (21.9 mmol)), X-22-1 660 B-3 (2.26 g (0.51 mmol)), GBL (75 g) and MMBAc (25 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 65,000 and 30,500, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 8 In Example 8, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), and m-TB (4. 5 g (2.24 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen. 64 g (21.9 mmol)), X-22-1 660 B-3 (2.26 g (0.51 mmol)), PGME (75 g) and MMBAc (25 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 61,000 and 28,000, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 9 In Example 9, ODPA (7.37 g (23.8 mmol)), PMDA (0.58 g (2.64 mmol)), and m-TB (4. 5 g (2.64 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen. 35 g (20.5 mmol)), 4,4'-DDS (1.31 g (5.28 mmol)), X-22-1 660 B-3 (2.67 g (0.61 mmol)), NMP (75 g) And MMBAC (25 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 68,000 and 31,500, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 10 In Example 10, ODPA (5.32 g (17.2 mmol)), PMDA (0.42 g (1.91 mmol)), and TFMB (5.97 g (5. 97 g) in a 200 mL four-necked flask under a stream of dry nitrogen. 18.6 mmol), X-22-1 660 B-3 (1.93 g (0.44 mmol)), NMP (75 g) and MMBAc (25 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 68,000 and 31,500, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 11 In Example 11, ODPA (5.40 g (17.4 mmol)), PMDA (0.42 g (1.93 mmol)), and TFMB (5.86 g (5.86 g (1.93 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen) 18.3 mmol)), X-22-1 660 B-3 (1.96 g (0.44 mmol)), 1,3,5-TAPOB (0.154 g (0.39 mmol)), NMP (75 g) and The mixture was stirred at 80 ° C. with MMBAC (25 g). After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 198,000 and 52,000, respectively.
  • Example 12 In Example 12, ODPA (7.35 g (23.7 mmol)), PMDA (0.57 g (2.63 mmol)), and m-TB (4. 5 g (2.63 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen. 17 g (19.7 mmol)), 4,4′-DDS (1.31 g (5.26 mmol)), X-22-1660 B-3 (2.66 g (0.61 mmol)), 1,3, 5-TAPOB (0.21 g (0.53 mmol)), NMP (75 g) and MMBAc (25 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 185,000 and 50,000, respectively.
  • Example 13 In Example 13, ODPA (6.16 g (19.8 mmol)), PMDA (0.49 g (2.26 mmol)), and X-22-168- were added to a 200 mL four-necked flask under a stream of dry nitrogen. P5-B (2.19 g (0.52 mmol)), m-TB (4.80 g (22.6 mmol)), NMP (75 g) and MMBAc (25 g) were added and heated and stirred at 80 ° C. . After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 67,000 and 32,000, respectively.
  • Example 14 In Example 14, ODPA (6.09 g (19.6 mmol)), BSAA (0.90 g (2.18 mmol)), and m-TB (4. 20 g) in a 200 mL four-necked flask under a stream of dry nitrogen. 53 g (21.3 mmol)), X-22-1 660 B-3 (2.12 g (0.49 mmol)), NMP (75 g) and MMBAc (25 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 65,000 and 31,000, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 15 In Example 15, ODPA (7.18 g (23.2 mmol)), BPAF (1.18 g (2.57 mmol)), and m-TB (5. 5 g (2.57 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen. 34 g (25.1 mmol)), X-22-1 660 B-3 (2.58 g (0.59 mmol)), NMP (75 g) and MMBAc (25 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 66,000 and 31,000, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 16 In Example 16, ODPA (7.74 g (25.0 mmol)), PMDA (0.61 g (2.77 mmol)), and CHDA (0.63 g (0.63 g) in a 200 mL four-necked flask under a stream of dry nitrogen. 5.55 mmol)), m-TB (4.58 g (21.6 mmol)), X-22-1 660 B-3 (2.81 g (0.64 mmol)), NMP (75 g), MMBAC (25 g) And the mixture was heated and stirred at 80.degree. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 71,000 and 34,000, respectively.
