WO2017119450A1 - Composition permettant de former un substrat pour dispositifs flexibles - Google Patents

Composition permettant de former un substrat pour dispositifs flexibles Download PDF

Info

Publication number
WO2017119450A1
WO2017119450A1 PCT/JP2017/000147 JP2017000147W WO2017119450A1 WO 2017119450 A1 WO2017119450 A1 WO 2017119450A1 JP 2017000147 W JP2017000147 W JP 2017000147W WO 2017119450 A1 WO2017119450 A1 WO 2017119450A1
Authority
WO
WIPO (PCT)
Prior art keywords
flexible device
composition
forming
substrate
polyimide
Prior art date
Application number
PCT/JP2017/000147
Other languages
English (en)
Japanese (ja)
Inventor
欣也 小山
浩 北
鎮嘉 葉
邦慶 何
Original Assignee
日産化学工業株式会社
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 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to CN201780005922.3A priority Critical patent/CN108473764B/zh
Priority to JP2017560407A priority patent/JP6905213B2/ja
Priority to KR1020187018920A priority patent/KR20180102081A/ko
Publication of WO2017119450A1 publication Critical patent/WO2017119450A1/fr

Links

Classifications

    • 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
    • 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
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
    • 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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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 adopted, that is, when a glass carrier is irradiated with a light beam having a wavelength of 308 nm 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.
  • the polymer substrate absorbs light having a specific wavelength.
  • the semi-alicyclic polyimide and the fully alicyclic polyimide which have been proposed as flexible display substrate materials so far, include an alicyclic moiety, so that the absorption of light in the visible light region is suppressed and the transparency is improved.
  • the LLO method is often not applicable to existing materials including semi-alicyclic polyimides and fully alicyclic polyimides. Therefore, in the field of flexible displays, absorption in the visible light region is suppressed and transparency is sufficiently excellent, and light of a specific wavelength (for example, 308 nm) that can be applied to the LLO method is sufficiently absorbed. There is a need for a substrate material having
  • the present invention has been made in view of such circumstances, and is excellent not only in heat resistance and flexibility, but also as a base film of a flexible device substrate such as a flexible display substrate having a feature of low retardation.
  • the present invention provides a composition for forming a flexible device substrate that gives a resin thin film having performance, and in particular a thin film capable of sufficiently absorbing light of a specific wavelength (308 nm) to which a laser lift-off method can be applied while ensuring transparency in the visible light region.
  • An object of the present invention is to provide a composition for forming a flexible device substrate that can form a film.
  • the present inventors have obtained a resin thin film in which titanium dioxide particles and silicon dioxide particles are blended with polyimide having an alicyclic skeleton in the main chain, and has excellent heat resistance, It has low retardation and also has the characteristics of excellent flexibility, and by making the blending amount of the silicon dioxide within a predetermined range, it has excellent heat resistance, low retardation, excellent flexibility, and transparency.
  • a specific amount of the titanium dioxide particles it is possible to realize a resin thin film that can sufficiently absorb light of a specific wavelength that can apply the LLO method while ensuring the transparency.
  • the present invention has been completed by finding that it can be suitably used for substrates for flexible devices such as flexible displays.
  • the present invention provides, as a first aspect, a polyimide having an alicyclic skeleton in the main chain, Titanium dioxide particles having a particle diameter of 3 nm to 200 nm,
  • the present invention relates to a composition for forming a flexible device substrate, comprising silicon dioxide particles having an average particle diameter of 100 nm or less calculated from a specific surface area value measured by a nitrogen adsorption method, and an organic solvent.
  • the titanium dioxide particles are in an amount of 0.1% by mass or more and 20% by mass or less based on a total mass of the polyimide, the titanium dioxide particles, and the silicon dioxide particles.
  • the present invention relates to a composition for forming a flexible device substrate.
  • a compound further comprising only a hydrogen atom, a carbon atom, a nitrogen atom and an oxygen atom, wherein the group is selected from the group consisting of a hydroxy group, an epoxy group and an alkoxy group having 1 to 5 carbon atoms.
  • a cross-linking agent comprising a compound having two or more and having a cyclic structure, It is related with the composition for flexible device board
  • the said titanium dioxide particle is the quantity of 3 mass% or more and 16 mass% or less with respect to the total mass of the said polyimide, the said titanium dioxide particle, and the said silicon dioxide particle, The flexible device as described in a 3rd viewpoint.
