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WO2018097142A1 - Composition pour former un substrat de dispositif flexible - Google Patents

Composition pour former un substrat de dispositif flexible Download PDF

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Publication number
WO2018097142A1
WO2018097142A1 PCT/JP2017/041876 JP2017041876W WO2018097142A1 WO 2018097142 A1 WO2018097142 A1 WO 2018097142A1 JP 2017041876 W JP2017041876 W JP 2017041876W WO 2018097142 A1 WO2018097142 A1 WO 2018097142A1
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Prior art keywords
flexible device
formula
composition
tetracarboxylic dianhydride
substrate
Prior art date
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Ceased
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PCT/JP2017/041876
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English (en)
Japanese (ja)
Inventor
鎮嘉 葉
浩 北
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Nissan Chemical Corp
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Nissan Chemical Corp
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Priority to JP2018552595A priority Critical patent/JP7011230B2/ja
Publication of WO2018097142A1 publication Critical patent/WO2018097142A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • 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
    • 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
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to a composition for forming a flexible device substrate, and more specifically, can be suitably used for forming a flexible device substrate such as a flexible display using a laser lift-off method particularly in the step of peeling the substrate from a carrier substrate. Relates to the composition.
  • Non-Patent Document 1 In manufacturing a flexible display, a polymer substrate made of polyimide or the like is provided on a glass carrier, and then a circuit or the like including an electrode or the like is formed on the substrate. Finally, the substrate is peeled off from the glass carrier together with the circuit or the like. There is a need.
  • the LLO method is employed, that is, when a glass carrier is irradiated with a light beam having a specific wavelength from the surface opposite to the surface on which a circuit or the like is formed, the light beam with the wavelength passes through the glass carrier. Only the nearby polymer (polyimide) absorbs this light and evaporates (sublimates). As a result, it has been reported that peeling of the substrate from the glass carrier can be performed selectively without affecting the circuit or the like provided on the substrate, which determines the performance of the display.
  • the LLO method is increasingly used as a substrate peeling method that is extremely superior in the manufacture of flexible displays.
  • the demand for polymer substrates for flexible displays to which the LLO method can be applied will increase.
  • Promising semi-alicyclic polyimides and fully alicyclic polyimides that have been proposed as flexible display substrate materials have excellent heat resistance, low retardation, excellent flexibility, and excellent transparency.
  • the substrate has a problem that it is difficult to peel off the glass carrier by the LLO method.
  • the present invention has been made in view of such circumstances, and maintains excellent performance such as excellent heat resistance, low retardation, excellent flexibility, and excellent transparency, and by the LLO method. It is an object of the present invention to provide a composition for forming a flexible device substrate that gives a resin thin film having excellent performance as a base film of a flexible device substrate such as a flexible display substrate that can be easily peeled from a glass carrier.
  • the present inventors have obtained a tetracarboxylic dianhydride component containing an alicyclic tetracarboxylic dianhydride and a diamine component containing a fluorine-containing aromatic diamine.
  • a tetracarboxylic dianhydride component containing an alicyclic tetracarboxylic dianhydride and a diamine component containing a fluorine-containing aromatic diamine.
  • the present invention provides, as a first aspect, a tetracarboxylic dianhydride component containing an alicyclic tetracarboxylic dianhydride and an aromatic tetracarboxylic dianhydride represented by the formula (D1), and a fluorine-containing aromatic. It is related with the composition for flexible device board
  • E represents a single bond, a carbonyl group, an oxygen atom, a sulfur atom, SO or SO 2.
  • the composition for forming a flexible device substrate according to the first aspect in which the alicyclic tetracarboxylic dianhydride includes an alicyclic tetracarboxylic dianhydride represented by the formula (C1).
  • C1 alicyclic tetracarboxylic dianhydride represented by the formula (C1).
  • B 1 represents a tetravalent group selected from the group consisting of formulas (X-1) to (X-12).
  • the said fluorine-containing aromatic diamine is related with the composition for flexible device board
  • B 2 represents a divalent group selected from the group consisting of formulas (Y-1) to (Y-34)).
  • the tetracarboxylic dianhydride component contains 1 mol of the aromatic tetracarboxylic dianhydride represented by the formula (D1) with respect to the total number of moles of the tetracarboxylic dianhydride component. It is related with the composition for flexible device board
  • the present invention relates to a composition for forming a flexible device substrate.
  • the present invention relates to the flexible device substrate forming composition according to the fifth aspect, wherein the mass ratio of the polyimide and the silicon dioxide particles is 7: 3 to 3: 7.
  • the said average particle diameter is related with the composition for flexible device board
  • substrate formation of the flexible device used for a laser lift-off method As a 9th viewpoint, it is related with the flexible device board
  • a step of applying the flexible device substrate forming composition according to any one of the first aspect to the seventh aspect to a base material, drying and heating to form a flexible device substrate The present invention relates to a method for manufacturing a flexible device substrate, including a peeling step of peeling the flexible device substrate from the base material by a laser lift-off method.
  • the present invention while maintaining excellent performance of excellent heat resistance, low retardation, excellent flexibility, and excellent transparency (high light transmittance, low yellowness), it is easy from a glass carrier by the LLO method.
  • a composition for forming a flexible device substrate that provides a resin thin film having excellent performance as a base film of a flexible device substrate such as a flexible display substrate that can be peeled off can be provided.
  • the flexible device substrate according to the present invention is excellent in heat resistance, low retardation, excellent in flexibility, and further excellent in transparency (high light transmittance, low yellowness) and maintaining excellent performance, Since it can be easily peeled from the glass carrier by the LLO method, it can be suitably used as a substrate for flexible devices, particularly flexible displays.
  • a composition, a substrate and a production method according to the present invention have characteristics such as high heat resistance, low retardation, high flexibility, high transparency (high light transmittance, low yellowness) and releasability by the LLO method. It can sufficiently cope with the required progress in the field of flexile device substrates, particularly flexible display substrates.