  • Example 17 In Example 17, BPDA (5.06 g (17.2 mmol)), PMDA (0.42 g (1.91 mmol)), and TFMB (5.98 g (5.98 g (1.91 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen) 18.7 mmol), X-22-1 660 B-3 (1.93 g (0.44 mmol)), NMP (75 g), and MMBAc (25 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 85,000 and 46,000, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 18 In Example 18, BPDA (5.06 g (17.2 mmol)), PMDA (0.42 g (1.91 mmol)), and TFMB (3.98 g (3.98 g) in a 200 mL four-necked flask under a stream of dry nitrogen. 12.4 mmol), 4,4'-DDS (1.55 g (6.23 mmol)), X-22-1 660 B-3 (1.93 g (0.44 mmol)), NMP (75 g), MMBAc (25 g) was added and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 75,000 and 45,000, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 19 In Example 19, BPDA (4.50 g (15.3 mmol)), PMDA (0.42 g (1.91 mmol)), and BPAF (0.88 g (b) in a 200 mL four-necked flask under a stream of dry nitrogen. 1.91 mmol), TFMB (3.99 g (12.5 mmol)), 4,4'-DDS (1.55 g (6.25 mmol)), and X-22-1 660 B-3 (1.94 g (1. 9 g)). 0.44 mmol), NMP (75 g), and MMBAc (25 g) were added and stirred while heating at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 73, 500 and 40, 000, respectively.
  • Example 20 In Example 20, BPDA (3.38 g (11.5 mmol)), PMDA (0.42 g (1.91 mmol)), and BPAF (2.64 g (b) in a 200 mL four-necked flask under a stream of dry nitrogen. 5.75 mmol)), TFMB (4.00 g (12.5 mmol)), 4,4'-DDS (1.55 g (6.25 mmol)), and X-22-1 660 B-3 (1.93 g (D). 0.44 mmol), NMP (75 g), and MMBAc (25 g) were added and stirred while heating at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 73,000 and 44,000, respectively.
  • Example 21 In Example 21, BPDA (2.25 g (7.64 mmol)), PMDA (0.42 g (1.91 mmol)), and BPAF (4.38 g (4.38 g) in a 200 mL four-necked flask under a stream of dry nitrogen). 9.55 mmol)), TFMB (4.00 g (12.5 mmol)), 4,4'-DDS (1.55 g (6.23 mmol)), and X-22-1660 B-3 (1.93 g) 0.44 mmol), NMP (75 g), and MMBAc (25 g) were added and stirred while heating at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 70,000 and 42,500, respectively.
  • Example 22 In Example 22, 0.12 g of 2-ethyl-4-methylimidazole is added to the varnish (100 g) obtained in Example 20 (the mass corresponding to 0.1 parts by mass with respect to 100 parts by mass of the polyimide precursor) ) To give a varnish of Example 22.
  • Example 23 In Example 23, to the varnish (100 g) obtained in Example 20, 0.36 g of 2-ethyl-4-methylimidazole (mass corresponding to 0.3 parts by mass with respect to 100 parts by mass of polyimide precursor) ) To give a varnish of Example 23.
  • Example 24 In Example 24, 0.12 g of 3,5-dihydroxybenzoic acid (mass corresponding to 0.1 parts by mass with respect to 100 parts by mass of a polyimide precursor) based on the varnish (100 g) obtained in Example 20 The varnish was added in Example 24.
  • Example 25 In Example 25, BPDA (3.38 g (11.5 mmol)), PMDA (0.42 g (1.92 mmol)), and BPAF (2.64 g (b) in a 200 mL four-necked flask under a stream of dry nitrogen.
  • Example 26 In Example 26, BPDA (3.38 g (11.5 mmol)), PMDA (0.42 g (1.92 mmol)), and BPAF (2.64 g (b) in a 200 mL four-necked flask under a stream of dry nitrogen. 5.75 mmol)), TFMB (3.87 g (12.1 mmol)), 4,4'-DDS (1.55 g (6.25 mmol)), and TAB-S (0.053 g (0.19 mmol)) ), X-22-1 660 B-3 (1.94 g (0.44 mmol)), NMP (75 g) and MMBAc (25 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 96,000 and 49,500, respectively.