  • the present invention relates to a composition for forming a substrate.
  • the polyimide imidizes a polyamic acid obtained by reacting a tetracarboxylic dianhydride component containing an alicyclic tetracarboxylic dianhydride and a diamine component containing a fluorine-containing aromatic diamine. It is related with the composition for flexible device board
  • the said alicyclic tetracarboxylic dianhydride is related with the composition for flexible device board
  • B 1 represents a tetravalent group selected from the group consisting of formulas (X-1) to (X-12).
  • a plurality of R's independently represent a hydrogen atom or a methyl group, and * represents a bond.
  • the said fluorine-containing aromatic diamine is related with the composition for flexible device board
  • the composition for forming a flexible device substrate according to any one of the first aspect to the seventh aspect wherein a mass ratio of the polyimide and the silicon dioxide particles is 7: 3 to 3: 7.
  • a mass ratio of the polyimide and the silicon dioxide particles is 7: 3 to 3: 7.
  • the average particle diameter of the said silicon dioxide particle is related with the composition for flexible device board
  • a step of applying the flexible device substrate forming composition according to any one of the first aspect to the tenth 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 composition for forming a flexible device substrate according to the present invention has a low coefficient of linear expansion, excellent heat resistance, high transparency and low retardation, and further excellent flexibility, particularly application of the laser lift-off method. It is possible to form a substrate for a flexible device such as a flexible display that can sufficiently absorb a light beam having a specific wavelength (308 nm) that can be reproduced with good reproducibility.
  • the flexible device substrate according to the present invention has various characteristics required for a substrate for a flexible device such as a flexible display, that is, a low linear expansion coefficient and high transparency in the visible light region (high light transmittance, low yellowness).
  • the laser lift-off method can be suitably used when peeling the substrate from the carrier base material because it exhibits low retardation, is excellent in flexibility, and particularly can sufficiently absorb light having a specific wavelength (308 nm).
  • a present invention is a substrate for a flexile device that requires characteristics such as high flexibility, low linear expansion coefficient, high transparency (high light transmittance, low yellowness), low retardation, particularly in the production process thereof.
  • the laser lift-off method can be adopted, and can sufficiently cope with the progress in the field of flexible device substrates.
  • composition for forming a flexible device substrate of the present invention contains the following specific polyimide, titanium dioxide particles, silicon dioxide particles and an organic solvent, and optionally contains a crosslinking agent and other components.
  • the polyimide used in the present invention is a polyimide having an alicyclic skeleton in the main chain, and preferably includes a tetracarboxylic dianhydride component including an alicyclic tetracarboxylic dianhydride and a fluorine-containing aromatic diamine. It is the polyimide obtained by imidating the polyamic acid obtained by making it react with the diamine component to contain. That is, the polyimide is preferably an imidized product of polyamic acid, and the polyamic acid is a diamine component including a tetracarboxylic dianhydride component including an alicyclic tetracarboxylic dianhydride and a fluorine-containing aromatic diamine.
  • the alicyclic tetracarboxylic dianhydride includes a tetracarboxylic dianhydride represented by the following formula (C1), and the fluorine-containing aromatic diamine is represented by the following formula (A1). It is preferable that the diamine contains.
  • 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).
  • diamines represented by the above formula (A1) compounds in which B 2 is represented by the formulas (Y-12) and (Y-13) are preferred.
  • a polyimide obtained by imidizing a polyamic acid obtained by reacting a tetracarboxylic dianhydride represented by the above formula (C1) and a diamine represented by the above formula (A1) is described below.
  • the monomer unit represented by Formula (2) is included.
  • a tetracarboxylic dianhydride component The alicyclic tetracarboxylic dianhydride, for example, the tetracarboxylic dianhydride represented by the above formula (C1) is preferably 90 mol% or more, and 95 mol% or more. More preferably, it is most preferable that all (100 mol%) are tetracarboxylic dianhydrides represented by the above formula (C1).
  • the fluorine-containing aromatic diamine is used with respect to the total number of moles of the diamine component.
  • the diamine represented by the above formula (A1) is preferably 90 mol% or more, and more preferably 95 mol% or more.