  • the composition for forming a flexible device substrate of the present invention comprises a tetracarboxylic dianhydride component containing a specific alicyclic tetracarboxylic dianhydride and an aromatic tetracarboxylic dianhydride represented by the formula (D1); Further, it contains a polyimide which is an imidized product of polyamic acid, which is a reaction product with a diamine component containing a specific fluorine-containing aromatic diamine, and an organic solvent, and optionally contains silicon dioxide particles, a crosslinking agent and other components.
  • E represents a single bond, a carbonyl group, an oxygen atom, a sulfur atom, SO or SO 2.
  • the polyimide used in the present invention is a polyimide having an alicyclic skeleton in the main chain, and preferably an alicyclic tetracarboxylic dianhydride and an aromatic tetracarboxylic acid represented by the above formula (D1). It is a polyimide obtained by imidizing a polyamic acid obtained by reacting a tetracarboxylic dianhydride component containing an anhydride and a diamine component containing a fluorine-containing aromatic diamine.
  • the polyimide is preferably an imidized polyamic acid
  • the polyamic acid includes an alicyclic tetracarboxylic dianhydride and an aromatic tetracarboxylic dianhydride represented by the formula (D1).
  • It is a reaction product of a tetracarboxylic dianhydride component containing and a diamine component containing a fluorine-containing aromatic diamine.
  • the alicyclic tetracarboxylic dianhydride includes an alicyclic tetracarboxylic dianhydride represented by the following formula (C1)
  • the fluorine-containing aromatic diamine is represented by the following formula (A1 It is preferable that it contains the diamine represented by this.
  • B 1 represents a tetravalent group selected from the group consisting of formulas (X-1) to (X-12). (In the formula, a plurality of R's independently represent a hydrogen atom or a methyl group, and * represents a bond.)
  • B 2 represents a divalent group selected from the group consisting of formulas (Y-1) to (Y-34)). (In the formula, * represents a bond.)
  • B 1 in the formula is represented by the formulas (X-1), (X-4), (X-6), (X-7) It is preferable that it is a compound represented by this.
  • B 2 in the formula is preferably a compound represented by the formula (Y-12) or (Y-13).
  • the aromatic tetracarboxylic dianhydride represented by the formula (D1) is a compound represented by the following formula selected from the group consisting of the formula (Z-1) to the formula (Z-6) Is mentioned.
  • aromatic tetracarboxylic dianhydrides represented by the formula (D1) compounds represented by the formulas (Z-1) and (Z-2) are preferable.
  • Preferred examples include the alicyclic tetracarboxylic dianhydride represented by the above formula (C1) and the aromatic tetracarboxylic dianhydride represented by the above formula (D1), and the above formula (A1).
  • the polyimide obtained by imidizing the polyamic acid obtained by reacting with the diamine to be produced contains a monomer unit represented by the formula (2) described later.
  • a flexible device substrate that is excellent in heat resistance, low retardation, excellent flexibility, and excellent in transparency, and that can be easily peeled off from a glass carrier by the LLO method.
  • the alicyclic tetracarboxylic dianhydride for example, the alicyclic tetracarboxylic dianhydride represented by the above formula (C1), relative to the total number of moles of the tetracarboxylic dianhydride component. It is preferably 70 mol% or more, more preferably 80 mol% or more, and the aromatic tetracarboxylic acid represented by the formula (D1) with respect to the total number of moles of the tetracarboxylic dianhydride component.
  • the acid dianhydride is preferably 1 mol% or more and 30 mol% or less, more preferably 5 mol% or more and 20 mol% or less.
  • the fluorine-containing aromatic diamine for example, the diamine represented by the formula (A1) is preferably 90% by mole or more, more preferably 95% by mole or more with respect to the total number of moles of the diamine component. .
  • the diamine represented by the said Formula (A1) may be sufficient as all (100 mol%) of a diamine component.
  • the polyimide used by this invention contains the monomer unit represented by following formula (1), and the monomer unit represented by following formula (1 ').
  • E 1 means a single bond or a carbonyl group.
  • those represented by the formula (1-1) or the formula (1-2) are preferable, and those represented by the formula (1-1) are more preferable.
  • the polyimide used in the present invention is represented by the formula (2) in addition to the monomer unit represented by the formula (1) and the monomer unit represented by the formula (1 ′). Further containing monomer units.
  • the polyimide used in the present invention includes a monomer unit represented by the above formula (1), a monomer unit represented by the formula (1 ′), and a monomer unit represented by the formula (2)
  • the monomer unit represented by the formula (1) + the monomer unit represented by the formula (2): the monomer unit represented by the formula (1 ′) 7: 3 to 19: 1
  • the polyimide of the present invention is a tetracarboxylic dianhydride containing an alicyclic tetracarboxylic dianhydride represented by the above formula (C1) and an aromatic tetracarboxylic dianhydride represented by the formula (D1).
  • C1 alicyclic tetracarboxylic dianhydride
  • D1 aromatic tetracarboxylic dianhydride
  • the monomer unit represented by the above formula (1), formula (1 ′) and formula (2) Other monomer units may be included.
  • the content ratio of the other monomer units is arbitrarily determined as long as the characteristics of the flexible device substrate formed from the composition for forming a flexible device substrate of the present invention are not impaired.
  • the ratio of the tetracarboxylic dianhydride component containing the alicyclic tetracarboxylic dianhydride represented by the formula (C1) and the aromatic tetracarboxylic dianhydride represented by the formula (D1) The monomer unit derived from the diamine component containing the diamine represented by the formula (A1), for example, the total number of moles of the monomer unit represented by the formula (1) and the monomer unit represented by the formula (1 ′) On the other hand, or when the monomer unit represented by the formula (2) is included, the monomer unit represented by the formula (1), the monomer unit represented by the formula (1 ′), and the formula (2) It is preferably less than 20 mol%, more preferably less than 10 mol%, and even more preferably less than 5 mol%, based on the total number of moles of the monomer units represented.