  • Mw weight average molecular weight
  • Mn number average mo
  • Example 27 In Example 27, BPDA (3.38 g (11.5 mmol)), PMDA (0.42 g (1.92 mmol)), and BPAF (2.64 g (b) in a 200 mL four-necked flask under a stream of dry nitrogen. 5.75 mmol)), TFMB (3.00 g (9.36 mmol)), 4,4'-DDS (2.33 g (9.36 mmol)), and X-22-1660 B-3 (1.94 g (D). 0.44 mmol), NMP (75 g), and MMBAc (25 g) were added and stirred while heating at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 68,000 and 40,000, respectively.
  • Example 28 In Example 28, BPDA (3.38 g (11.5 mmol)), PMDA (0.42 g (1.92 mmol)), and BPAF (2.64 g (b) in a 200 mL four-necked flask under a stream of dry nitrogen. 5.75 mmol), TFMB (2.00 g (6.27 mmol)), 4,4'-DDS (3.09 g (12.46 mmol)), X-22-1 660 B-3 (1.94 g (0) .44 mmol)), NMP (75 g) and MMBAc (25 g) were added and stirred while heating at 80.degree. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 64,000 and 37,000, respectively.
  • Example 29 In Example 29, ODPA (7.37 g (23.8 mmol)), PMDA (0.58 g (2.64 mmol)), and m-TB (4. 5 g (2.64 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen. 35 g (20.5 mmol)), 4,4'-DDS (1.31 g (5.28 mmol)), X-22-1 660 B-3 (2.67 g (0.61 mmol)), NMP (90 g) And MMBAC (10 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 70,000 and 32,500, respectively.
  • Example 30 In Example 30, ODPA (7.37 g (23.8 mmol)), PMDA (0.58 g (2.64 mmol)), and m-TB (4. 5 g (2.64 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen. 35 g (20.5 mmol)), 4,4'-DDS (1.31 g (5.28 mmol)), X-22-1 660 B-3 (2.67 g (0.61 mmol)), NMP (63 g) And MMBAC (37 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 67, 500 and 31,500, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 31 In Example 31, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), and m-TB (4. 5 g (2.24 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen. 64 g (21.9 mmol)), X-22-1 660 B-3 (2.26 g (0.51 mmol)), NMP (55 g) and MMBAc (45 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 63,000 and 30,000, respectively.
  • Example 32 In Example 32, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), and m-TB (4. 5 g (2.24 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen. 64 g (21.9 mmol)), X-22-1 660 B-3 (2.26 g (0.51 mmol)), NMP (96 g) and MMBAc (4 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 70,000 and 33,000, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 33 In Example 33, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), and m-TB (4. 5 g (2.24 mmol)) in a 200 mL four-necked flask under a stream of dry nitrogen. 64 g (21.9 mmol)), X-22-1 660 B-3 (2.26 g (0.51 mmol)), NMP (30 g) and MMBAc (70 g) were added, and the mixture was heated and stirred at 80 ° C. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 59,000 and 28,000, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Example 34 In Example 34, ODPA (4.41 g (14.2 mmol)), PMDA (0.62 g (2.84 mmol)), and PMDA-HS (2. 55 g (11.4 mmol)), m-TB (5.90 g (27.8 mmol)), X-22-1 660 B-3 (2.88 g (0.65 mmol)), NMP (75 g), MMBAc (25 g) was added and the mixture was heated and stirred at 80.degree. After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 67,000 and 30,000, respectively.
  • Example 35 In Example 35, PMDA-HS (6.20 g (27.7 mmol)), PMDA (0.67 g (3.07 mmol)), and m-TB (m-TB) in a 200 mL four-necked flask under a stream of dry nitrogen 6.38 g (30.0 mmol)), X-22-1 660 B-3 (3.11 g (0.71 mmol)), NMP (75 g) and MMBAc (25 g) were added and heated and stirred at 80 ° C. . After 8 hours, cool down to a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 55,000 and 25,000, respectively.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • compositions of the varnishes synthesized in Examples 1 to 35 and Comparative Examples 1 to 7 and the results of evaluation carried out using those varnishes are shown in Tables 1A-1, 1A-2, 1B-1, and 1B-2. , Table 1C, and Table 1D.