  • 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 (2).
  • the polyimide used by this invention is a diamine containing the alicyclic tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride represented by the above-mentioned formula (C1), and the diamine represented by a formula (A1).
  • C1 alicyclic tetracarboxylic dianhydride
  • A1 diamine represented by a formula (A1).
  • other monomer units may be included.
  • the content ratio of the other monomer units is arbitrarily determined as long as the properties of the resin thin film suitable as a flexible device substrate formed from the composition of the present invention are not impaired.
  • the ratio is derived from the alicyclic tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride represented by the formula (C1) and the diamine component containing the diamine represented by the formula (A1).
  • the total number of moles of monomer units is preferably less than 20 mol%, more preferably less than 10 mol%, and even more preferably less than 5 mol%.
  • Examples of such other monomer units include, but are not limited to, monomer units 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.
  • the polyimide used by this invention contains the diamine represented by the alicyclic tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride represented by the above-mentioned formula (C1), and a formula (A1).
  • the polyimide containing each monomer unit is represented by the above formula (C1) as a tetracarboxylic dianhydride component.
  • 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.
  • tetracarboxylic dianhydride represented by the formula (5)
  • tetracarboxylic dianhydrides in which A in the formula (5) is a tetravalent group represented by any one of the above formulas (A-1) to (A-4) are preferable.
  • 4,8-bis (trifluoromethoxy) benzo [1,2-c: 4,5 -C '] difuran-1,3,5,7-tetraone can benzo
  • 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 content of the polyimide is usually 10% by mass or more, preferably 20% by mass or more, more preferably based on the total solid content of the composition for forming a flexible device substrate.
  • the optical properties of the low retardation film thickness direction retardation (R th ) and linear expansion coefficient (CTE) do not decrease)
  • it is usually 80% by mass or less, preferably 75% by mass or less. More preferably, it is 70 mass% or less.
  • solid content means the remaining components remove
  • the polyimide used in the present invention is represented by the tetracarboxylic dianhydride component including the alicyclic tetracarboxylic dianhydride represented by the above formula (C1) and the above formula (A1). It is obtained by imidizing a polyamic acid obtained by reacting a diamine component containing a fluorine-containing aromatic diamine.
  • the reaction for obtaining a polyamic acid from the above two components is advantageous in that it can proceed relatively easily in an organic solvent and no by-product is produced.
  • the charging ratio (molar ratio) between the tetracarboxylic dianhydride component and the diamine component in such a reaction 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 0.95. About 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 method of reacting the tetracarboxylic dianhydride component and the diamine component in an organic solvent for example, a dispersion or solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid dianhydride component is stirred here.
  • the method of adding a diamine component the method of adding a tetracarboxylic dianhydride component and a diamine compound component alternately, etc. are mentioned, As long as the target polyamic acid is obtained, it is not limited to these methods.
  • 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 raw material concentration. However, if the concentration is too low, it will be difficult to obtain a high molecular weight polyamic acid, and if the concentration is too high, the viscosity of the reaction solution will become too high and uniform stirring will occur.
  • 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. If necessary, the initial reaction can be carried out 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 amines such as pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, 1-ethylpiperidine, etc.
  • pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • Examples of acid anhydrides include aliphatic carboxylic acid anhydrides such as acetic anhydride, and aromatic carboxylic acid anhydrides such as trimellitic anhydride and pyromellitic anhydride. This is preferable because it can be easily purified.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the dehydration cyclization rate (imidation 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 may be used as it is, or may be diluted or concentrated, and may be combined with titanium dioxide, silicon dioxide, etc., which will be described later, to form a flexible device substrate forming composition. .
  • the filtrate 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
  • Titanium dioxide (titania) used in the present invention is not particularly limited, but titanium dioxide in the form of particles, for example, particles having a particle diameter of 3 nm to 200 nm, preferably 3 nm to 50 nm, more preferably 3 nm to 20 nm are preferably used. it can.
  • the particle diameter of the titanium dioxide particles is represented as a primary particle diameter obtained by observing titanium dioxide particles in a titanium dioxide sol described later with an electron microscope.
  • Titanium dioxide may have an anatase type, a rutile type, an anatase / rutile mixed type, or a brookite type crystal structure. Among these, those containing a rutile type are desirable.