  • Examples of such other monomer units include, but are not limited to, monomer units having other polyimide structures represented by the formula (3).
  • A represents a tetravalent organic group, preferably a tetravalent group represented by any of the following formulas (A-1) to (A-4).
  • B represents a divalent organic group, preferably a divalent group represented by any one of formulas (B-1) to (B-11).
  • * represents a bond.
  • B represents the above formulas (Y-1) to ( Y-34) may be a divalent group.
  • A represents the above formulas (X-1) to (X It may be a tetravalent group represented by any of -12).
  • a and B may contain only a monomer unit composed of only one of the groups exemplified by the following formula, for example.
  • at least one of A and B may contain two or more monomer units selected from two or more groups exemplified below.
  • each monomer unit is bonded in an arbitrary order.
  • a polyimide having a monomer unit represented by the above formula (1) and a monomer unit represented by the formula (1 ′) is bicyclo [2,2 as an alicyclic tetracarboxylic dianhydride. , 2] octane-2,3,5,6-tetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as aromatic tetracarboxylic dianhydride, or A tetracarboxylic dianhydride component including 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and a diamine component including a diamine represented by the following formula (4) are polymerized in an organic solvent.
  • polyimide used in the present invention has a monomer unit represented by the above formula (2) in addition to the monomer unit represented by the above formula (1) and the monomer unit represented by the formula (1 ′),
  • Polyimides containing monomer units represented by formula (1), formula (1 ′) and formula (2) are bicyclo [2,2,2] octane-2 as alicyclic tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as 3,5,6-tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride, or 3,3 ′, 4
  • a tetracarboxylic dianhydride component including 1,2,3,4-cyclobutanetetracarboxylic dianhydride and a diamine represented by the following formula (4) Polymerization
  • Examples of the diamine represented by the above formula (4) include 2,2′-bis (trifluoromethyl) benzidine, 3,3′-bis (trifluoromethyl) benzidine, and 2,3′-bis (trifluoromethyl).
  • Benzidine is mentioned.
  • the flexible device substrate of the present invention has excellent heat resistance, low retardation, excellent flexibility, and excellent transparency (high light transmittance, 2,2′-bis (trifluoro) represented by the following formula (4-1) from the viewpoint of maintaining excellent performance (low yellowness) and being easily peelable from the glass carrier by the LLO method.
  • Methyl) benzidine or 3,3′-bis (trifluoromethyl) benzidine represented by the following formula (4-2) is preferably used, and in particular, 2,2′-bis (trifluoromethyl) benzidine is preferably used. preferable.
  • the tetracarboxylic acid in which the polyimide used by this invention contains the alicyclic tetracarboxylic dianhydride represented by the above-mentioned formula (C1) and the aromatic tetracarboxylic dianhydride represented by the formula (D1)
  • a monomer unit derived from a diamine component containing a dianhydride component and a diamine represented by the formula (A1) for example, a monomer unit represented by the above formula (1), a monomer unit represented by the formula (1 ′)
  • formula (1), formula (1 ′), formula (2) and formula (3) In addition to the above-mentioned three types of tetracarboxylic dianhydrides as a tetracarboxylic dianhydride component, the polyimide containing each monomer unit represented by) is a tetracarboxylic dianhydride represented by the following formula (5):
  • a in the above formula (5) and B in the formula (6) have the same meaning as A and B in the above formula (3), respectively.
  • examples of the tetracarboxylic dianhydride represented by the formula (5) include pyromellitic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride, 11, 11- Bis (trifluoromethyl) -1H-difluoro [3,4-b: 3 ′, 4′-i] xanthene-1,3,7,9- (11H-tetraone), 6,6′-bis (trifluoro Methyl)-[5,5′-biisobenzofuran] -1,1 ′, 3,3′-tetraone, 4,6,10,12-tetrafluorodifuro [3,4-b: 3 ′, 4 ′ -I] dibenzo [b, e] [1,4] dioxin-1,3,7,9-tetraone, 4,8-bis (trifluoromethoxy) benzo [1,2-c: 4,5-c ' Difuran-1,
  • Alicyclic tetracarboxylic dianhydrides such as, but not limited to, aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride.
  • aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride.
  • Examples of the diamine represented by the formula (6) include 2- (trifluoromethyl) benzene-1,4-diamine, 5- (trifluoromethyl) benzene-1,3-diamine, and 5- (trifluoromethyl).
  • aromatic diamines in which B in the formula (6) is a divalent group represented by any one of the formulas (B-1) to (B-11) are preferable, that is, 2,2 ′.
  • -Bis (trifluoromethoxy)-(1,1'-biphenyl) -4,4'-diamine [other name: 2,2'-dimethoxybenzidine], 4,4 '-(perfluoropropane-2,2- Diyl) dianiline, 2,5-bis (trifluoromethyl) benzene-1,4-diamine, 2- (trifluoromethyl) benzene-1,4-diamine, 2-fluorobenzene-1,4-diamine, 4, 4′-oxybis [3- (trifluoromethyl) aniline], 2,2 ′, 3,3 ′, 5,5 ′, 6,6′-octafluoro [1,1′-biphenyl] -4,4 ′ -
  • the polyimide used in the present invention contains the alicyclic tetracarboxylic dianhydride represented by the above formula (C1) and the aromatic tetracarboxylic dianhydride represented by the formula (D1). It is obtained by imidizing a polyamic acid obtained by reacting a tetracarboxylic dianhydride component with a diamine component containing a fluorine-containing aromatic diamine.
  • bicyclo [2,2,2] octane-2,3,5,6-tetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic acid Dianhydrides or bicyclo [2,2,2] octane-2,3,5,6-tetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, and
  • the charging ratio (molar ratio) of the diamine component in the reaction between the tetracarboxylic dianhydride component and the diamine component is appropriately set in consideration of the molecular weight of the polyamic acid and the polyimide obtained by subsequent imidization.