  • SP in a table
  • surface is SP value.
  • VP in a table
  • surface is a vapor pressure in 20 degreeC.
  • Example 36 In Example 36, using the varnish obtained in Example 1, a polyimide resin film was produced by the method described in the third item. Thereafter, a touch panel was manufactured by the method described in the above-mentioned 17th item.
  • Example 37 SiON (film forming temperature: 350 ° C., film thickness 200 nm) was formed on the polyimide resin film by plasma CVD. A touch panel was produced in the same manner as in Example 36 except for the film formation.
  • Example 38 SiO 2 (film forming temperature: 350 ° C., film thickness 100 nm) and SiN (film forming temperature: 350 ° C., film thickness 100 nm) were formed in this order on the polyimide resin film by plasma CVD.
  • a touch panel was produced in the same manner as in Example 36 except for the film formation.
  • Example 39 SiN (film forming temperature: 350 ° C., film thickness 100 nm) and SiO 2 (film forming temperature: 350 ° C., film thickness 100 nm) were formed in this order on the polyimide resin film by plasma CVD.
  • a touch panel was produced in the same manner as in Example 36 except for the film formation.
  • Example 40 SiO 2 (film forming temperature: 350 ° C., film thickness 200 nm) was formed on the polyimide resin film by plasma CVD. A touch panel was produced in the same manner as in Example 36 except for the film formation.
  • Example 41 In Example 41, using the varnish obtained in Example 5, a polyimide resin film was produced by the method shown in the third item. Thereafter, a touch panel was manufactured by the method described in the above-mentioned 17th item.
  • Example 42 SiON (film forming temperature: 350 ° C., film thickness 200 nm) was formed on the polyimide resin film by plasma CVD.
  • a touch panel was produced in the same manner as in Example 41 except for the film formation.
  • Example 43 SiO 2 (film forming temperature: 350 ° C., film thickness 100 nm) and SiN (film forming temperature: 350 ° C., film thickness 100 nm) were formed in this order on the polyimide resin film by plasma CVD.
  • a touch panel was produced in the same manner as in Example 41 except for the film formation.
  • Example 44 In Example 44, SiN (film forming temperature: 350 ° C., film thickness 100 nm) and SiO 2 (film forming temperature: 350 ° C., film thickness 100 nm) were formed in this order on the polyimide resin film by plasma CVD. A touch panel was produced in the same manner as in Example 41 except for the film formation.
  • Example 45 SiO 2 (film forming temperature: 350 ° C., film thickness 200 nm) was formed by plasma CVD on the polyimide resin film.
  • a touch panel was produced in the same manner as in Example 41 except for the film formation.
  • Example 46 In Example 46, the varnish obtained in Example 14 was used to prepare a polyimide resin film by the method described in the third item. Thereafter, a touch panel was manufactured by the method described in the above-mentioned 17th item.
  • Example 47 In Example 47, the varnish obtained in Example 4 was used to prepare a polyimide resin film by the method described in the third item. Thereafter, a touch panel was manufactured by the method described in the above-mentioned 17th item.