  • titania-based colloidal particles having the above particle diameter values can be suitably used, and titania sol can be used as the colloidal titania.
  • the titania colloidal particles used in the present invention may be single colloidal particles, a mixture with other high refractive index metal oxides described later, or composite oxide colloidal particles.
  • the method for producing the titania colloidal particles is not particularly limited, and can be produced by a conventional method, for example, 1) an ion exchange method, 2) a peptization method, or the like.
  • Ion exchange method A method of treating an acidic salt of titanium with a hydrogen ion exchange resin, or a method of treating a basic salt of titanium with a hydroxyl type anion exchange resin.
  • Peptization A method in which the gel obtained by neutralizing the acidic salt of titanium with a salt or neutralizing the basic salt of titanium with an acid is washed with an acid or a base ( Japanese Patent Publication No. 4-27168), a method of hydrolyzing an alkoxide of titanium (Japanese Patent Laid-Open No. 2003-176120), or a method of hydrolyzing a basic salt of titanium with heating (Japanese Patent Laid-Open No. 10-245224) ) And the like.
  • Examples of the other metal oxides include Fe 2 O 3 , ZrO 2 , SnO 2 , Ta 2 O 5 , Nb 2 O 5 , Y 2 O 3 , MoO 3 , WO 3 , PbO, In 2 O 3 , Examples include Bi 2 O 3 and SrO, which can be produced in the same manner as the titania colloidal particles.
  • composite oxides TiO 2 -SnO 2, TiO 2 -ZrO 2, TiO 2 -ZrO 2 -SnO 2, TiO 2 -ZrO 2 -CeO 2 , and the like, as a method for compounding is
  • methods disclosed in JP 2014-38293 A, JP 2001-122621 A, JP 2000-063119 A, and the like can be employed.
  • organic solvents in the above titania 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-pyrrolidone Cyclic ethers such as ⁇ -butyrolactone; glycols such as ethyl cellosolve and ethylene glycol; acetonitrile and the like.
  • the titania sol has a viscosity of about 0.6 mPa ⁇ s to 100 mPa ⁇ s at 20 ° C.
  • titania colloidal particles examples include, for example, Product name Neutral titania sol TTO-W-5 (Rutile ultrafine titanium oxide aqueous sol, silica surface treatment, manufactured by Ishihara Sangyo Co., Ltd.) Product name TKS-201 (Anatase type acidic sol, manufactured by Teika Co., Ltd.), Product name KS-202 (Anatase type acidic sol, manufactured by Teika Co., Ltd.), Product name TKS-203 (Anatase type neutral sol, Taker ( ) Product name CSB (anaters type water-based acidic sol, manufactured by Sakai Chemical Industry Co., Ltd.), product name CSB-M (anaters type water-based neutral sol, manufactured by Sakai Chemical Industry Co., Ltd.), Product name DC-Ti, DCN-Ti, DCB-Ti (above amorphous water-based sol, manufactured by Fuji Titanium Industry Co., Ltd.), organic sol (anatata sol TTO-W-5 (
  • the content of the titanium dioxide is usually 0.1 mass relative to the total mass of the polyimide, titanium dioxide particles, and silicon dioxide particles in the flexible device substrate-forming composition from the viewpoint of ensuring absorption of light having a wavelength of 308 nm. % Or more, preferably 1% by mass or more, more preferably 2% by mass or more, from the viewpoint of obtaining a thin film excellent in transparency in the visible light region with good reproducibility, usually 30% by mass or less, preferably 25% by mass or less, More preferably, it is 20 mass% or less.
  • the total amount of the polyimide, titanium dioxide particles, and silicon dioxide particles in the composition for forming a flexible device substrate is used. It is preferable that the titanium content is 3 mass% or more and 16 mass% or less.
  • the silicon dioxide (silica) used in the present invention is not particularly limited, but silicon dioxide in the form of particles, for example, the average particle diameter is 100 nm or less, preferably 5 nm to 100 nm, more preferably 5 nm to 55 nm, and a highly transparent thin film is formed. From the viewpoint of obtaining good 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.
  • This substitution can be performed by a usual method such as a distillation method or an ultrafiltration method.
  • 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.