  • the tetracarboxylic dianhydride component can usually be about 0.8 to 1.2, for example about 0.9 to 1.1, preferably about 0.1. It is about 95 to 1.02. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.
  • the organic solvent used in the reaction between the tetracarboxylic dianhydride component and the diamine component is not particularly limited as long as it does not adversely affect the reaction and the produced polyamic acid dissolves. Specific examples are given below.
  • the solvent does not dissolve the polyamic acid, it may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.
  • water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the generated polyamic acid, it is preferable to use a dehydrated and dried organic solvent as much as possible.
  • a dispersion or solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic dianhydride is added here.
  • a method of alternately adding a tetracarboxylic dianhydride component and a diamine compound component may be used.
  • the tetracarboxylic dianhydride component and / or the diamine component are composed of a plurality of types of compounds, they may be reacted in a premixed state, individually individually, or further individually. Low molecular weight substances may be mixed and reacted to form high molecular weight substances.
  • the temperature at the time of synthesizing the polyamic acid may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, and can be selected, for example, from -20 ° C to 150 ° C. C. to 100.degree. C., usually about 0 to 100.degree. C., preferably about 0 to 70.degree.
  • the reaction time depends on the reaction temperature and the reactivity of the raw material, it cannot be defined unconditionally, but is usually about 1 to 100 hours.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult.
  • the total concentration of the tetracarboxylic dianhydride component and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 40% by mass.
  • the initial stage of the reaction can be performed at a high concentration, and then an organic solvent can be added.
  • Examples of the method for imidizing the polyamic acid include thermal imidization in which the polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.
  • the temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
  • the chemical (catalyst) imidization of polyamic acid is carried out by adding a basic catalyst and an acid anhydride to a polyamic acid solution, and igniting the system under a temperature condition of ⁇ 20 to 250 ° C., preferably 0 to 180 ° C. This can be done by stirring.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 1.5 to 20 mol times the amide acid group of the polyamic acid, and the amount of the acid anhydride is 1 to 50 mol of the amide acid group of the polyamic acid. Double, preferably 2 to 30 mole times.
  • Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, 1-ethylpiperidine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the dehydration cyclization rate (imidization rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the use and purpose. Particularly preferably, it is 50% or more.
  • the filtrate after filtering the reaction solution, the filtrate can be used as it is, or diluted or concentrated to form a flexible device substrate-forming composition, which is mixed with silicon dioxide or the like to be described later. And it is good also as a composition for flexible device board
  • filtration when filtration is performed, not only can the contamination of the resin thin film obtained be deteriorated in heat resistance, flexibility, or deterioration of linear expansion coefficient characteristics, but also efficiently obtain a composition for forming a flexible device substrate. Can do.
  • the polyimide used in the present invention has a weight average molecular weight (Mw) in terms of polystyrene of gel permeation chromatography (GPC) in consideration of the strength of the resin thin film, workability when forming the resin thin film, uniformity of the resin thin film, and the like. ) Is preferably 5,000 to 200,000.
  • the reaction solution may be poured into a poor solvent and precipitated.
  • the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, isopropanol, and water.
  • a polymer precipitated in a poor solvent and collected by filtration can be dried at normal temperature or under reduced pressure at room temperature or by heating.
  • the polymer collected by precipitation is re-dissolved in an organic solvent and re-precipitation is collected 2 to 10 times, impurities in the polymer can be reduced.
  • the organic solvent for dissolving the resin component in the reprecipitation collection step is not particularly limited. Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetra Methyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, ⁇ -butyrolactone, 1,3-dimethyl-imidazolidinone, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate , Propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pent
  • the composition for forming a flexible device substrate of the present invention can contain silicon dioxide (silica).
  • Silicon dioxide (silica) that can be used is not particularly limited, but silicon dioxide in the form of particles, for example, an average particle diameter of 100 nm or less, for example, 5 nm to 100 nm, preferably 5 nm to 55 nm, and a highly transparent thin film with high reproducibility.
  • the thickness is preferably 5 nm to 50 nm, more preferably 5 nm to 45 nm, still more preferably 5 nm to 35 nm, and still more preferably 5 nm to 30 nm.
  • the average particle diameter of silicon dioxide particles is an average particle diameter value calculated from specific surface area values measured by a nitrogen adsorption method using silicon dioxide particles.
  • colloidal silica having the above average particle size can be suitably used, and silica sol can be used as the colloidal silica.
  • silica sol there can be used an aqueous silica sol produced by a known method using a sodium silicate aqueous solution as a raw material, and an organosilica sol obtained by substituting water as a dispersion medium of the aqueous silica sol with an organic solvent.
  • alkoxysilanes such as methyl silicate and ethyl silicate are obtained by hydrolysis and condensation in an organic solvent such as alcohol in the presence of a catalyst (for example, an alkali catalyst such as ammonia, an organic amine compound, or sodium hydroxide).
  • a silica sol obtained by replacing the silica sol with another organic solvent can be used.
  • the present invention preferably uses an organosilica sol whose dispersion medium is an organic solvent.
  • Examples of the organic solvent in the above-described organosilica sol include: lower alcohols such as methyl alcohol, ethyl alcohol and isopropanol; linear amides such as N, N-dimethylformamide and N, N-dimethylacetamide; N-methyl-2- Examples include cyclic amides such as pyrrolidone; ethers such as ⁇ -butyrolactone; glycols such as ethyl cellosolve and ethylene glycol, acetonitrile, and the like. This substitution can be performed by a usual method such as a distillation method or an ultrafiltration method.
  • the viscosity of the organosilica sol is about 0.6 mPa ⁇ s to 100 mPa ⁇ s at 20 ° C.
  • organosilica sols examples include, for example, trade name MA-ST-S (methanol-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), trade name MT-ST (methanol-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.).