  • Example 48 In Example 48, the varnish obtained in Example 22 was used to prepare a polyimide resin film by the method described in the third item. Thereafter, a touch panel was manufactured by the method described in the above-mentioned 17th item.
  • Example 49 In Example 49, the varnish obtained in Example 26 was used to prepare a polyimide resin film by the method described in the third item. Thereafter, a touch panel was manufactured by the method described in the above-mentioned 17th item.
  • the polyimide precursor resin composition, the polyimide resin composition, the polyimide resin film, the method of producing a laminate, the method of producing a color filter, the method of producing a liquid crystal element, and the method of producing an organic EL element according to the present invention A polyimide precursor resin composition having good slit coatability and suppressing white turbidity and residual stress of the obtained polyimide film, a polyimide resin composition using the same, a polyimide resin film, and a method for producing a laminate It is suitable for the manufacturing method of a color filter, the manufacturing method of a liquid crystal element, and the manufacturing method of an organic EL element.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Electroluminescent Light Sources (AREA)
  • Laminated Bodies (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine de précurseur de polyimide, qui contient : un précurseur de polyimide (A) contenant une structure représentée par la formule générale (1) et un motif structural représenté par la formule générale (2) ; et un solvant (B). Le précurseur de polyimide (A) contient 5 à 30 % en masse de la structure représentée par la formule générale (1), la quantité du précurseur de polyimide (A) total étant de 100 % en masse. Le solvant (B) contient au moins un solvant (B1) ayant un paramètre de solubilité de 7,7 à 9,0, et au moins un solvant (B2) ayant un paramètre de solubilité supérieur à 9,0 mais non supérieur à 12,5. (Dans la formule générale (1), R1 et R2 représentent chacun d'une manière indépendante un groupe organique monovalent ayant 1 à 20 atomes de carbone, et m représente un entier de 3 à 200.) (Dans la formule générale (2), R3 représente un groupe organique divalent, R4 représente un groupe organique tétravalent, et Y1 et Y2 représentent chacun d'une manière indépendante un atome d'hydrogène, un groupe organique monovalent ayant 1 à 10 atomes de carbone, ou un groupe alkylsilyle monovalent ayant 1 à 10 atomes de carbone.)
PCT/JP2018/033281 2017-09-26 2018-09-07 Composition de résine de précurseur de polyimide, composition de résine de polyimide, film de résine de polyimide, procédé de production d'un produit stratifié, procédé de production d'un filtre couleur, procédé de production d'un élément cristal liquide, et procédé de production d'un élément el organique WO2019065164A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201880061722.4A CN111133054B (zh) 2017-09-26 2018-09-07 聚酰亚胺前体树脂组合物、聚酰亚胺树脂组合物、聚酰亚胺树脂膜
KR1020207008170A KR20200052303A (ko) 2017-09-26 2018-09-07 폴리이미드 전구체 수지 조성물, 폴리이미드 수지 조성물, 폴리이미드 수지막, 적층체의 제조 방법, 컬러 필터의 제조 방법, 액정 소자의 제조 방법 및 유기 el 소자의 제조 방법
JP2018548158A JPWO2019065164A1 (ja) 2017-09-26 2018-09-07 ポリイミド前駆体樹脂組成物、ポリイミド樹脂組成物、ポリイミド樹脂膜、積層体の製造方法、カラーフィルタの製造方法、液晶素子の製造方法および有機ｅｌ素子の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-184501 2017-09-26
JP2017184501 2017-09-26