  • 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 content of silicon dioxide is based on the total mass of polyimide, titanium dioxide particles, and silicon dioxide particles in the composition for forming a flexible device substrate. Usually 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more. From the viewpoint of the mechanical strength of the membrane, it is usually 80% by mass or less, preferably 75% by mass or less, more preferably 70% by mass. It is as follows.
  • 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 the formulas selected from the group consisting of the following formulas (K1) to (K5).
  • formula (K4) As one preferred embodiment of formula (K4), formula (K4- As one of the preferred embodiments of the compound represented by 1), the compound represented by the formula (5-1) is exemplified.
  • 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 amount of the crosslinking agent is appropriately determined according to the type of the crosslinking agent, etc., it cannot be specified unconditionally.
  • the total amount of the polyimide, the titanium dioxide, and the silicon dioxide is usually the amount of the resin thin film obtained. From the viewpoint of ensuring flexibility 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 or more, preferably 1% by mass or more.
  • the composition for forming a flexible device substrate of the present invention contains an organic solvent in addition to the polyimide, titanium dioxide, silicon dioxide and, optionally, a crosslinking agent.
  • 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.
  • 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, titanium dioxide, silicon dioxide, an organic solvent, and optionally a crosslinking agent.
  • 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.
  • composition for forming a flexible device substrate of the present invention can be obtained by dissolving the polyimide obtained by the above-mentioned method, titanium dioxide and silicon dioxide, and optionally a crosslinking agent in the above-mentioned organic solvent. Titanium dioxide, silicon dioxide, and a crosslinking agent as required may be added to the subsequent reaction solution, and the organic solvent may be further added as desired.
  • [Flexible device substrate] The organic solvent is removed by applying the composition for forming a flexible device substrate of the present invention described above to a substrate, drying and heating, high heat resistance, high transparency, moderate flexibility, and moderate A resin thin film having a linear expansion coefficient and having a small retardation and selectively absorbing light having a wavelength of 308 nm, that is, a flexible device substrate can be obtained.
  • the flexible device substrate that is, the flexible device comprising the polyimide, the titanium dioxide, silicon dioxide, and optionally a crosslinking agent, that is, the flexible device comprising the cured product of the flexible device substrate forming composition of the present invention.
  • Substrates are also the subject of the present invention.
  • 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 wavelength of 308 nm 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, include a range of less than 650 mJ / cm 2, for instance, the range of 500 mJ / cm 2 to 530mJ / cm 2, the range of 500 mJ / cm 2 to 515mJ / cm 2 Etc.
  • the resin thin film according to a preferred embodiment of the present invention thus obtained can achieve high transparency with a light transmittance of 85% or more at a wavelength of 550 nm.
  • the light transmittance at a wavelength of 308 nm is 5% or less, that is, it is possible to achieve sufficient light absorption at the wavelength that enables the resin thin film to be peeled 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 are both featuring a very small.
  • the resin thin film has a thickness direction retardation R th of less than 700 nm, for example, 450 nm or less, for example, 1 nm to 410 nm, and in-plane retardation R 0 is less than 4.5.
  • R th thickness direction retardation
  • in-plane retardation R 0 is less than 4.5.
  • the birefringence ⁇ n has a very low value of less than 0.015, for example, 0.0028 to 0.0144.
  • 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.
  • CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • BODAxx bicyclo [2,2,2] octane-2,3,5,6-tetracarboxylic dianhydride
  • TFMB 2,2′-bis (trifluoromethyl) benzidine
  • NMP N-methyl-2-pyrrolidone
  • GBL ⁇ -butyrolactone
  • titania sol (TiO 2 -GBL)
  • methanol-dispersed titania sol manufactured by Nissan Chemical Industries, Ltd .: TiO 2 -MeOH (“Sun Colloid (registered trademark) HT-R305M7-20”, rutile type, solid content of titania: 30.6% by mass ) 91.13 g and ⁇ -butyrolactone 82.02 g.
  • 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.
  • titania sol TiO 2 -GBL in which the solvent was replaced with ⁇ -butyllactone was about 107 0.0 g was obtained (titania solid content concentration: 26.06% by mass).
  • titania sol the primary particle diameter of titanium dioxide particles observed with an electron microscope was 10 to 12 nm.
  • the average particle diameter calculated from the specific surface area value measured by the nitrogen adsorption method was 22 nm.