  • Product name XBA-ST xylene / n-butanol mixed solvent dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
  • product name EAC-ST ethyl acetate dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
  • product Name PMA-ST propylene glycol monomethyl ether acetate dispersed silica sol, Nissan Chemical Industries, Ltd.
  • Trade name MEK-ST methyl ethyl ketone dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
  • trade name MEK-ST-UP methyl ethyl ketone dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.
  • trade name MEK-ST-L examples thereof include, but are not limited to, methyl ethyl ketone-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd., and trade name MIBK-ST (methyl isobutyl ketone-dispersed silica sol, manufactured by Nissan Chemical Industries
  • the composition for forming a flexible device substrate of the present invention may further contain a cross-linking agent, and the cross-linking agent used here is a compound composed only of hydrogen atoms, carbon atoms, nitrogen atoms and oxygen atoms. And a crosslinking agent comprising a compound having two or more groups selected from the group consisting of a hydroxy group, an epoxy group, and an alkoxy group having 1 to 5 carbon atoms, and having a ring structure.
  • a cross-linking agent it is possible to realize a composition for forming a flexible device substrate that not only provides excellent solvent resistance but also provides a resin thin film suitable for a flexible device substrate with good reproducibility, as well as improved storage stability. can do.
  • the total number of hydroxy groups, epoxy groups and alkoxy groups having 1 to 5 carbon atoms per compound in the crosslinking agent is preferably 3 or more from the viewpoint of realizing the solvent resistance of the resulting resin thin film with good reproducibility. From the viewpoint of realizing the flexibility of the resulting resin thin film with good reproducibility, it is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.
  • ring structure possessed by the crosslinking agent include aryl rings such as benzene, nitrogen-containing heteroaryl rings such as pyridine, pyrazine, pyrimidine, pyridazine, 1,3,5-triazine, cyclopentane, cyclohexane, cycloheptane, etc.
  • cyclic amines such as cycloalkane ring, piperidine, piperazine, hexahydropyrimidine, hexahydropyridazine, hexahydro-1,3,5-triazine and the like.
  • the number of ring structures per compound in the crosslinking agent is not particularly limited as long as it is 1 or more. However, from the viewpoint of obtaining a resin thin film having high flatness by ensuring the solubility of the crosslinking agent in a solvent, 1 or 2 is preferable.
  • the ring structures may be condensed with each other, and an alkane having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a propane-2,2-diyl group, etc.
  • the ring structures may be bonded to each other through a linking group such as a diyl group.
  • the molecular weight of the crosslinking agent is not particularly limited as long as it has crosslinking ability and dissolves in the solvent to be used, but the solvent resistance of the resulting resin thin film, the solubility of the crosslinking agent itself in an organic solvent, and easy availability In consideration of properties, price, etc., it is preferably about 100 to 500, more preferably about 150 to 400.
  • the crosslinking agent may further have a group that can be derived from a hydrogen atom, a carbon atom, a nitrogen atom, and an oxygen atom, such as a ketone group or an ester group (bond).
  • crosslinking agent examples include compounds represented by any of the following formulas (K1) to (K5).
  • One preferred embodiment of formula (K4) is represented by formula (K4-1).
  • One preferred embodiment of the compound represented by formula (K5) is a compound represented by formula (K5-1).
  • each A 1 and A 2 independently represents an alkane-diyl group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a propane-2,2-diyl group, Among them, A 1 is preferably a methylene group or an ethylene group, more preferably a methylene group, and A 2 is preferably a methylene group or a propane-2,2-diyl group.
  • Each X is independently of each other hydroxy group, epoxy group (oxa-cyclopropyl group), methoxy group, ethoxy group, 1-propyloxy group, isopropyloxy group, 1-butyloxy group, t-butyloxy group, etc.
  • An alkoxy group having 1 to 5 carbon atoms is represented.
  • X is preferably an epoxy group in the formulas (K1) and (K5), and has 1 to 5 carbon atoms in the formulas (K2) and (K3) in consideration of the availability, price, etc. of the crosslinking agent.
  • An alkoxy group is preferable, and a hydroxy group is preferable in the formula (K4).
  • each n represents the number of — (A 1 -X) groups bonded to the benzene ring, and is an integer of 1 to 5 independently of each other, preferably 2 to 3, more preferably 3.
  • each A 1 is preferably the same group, and each X is preferably the same group.
  • the compounds represented by the above formulas (K1) to (K5) are skeleton compounds such as aryl compounds, heteroaryl compounds, and cyclic amines having the same ring structure as the ring structure in these compounds, epoxy alkyl halide compounds, It can be obtained by reacting an alkoxy halide compound or the like with a carbon-carbon coupling reaction or an N-alkylation reaction, or hydrolyzing the resulting alkoxy moiety.
  • a commercial item may be used for a crosslinking agent, and what was synthesize
  • combining method may be used for it.
  • Commercially available products include CYMEL (registered trademark) 300, 301, 303LF, 303ULF, 304, 350, 3745, XW3106, MM-100, 323, 325, 327, 328, Same 385, Same 370, Same 373, Same 380, Same 1116, Same 1130, Same 1133, Same 1141, Same 1161, Same 1168, Same 3020, Same 202, Same 203, Same 1156, Same MB-94, Same MB- 96, MB-98, 247-10, 651, 658, 683, 683, 688, 1158, MB-14, MI-12-I, MI-97-IX, U-65 UM-15, U-80, U-21-511, U-21-510, U-216-8, U-227-8, U-1050-10, U-1052 -8, the same
  • TEPIC registered trademark
  • V, S, HP, etc. L, PAS, VL, UC manufactured by Nissan Chemical Industries, Ltd.
  • TM-BIP-A manufactured by Asahi Organic Materials Co., Ltd.