Publications (1)

Publication Number Publication Date
WO2019065164A1 true WO2019065164A1 (fr) 2019-04-04

Family

ID=65901303

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/033281 WO2019065164A1 (fr) 2017-09-26 2018-09-07 Composition de résine de précurseur de polyimide, composition de résine de polyimide, film de résine de polyimide, procédé de production d'un produit stratifié, procédé de production d'un filtre couleur, procédé de production d'un élément cristal liquide, et procédé de production d'un élément el organique

Country Status (5)

Country Link
JP (1) JPWO2019065164A1 (fr)
KR (1) KR20200052303A (fr)
CN (1) CN111133054B (fr)
TW (1) TW201920485A (fr)
WO (1) WO2019065164A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021241763A1 (fr) * 2020-05-28 2021-12-02
CN114341270A (zh) * 2019-09-24 2022-04-12 东丽株式会社 树脂膜、电子器件、树脂膜的制造方法及电子器件的制造方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111812943A (zh) * 2020-08-07 2020-10-23 武汉柔显科技股份有限公司 一种感光性树脂组合物、感光性树脂膜及图案形成方法
CN115210320A (zh) * 2020-09-21 2022-10-18 株式会社Lg化学 制造柔性显示装置用复合基底、使用其的制造柔性显示装置的方法和柔性显示装置用层合体

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0291124A (ja) * 1988-09-29 1990-03-30 Nippon Steel Chem Co Ltd ポリイミド共重合体及びその製造方法
JPH0291125A (ja) * 1988-09-29 1990-03-30 Nippon Steel Chem Co Ltd シリコーンポリイミド及びその製造方法
WO1991010699A1 (fr) * 1990-01-18 1991-07-25 Nippon Steel Chemical Co., Ltd. Resine pour proteger des semi-conducteurs
WO2006082814A1 (fr) * 2005-02-01 2006-08-10 National University Corporation Nagoya Institute Of Technology Polyimide hyper-ramifie modifie au siloxane
JP2010155895A (ja) * 2008-12-26 2010-07-15 Asahi Kasei E-Materials Corp 組成物、組成物からなる塗膜、塗膜を含む積層体、及び積層体を組み込んだ電子機器
WO2011122199A1 (fr) * 2010-03-31 2011-10-06 Jsr株式会社 Procédé de fabrication d'un substrat d'élément et composition à utiliser ici
JP2013050549A (ja) * 2011-08-30 2013-03-14 Asahi Glass Co Ltd ネガ型感光性樹脂組成物、隔壁、光学素子
WO2013047451A1 (fr) * 2011-09-29 2013-04-04 Jsr株式会社 Composition de résine et procédé de fabrication de film l'utilisant
WO2014098235A1 (fr) * 2012-12-21 2014-06-26 旭化成イーマテリアルズ株式会社 Précurseur de polyimide et composition de résine le contenant

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5948545B2 (ja) 1976-01-17 1984-11-27 サンケン電気株式会社 半導体装置用のリ−ド線
US5094919A (en) * 1988-06-30 1992-03-10 Nippon Steel Chemical Co., Ltd. Polyimide copolymers and process for preparing the same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0291124A (ja) * 1988-09-29 1990-03-30 Nippon Steel Chem Co Ltd ポリイミド共重合体及びその製造方法
JPH0291125A (ja) * 1988-09-29 1990-03-30 Nippon Steel Chem Co Ltd シリコーンポリイミド及びその製造方法
WO1991010699A1 (fr) * 1990-01-18 1991-07-25 Nippon Steel Chemical Co., Ltd. Resine pour proteger des semi-conducteurs
WO2006082814A1 (fr) * 2005-02-01 2006-08-10 National University Corporation Nagoya Institute Of Technology Polyimide hyper-ramifie modifie au siloxane
JP2010155895A (ja) * 2008-12-26 2010-07-15 Asahi Kasei E-Materials Corp 組成物、組成物からなる塗膜、塗膜を含む積層体、及び積層体を組み込んだ電子機器
WO2011122199A1 (fr) * 2010-03-31 2011-10-06 Jsr株式会社 Procédé de fabrication d'un substrat d'élément et composition à utiliser ici
JP2013050549A (ja) * 2011-08-30 2013-03-14 Asahi Glass Co Ltd ネガ型感光性樹脂組成物、隔壁、光学素子
WO2013047451A1 (fr) * 2011-09-29 2013-04-04 Jsr株式会社 Composition de résine et procédé de fabrication de film l'utilisant
WO2014098235A1 (fr) * 2012-12-21 2014-06-26 旭化成イーマテリアルズ株式会社 Précurseur de polyimide et composition de résine le contenant