  • the specific surface area of the dry powder of silica sol was measured using a specific surface area measuring device Monosorb MS-16 manufactured by Yuasa Ionics Co., Ltd., and the measured specific surface area S (m 2 / g) was used as D.
  • Example 1 At room temperature, 1 g of the polyimide solution prepared in the synthesis example (PI, polyimide solid content concentration: 10.5 mass%) was added to the GBL-M silica sol prepared in the preparation example (silica solid content concentration: 25.25 mass%). 9703g and GBL 0.946g were added, and it stirred for 30 minutes, and obtained the composition for flexible device board
  • TiO 2 -GBL titania sol (titania solid content concentration: 26.06 mass%) 0.1343 g and GBL 0.95 g were added and stirred for 30 minutes to obtain a composition for forming a flexible device substrate.
  • Example 3 At room temperature, 1 g of the polyimide solution prepared in the synthesis example (PI, polyimide solid content concentration: 10.5 mass%) was added to the GBL-M silica sol prepared in the preparation example (silica solid content concentration: 25.25 mass%).
  • Example 4 At room temperature, 1 g of the polyimide solution prepared in the synthesis example (PI, polyimide solid content concentration: 10.5 mass%) was added to the GBL-M silica sol prepared in the preparation example (silica solid content concentration: 25.25 mass%).
  • TiO 2 -GBL titania sol (titania solid content concentration: 26.06 mass%) 0.0302 g and GBL 0.5648 g were added and stirred for 30 minutes to obtain a composition for forming a flexible device substrate.
  • Example 5 At room temperature, 1 g of the polyimide solution prepared in the synthesis example (PI, polyimide solid content concentration: 10.5 mass%) was added to the GBL-M silica sol prepared in the preparation example (silica solid content concentration: 25.25 mass%).
  • Example 6 At room temperature, 1 g of the polyimide solution prepared in the synthesis example (PI, polyimide solid content concentration: 10.5 mass%) was added to the GBL-M silica sol prepared in the preparation example (silica solid content concentration: 25.25 mass%).
  • Example 7 At room temperature, 1 g of the polyimide solution prepared in the synthesis example (PI, polyimide solid content concentration: 10.5 mass%) was added to the GBL-M silica sol prepared in the preparation example (silica solid content concentration: 25.25 mass%).
  • TiO 2 -GBL titania sol (titania solid content concentration: 26.06 mass%) 0.04029 g and GBL 0.335 g were added and stirred for 30 minutes to obtain a composition for forming a flexible device substrate.
  • Example 8 At room temperature, 1 g of the polyimide solution prepared in the synthesis example (PI, polyimide solid content concentration: 10.5 mass%) was added to the GBL-M silica sol prepared in the preparation example (silica solid content concentration: 25.25 mass%). 5718 g, TiO 2 -GBL titania sol (titania solid content concentration: 26.06 mass%) 0.05 g, GBL 1.264 g were added, and TEPIC-L (purity 99%) 0.029 g was added, and the mixture was stirred for 30 minutes. Then, a composition for forming a flexible device substrate was obtained.
  • PI polyimide solid content concentration: 10.5 mass%
  • Example 9 At room temperature, 1 g of the polyimide solution prepared in the synthesis example (PI, polyimide solid content concentration: 10.5 mass%) was added to the GBL-M silica sol prepared in the preparation example (silica solid content concentration: 25.25 mass%). 5198 g, TiO 2 -GBL titania sol (titania solid content concentration: 26.06 mass%) 0.1 g and GBL 1.266 g were added, and TEPIC-L (purity 99%) 0.029 g was further added, followed by stirring for 30 minutes. Then, a composition for forming a flexible device substrate was obtained.
  • PI polyimide solid content concentration: 10.5 mass%
  • Example 10 At room temperature, 1 g of the polyimide solution prepared in the synthesis example (PI, polyimide solid content concentration: 10.5 mass%) was added to the GBL-M silica sol prepared in the preparation example (silica solid content concentration: 25.25 mass%). 4678 g, TiO 2 -GBL titania sol (titania solid content concentration: 26.06 mass%) 0.1511 g and GBL 1.268 g were added, and TEPIC-L (purity 99%) 0.029 g was added, and the mixture was stirred for 30 minutes. Then, a composition for forming a flexible device substrate was obtained.