  • 1,3,4,6-tetrakis (methoxymethyl) ) Glycoluril hereinafter abbreviated as TMG) (Tokyo Chemical Industry Co., Ltd.) 4,4'-methylenebis (N, N-diglycidylaniline) (Aldrich), HP-4032D, HP-7200L, HP-7200, HP-7200H, HP-7200HH, HP-7200HHH, HP- 4700, HP-4770, HP-5000, HP-6000, HP-4710, EXA-4850-150, EXA-4850-1000, EXA-4816, HP-820 (DIC Corporation), TG-G (Shikoku Chemicals) Kogyo Co., Ltd.).
  • the blending amount of the crosslinking agent is appropriately determined according to the type of the crosslinking agent and the like, and thus cannot be specified unconditionally, but is usually obtained with respect to the mass of the polyimide or the total mass of the polyimide and the silicon dioxide. From the viewpoint of ensuring flexibility of the obtained resin thin film and suppressing embrittlement, it is 50% by mass or less, preferably 100% by mass or less, and from the viewpoint of ensuring solvent resistance of the resulting resin thin film, 0.1% by mass. Above, preferably 1% by mass or more.
  • the composition for forming a resin thin film of the present invention contains an organic solvent in addition to the polyimide, optional silicon dioxide, a crosslinking agent and the like.
  • This organic solvent is not specifically limited, For example, the thing similar to the specific example of the reaction solvent used at the time of preparation of the said polyamic acid and a polyimide is mentioned. More specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, ⁇ - Examples include butyrolactone.
  • an organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and ⁇ -butyrolactone are preferable in view of obtaining a resin film having high flatness with good reproducibility.
  • composition for forming flexible device substrate is a composition for forming a flexible device substrate containing the polyimide, an organic solvent, and optionally silicon dioxide, a crosslinking agent and the like.
  • the composition for forming a flexible device substrate of the present invention is uniform and phase separation is not observed.
  • the solid content in the composition for forming a flexible device substrate of the present invention is usually in the range of 0.5 to 30% by mass, preferably 5% by mass or more and 20% by mass from the viewpoint of film uniformity. It is as follows.
  • solid content means the remaining components remove
  • the viscosity of the composition for forming a flexible device substrate is appropriately determined in consideration of the coating method used, the thickness of the resin thin film to be produced, and the like, but is usually 1 to 50,000 mPa ⁇ s at 25 ° C. .
  • various other organic or inorganic low-molecular or high-molecular compounds may be blended with the composition for forming a flexible device substrate of the present invention.
  • a catalyst an antifoaming agent, a leveling agent, a surfactant, a dye, a plasticizer, fine particles, a coupling agent, a sensitizer, and the like can be used.
  • the catalyst may be added for the purpose of reducing the retardation and linear expansion coefficient of the resin thin film.
  • the composition for forming a flexible device substrate of the present invention can be obtained by dissolving the polyimide obtained by the above-described method, and optionally silicon dioxide, a crosslinking agent, etc. in the above-mentioned organic solvent, If desired, silicon dioxide, a crosslinking agent or the like may be added to the reaction solution, and the organic solvent may be further added if desired.
  • the organic solvent is removed by applying the composition for forming a flexible device substrate of the present invention described above to a base material and drying and heating, and has excellent heat resistance, low retardation, excellent flexibility, and further transparency.
  • a resin thin film that can be easily peeled off from a glass carrier by the LLO method, that is, a flexible device substrate.
  • substrate formation of this invention are also this invention. It is a target of.
  • a base material used for manufacturing a flexible device substrate for example, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetylcellulose, ABS, AS, norbornene resin, etc.), metal , Stainless steel (SUS), wood, paper, glass, silicon wafer, slate, and the like.
  • plastic polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetylcellulose, ABS, AS, norbornene resin, etc.
  • metal Stainless steel
  • wood paper, glass, silicon wafer, slate, and the like.
  • the base material to be applied is glass or a silicon wafer from the viewpoint that existing equipment can be used, and the obtained flexible device substrate exhibits good peelability. Therefore, it is more preferable that it is glass.
  • a linear expansion coefficient of the base material to apply from a viewpoint of the curvature of the base material after coating, Preferably it is 40 ppm / degrees C or less, More preferably, it is 30 ppm / degrees C or less.
  • the method for applying the composition for forming a flexible device substrate on the base material is not particularly limited, and examples thereof include a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, and a bar coating method. , Die coating method, ink jet method, printing method (letter plate, intaglio plate, planographic plate, screen printing, etc.) and the like, and these can be appropriately used according to the purpose.
  • the heating temperature is preferably 300 ° C. or lower. If the temperature exceeds 300 ° C., the resulting resin thin film becomes brittle, and a resin thin film particularly suitable for display substrate use may not be obtained. Also, considering the heat resistance and linear expansion coefficient characteristics of the resulting resin thin film, after heating the applied flexible device substrate forming composition at 40 ° C. to 100 ° C. for 5 minutes to 2 hours, the heating temperature is gradually increased as it is. It is desirable to raise the temperature and finally heat at over 175 ° C. to 280 ° C. for 30 minutes to 2 hours. Thus, by heating at a temperature of two or more stages of drying the solvent and promoting molecular orientation, the low thermal expansion characteristics can be expressed with higher reproducibility.
  • the applied composition for forming a flexible device substrate is heated at 40 ° C. to 100 ° C. for 5 minutes to 2 hours, then at a temperature exceeding 100 ° C. to 175 ° C. for 5 minutes to 2 hours, and then at a temperature exceeding 175 ° C. to 280 ° C. It is preferable to heat for 5 minutes to 2 hours.
  • the appliance used for heating include a hot plate and an oven.
  • the heating atmosphere may be under air or under an inert gas such as nitrogen, and may be under normal pressure or under reduced pressure, and different pressures are applied at each stage of heating. May be.
  • the thickness of the resin thin film is appropriately determined in consideration of the type of the flexible device within a range of about 1 to 200 ⁇ m, but usually 1 to 60 ⁇ m when it is assumed to be used as a substrate for a flexible display.
  • the thickness is about 5 to 50 ⁇ m, and the thickness of the coating before heating is adjusted to form a resin thin film having a desired thickness.