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114341270A (zh) * 2019-09-24 2022-04-12 东丽株式会社 树脂膜、电子器件、树脂膜的制造方法及电子器件的制造方法
CN114341270B (zh) * 2019-09-24 2024-03-08 东丽株式会社 树脂膜、电子器件、树脂膜的制造方法及电子器件的制造方法
JPWO2021241763A1 (fr) * 2020-05-28 2021-12-02
WO2021241763A1 (fr) * 2020-05-28 2021-12-02 旭化成株式会社 Composition de résine

Also Published As

Publication number Publication date
TW201920485A (zh) 2019-06-01
CN111133054A (zh) 2020-05-08
CN111133054B (zh) 2022-11-11
KR20200052303A (ko) 2020-05-14
JPWO2019065164A1 (ja) 2020-09-03

Similar Documents

Publication Publication Date Title
TWI710584B (zh) 聚醯亞胺樹脂、聚醯亞胺樹脂組成物、使用其的觸控面板及其製造方法、彩色濾光片及其製造方法、液晶元件及其製造方法、有機el元件及其製造方法
JP6787124B2 (ja) 樹脂積層膜、それを含む積層体、ｔｆｔ基板、有機ｅｌ素子カラーフィルターならびにそれらの製造方法。
JP5773090B1 (ja) ポリイミド前駆体、それから得られるポリイミド樹脂膜、ならびにそれを含む表示素子、光学素子、受光素子、タッチパネル、回路基板、有機ｅｌディスプレイ、および、有機ｅｌ素子ならびにカラーフィルタの製造方法
JP5928447B2 (ja) フレキシブル基板、表示デバイスおよび受光デバイス
US9493614B2 (en) Polyimide precursor, polyimide, flexible substrate prepared therewith, color filter and production method thereof, and flexible display device
WO2019065164A1 (fr) Composition de résine de précurseur de polyimide, composition de résine de polyimide, film de résine de polyimide, procédé de production d'un produit stratifié, procédé de production d'un filtre couleur, procédé de production d'un élément cristal liquide, et procédé de production d'un élément el organique
JPWO2017126409A1 (ja) ポリイミドフィルムの製造方法、ポリイミドフィルム、ポリアミド酸溶液及び感光性組成物
JP7140108B2 (ja) 導電層付きフィルムおよびタッチパネル
JPWO2017068936A1 (ja) ディスプレイ基板用樹脂組成物、並びに、それを用いた耐熱性樹脂フィルム、有機ｅｌディスプレイ基板及び有機ｅｌディスプレイの製造方法
JP2020023671A (ja) ポリイミド前駆体樹脂組成物、ポリイミド樹脂組成物およびその膜状物、それを含む積層体、ならびにフレキシブルデバイス
JP2015227418A (ja) 樹脂膜、それを含む積層体、それを用いた有機ｅｌ素子基板、カラーフィルター基板およびそれらの製造方法ならびにフレキシブル有機ｅｌディスプレイ
JP2019101440A (ja) ポジ型感光性樹脂組成物、硬化膜、半導体装置および硬化膜のレリーフパターンの製造方法
WO2018029766A1 (fr) Film multicouche en résine, stratifié contenant celui-ci, substrat tft, filtre coloré d'élément électroluminescent organique, et procédés de fabrication associés
CN113166409B (zh) 聚酰亚胺前体、聚酰亚胺、聚酰亚胺树脂膜、及柔性器件

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018548158

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18862334

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20207008170

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18862334

Country of ref document: EP

Kind code of ref document: A1