  • the method for peeling the resin thin film formed in this way from the substrate is not particularly limited, and the resin thin film is cooled together with the substrate, and a thin film is cut and peeled or tension is applied via a roll. And a method of peeling off.
  • a laser lift-off (LLO) method can be adopted as a method for peeling a resin thin film from a substrate. That is, by irradiating the base material with a light beam having a specific wavelength from the surface opposite to the surface on which the resin thin film of the base material is formed, the light beam with the wavelength passes through the base material (for example, a glass carrier).
  • the resin thin film can be peeled off from the base material by absorbing this light only in the vicinity of the polyimide and evaporating the polyimide in the portion.
  • the laser beam used for peeling the resin thin film from the substrate by the laser lift-off method is not particularly limited, but an excimer laser is preferable.
  • the oscillation wavelength is ArF (193 nm), KrF (248 nm), XeCl (308 nm). ) And XeF (353 nm), and XeCl (308 nm) is particularly preferable.
  • the energy density of the irradiated laser beam typically, it includes a range of 200 mJ / cm 2 to 500 mJ / cm 2, for example, a range of 260 mJ / cm 2 to 420mJ / cm 2, 317mJ / cm 2 to 420 mJ / Examples include a range of cm 2, a range of 260 mJ / cm 2 to 330 mJ / cm 2, a range of 317 mJ / cm 2 to 330 mJ / cm 2, and a range of 260 mJ / cm 2 to 317 mJ / cm 2 .
  • the resin thin film according to a preferred embodiment of the present invention thus obtained can achieve high transparency with a light transmittance of 84% or more at a wavelength of 550 nm.
  • the light transmittance at a wavelength of 308 nm is 1% or less, that is, sufficient light absorption at the wavelength can be achieved that makes it possible to peel the resin thin film from the substrate to which the laser lift-off method is applied.
  • the resin thin film can have a low coefficient of linear expansion coefficient of, for example, 40 ppm / ° C. or less, particularly 10 ppm / ° C. to 35 ppm / ° C. at 30 ° C. to 220 ° C., and has excellent dimensional stability during heating. It is.
  • the resin thin film has an in-plane retardation R 0 represented by the product of birefringence (difference between two in-plane orthogonal refractive indexes) and a film thickness when the wavelength of incident light is 590 nm,
  • the film thickness thickness direction retardation R th represented is featuring in that both small.
  • the resin thin film described above has the above-mentioned characteristics, it satisfies the conditions necessary for a base film of a flexible device substrate, and is particularly preferably used as a base film for a substrate of a flexible device, particularly a flexible display. it can.
  • the resin thin film has a thickness direction retardation R th of 700 nm or less, such as 450 nm or less, or 1 to 410 nm, and an in-plane retardation R 0 is smaller than 4.5, for example.
  • R th thickness direction retardation
  • R 0 an in-plane retardation R 0 is smaller than 4.5
  • it is 0.1 to 4.2
  • the birefringence ⁇ n is smaller than 0.001.
  • the apparatus and conditions used for sample preparation and physical property analysis and evaluation are as follows. 1) Measurement of number average molecular weight and weight average molecular weight The number average molecular weight (hereinafter abbreviated as Mn) and the weight average molecular weight (hereinafter abbreviated as Mw) of a polymer were measured by a device: Showdex GPC-101, manufactured by Showa Denko KK Column: KD803 and KD805, column temperature: 50 ° C., elution solvent: DMF, flow rate: 1.5 ml / min, calibration curve: standard polystyrene.
  • Mn number average molecular weight
  • Mw weight average molecular weight of a polymer were measured by a device: Showdex GPC-101, manufactured by Showa Denko KK Column: KD803 and KD805, column temperature: 50 ° C., elution solvent: DMF, flow rate: 1.5 ml / min, calibration curve: standard polystyrene.
  • 5% weight loss temperature (Td 5% ) 5% weight loss temperature (Td 5% [° C.]) is measured by using TGA Q500 manufactured by TA Instruments Inc. and raising the temperature of about 5 to 10 mg of resin thin film to 50 to 800 ° C. at 10 ° C./min in nitrogen. I asked for it.
  • the thickness direction retardation (R th ) and the in-plane retardation (R 0 ) are calculated by the following equations.
  • R th [(Nx + Ny) / 2 ⁇ Nz]
  • ⁇ d [( ⁇ Nxz ⁇ d) + ( ⁇ Nyz ⁇ d) / 2 Nx
  • Ny Two in-plane orthogonal refractive indexes (Nx> Ny, Nx is also called the slow axis, and Ny is also called the fast axis)
  • Nz Refractive index in the thickness (perpendicular) direction with respect to the surface d: Film thickness ⁇ Nxy: Difference between two refractive indexes in the surface (Nx ⁇ Ny) (birefringence)
  • ⁇ Nxz difference between in-plane refractive index Nx and thickness direction refractive index Nz (birefringence)
  • Preparation Example 1 Preparation of silica sol (GBL-M) In a 1000 mL round bottom flask, 350 g of methanol-dispersed silica sol manufactured by Nissan Chemical Industries, Ltd .: MA-ST-M (silica solid content concentration: 40.4) % By weight) and 419 g of ⁇ -butyllactone. Then, the flask was connected to a vacuum evaporator to reduce the pressure in the flask, and immersed in a warm water bath at about 35 ° C. for 20 to 50 minutes, so that silica sol (GBL-M) in which the solvent was substituted from methanol to ⁇ -butyllactone was reduced. 560.3 g was obtained (silica solid content concentration: 25.25% by mass).
  • Synthesis Example 1 Synthesis of Polyimide I (PI-I) In a 250 mL three-necked flask equipped with Dean Stark, a nitrogen inlet / outlet, and a mechanical stirrer, TFMB 6.4046 g (0.02 mol) ), And immediately after that 22.24 g of GBL was added and stirring was started. After the diamine was completely dissolved in the solvent, immediately after adding 2.505 g (0.01 mol) of BODAxx, 6.67 g of GBL and 0.222 g of 1-ethylpiperidine were added, and 3.5 hours under nitrogen. Heated to 140 ° C.
  • Synthesis Example 2 Synthesis of Polyimide II (PI-II) By performing the same operation as in Synthesis Example 1 except that s-BPDA (0.002 mol) was used instead of BTDA (0.002 mol), polyimide was obtained. II (PI-II) was obtained.
  • Synthesis Example 3 Synthesis of Polyimide A (PI-A) 25.61 g (0.08 mol) of TFMB was placed in a 250 mL reaction three-necked flask equipped with a nitrogen inlet / outlet, a mechanical stirrer, and a condenser. Thereafter, 173.86 g of GBL was added and stirring was started. Immediately after the diamine was completely dissolved in the solvent, 10 g (0.04 mol) of stirred BODAxx, 7.84 g (0.04 mol) of CBDA and 43.4 g of GBL were added and heated to 140 ° C. under nitrogen. . Thereafter, 0.348 g of 1-ethylpiperidine was added into the solution and heated to 180 ° C.
  • PI-A Polyimide A
  • Example 2 Polyimide I / silica sol composite resin thin film
  • PI-I polyimide
  • GBL-M silica sol
  • Example 3 Polyimide II resin thin film
  • the resin thin film was obtained by baking for 60 minutes.
  • Example 4 Polyimide II / silica sol composite resin thin film
  • 1 g of the polyimide (PI-II) of Synthesis Example 2 dissolved in GBL solvent so as to be 10% by mass was slowly pressure-filtered through a 5 ⁇ m filter. .
  • the filtrate is then added to 9.241 g of silica sol (GBL-M) (18-23 nm SiO 2 nanoparticles dispersed in GBL at 25.25%), mixed for 30 minutes, Maintained overnight.
  • the solution is then coated on a glass substrate and baked in air at a temperature of 50 ° C. for 30 minutes, at 140 ° C. for 30 minutes and at 200 ° C. for 60 minutes, and in a ⁇ 99 kpa vacuum atmosphere at 280 ° C. for 60 minutes.
  • a resin thin film was obtained.
  • Example 5 Polyimide A resin thin film At room temperature, 1 g of the polyimide (PI-A) of Synthesis Example 3 dissolved in GBL solvent so as to be 10% by mass was slowly filtered under pressure through a 5 ⁇ m filter. Thereafter, the solution was coated on a glass substrate and baked in an air atmosphere at a temperature of 50 ° C. for 30 minutes, at 140 ° C. for 30 minutes and at 200 ° C. for 60 minutes to obtain a resin thin film.
  • PI-A polyimide
  • GBL solvent so as to be 10% by mass
  • Example 6 Polyimide A / silica sol composite resin thin film
  • PI-A polyimide
  • GBL-M silica sol
  • the resin thin films of the present invention shown in Examples 1 to 4 have a low coefficient of linear expansion [ppm / ° C.] (50 to 200 ° C.), and light transmittance at 550 nm after curing [ %] Was good, the light transmittance [%] at 308 nm was low, and the retardation was suppressed to a low value.
  • the resin thin films of the present invention obtained in Examples 1 to 4 do not break even when they are held with both hands and bent at an acute angle (about 30 degrees), and the high flexibility required for a flexible display substrate. Also had.
  • the resin thin films of the present invention shown in Examples 1 and 3 can be peeled off by the LLO method.
  • the resin thin film of Example 5 formed from polyimide (PI-A) synthesized without using the aromatic tetracarboxylic dianhydride represented by the formula (D1) was not peeled off under the same conditions.
  • the resin thin film of Example 6 formed by adding SiO 2 to PI-A was not peeled off.

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Abstract

La présente invention concerne une composition pour former un substrat de dispositif flexible qui a une excellente résistance à la chaleur, un faible retard, une excellente flexibilité et une excellente transparence et qui conserve ainsi d'excellentes performances tout en donnant un film mince de résine ayant d'excellentes performances en tant que film de base pour un substrat de dispositif flexible, par exemple, un substrat d'affichage flexible qui peut être facilement détaché d'un support de verre par un procédé LLO. L'invention concerne une composition pour former un substrat de dispositif flexible comprenant : un polyimide qui est un produit de réaction d'un composant de dianhydride d'acide tétracarboxylique contenant un dianhydride tétracarboxylique alicyclique et un dianhydride tétracarboxylique aromatique représenté par la formule (D1) et un composant diamine contenant une diamine aromatique contenant du fluor ; et un solvant organique (dans la formule, E représente une simple liaison, un groupe carbonyle, un atome d'oxygène, un atome de soufre, SO, ou SO2).
PCT/JP2017/041876 2016-11-24 2017-11-21 Composition pour former un substrat de dispositif flexible Ceased WO2018097142A1 (fr)

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Cited By (5)

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JP2020029486A (ja) * 2018-08-20 2020-02-27 河村産業株式会社 ポリイミド粉体、ポリイミドワニス、ポリイミドフィルムおよびポリイミド多孔質膜
JPWO2021153379A1 (fr) * 2020-01-31 2021-08-05
CN113490543A (zh) * 2019-02-28 2021-10-08 富士胶片株式会社 聚合物及其制造方法、使用该聚合物的气体分离膜、气体分离模块、及气体分离装置、以及间苯二胺化合物
WO2023085041A1 (fr) * 2021-11-11 2023-05-19 三菱瓦斯化学株式会社 Résine de polyimide, vernis et film de polyimide
US11806661B2 (en) 2019-02-28 2023-11-07 Fujifilm Corporation Polymer and method for producing the same, gas separation membrane, gas separation module, and gas separation apparatus using the polymer, and m-phenylenediamine compound

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JP2015004062A (ja) * 2013-06-21 2015-01-08 奇美實業股▲分▼有限公司 フレキシブル基板用組成物及びフレキシブル基板
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