  • PI polyimide solid content concentration: 10.5 mass%
  • Example 11 At room temperature, 1 g of the polyimide solution prepared in the synthesis example (PI, polyimide solid content concentration: 10.5 mass%) was added to the GBL-M silica sol prepared in the preparation example (silica solid content concentration: 25.25 mass%). 5458 g, TiO 2 -GBL titania sol (titania solid content concentration: 26.06 mass%) 0.0755 g, and GBL 0.5654 g were added and stirred for 30 minutes to obtain a composition for forming a flexible device substrate.
  • 5% weight loss temperature (Td 5% ) 5% weight loss temperature (Td 5% [° C.]) is measured by using a TGA Q500 manufactured by TA Instruments Inc. and raising the temperature of about 5 to 10 mg of thin film from nitrogen to 50 to 800 ° C. at a rate of 10 ° C./min. I asked for it.
  • CIE b value (CIE b * ) was measured using a SA4000 spectrometer manufactured by Nippon Denshoku Industries Co., Ltd., at room temperature, using air as a reference.
  • T 308nm , T 550nm Light transmittance at wavelengths of 308 nm and 550 nm (T 308 nm , T 550 nm [%]) was measured using UV-3600 manufactured by Shimadzu Corporation at room temperature and with reference as air.
  • Retardation (R th , R 0 ) Thickness direction retardation (R th ) and in-plane retardation (R 0 ) were measured at room temperature using KOBURA 2100ADH manufactured by Oji Scientific Instruments.
  • the thickness direction retardation (R th ) and the in-plane retardation (R 0 ) are calculated by the following equations.
  • Table 1 shows the results of optical characteristics of the resin thin films obtained from the respective flexible device substrate forming compositions
  • Table 2 shows the results of heat resistance and solvent resistance tests.
  • the resin thin films obtained from the flexible device substrate forming compositions of Examples 2 to 11 have a high light transmittance [%] at a wavelength of 550 nm, while the light transmittance at a wavelength of 308 nm is 5%. The results suggesting that the laser lift-off method can be applied.
  • the resin thin film also has a low yellowness (CIE b * ), a thickness direction retardation R th of 404 nm or less, an in-plane retardation R 0 of 4.2 nm or less, and a birefringence ⁇ n of less than 0.015. The value was extremely low.
  • the resin thin film had a low coefficient of linear expansion [ppm / ° C.] (30 to 220 ° C.) (less than 31 ppm / ° C.), improved heat resistance, and flexibility. . Furthermore, in Example 8 thru
  • Laser light source Maxima laser XeCl (308 nm) Energy Density: 420mJ / cm 2, 500mJ / cm 2, 515mJ / cm 2, 530mJ / cm 2, 560mJ / cm 2, 630mJ / cm 2 Stage moving speed: 7.8 mm / sec Laser beam size: 14 mm ⁇ 1.3 mm (maximum energy size: 7.8 mm ⁇ 1.3 mm), laser beam overlapping scanning range is 80% The results are shown in Table 3. In the table, ⁇ represents that the resin thin film was peeled off, ⁇ represents that there was a partial defect, and ⁇ represents that no peeling occurred.
  • Example 11 As shown in Table 3, it was confirmed that the resin thin film of the present invention shown in Example 11 can be peeled off by the LLO method. On the other hand, the resin thin film of Example 1 containing no TiO 2 was not peeled off under the same conditions.
  • the composition for forming a flexible device substrate of the present invention has characteristics such as a low linear expansion coefficient, high transparency (high light transmittance, low yellowness), low retardation, and excellent solvent resistance. That is, it is a material that can form a resin thin film that satisfies the requirements as a base film of a flexible device substrate.
  • the resin thin film sufficiently absorbs light of a specific wavelength (308 nm) and can be applied with a laser lift-off method, it is particularly preferably used as a base film of a flexible device substrate for mass production of flexible devices. I can expect to be able to.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention vise à fournir une composition de formation d'un substrat pour dispositifs flexibles, ladite composition formant un film mince de résine caractérisé en ce qu'il présente une excellente résistance à la chaleur et un faible retard, en particulier un film mince de résine qui est approprié en tant que substrat pour dispositifs flexibles, et qui forme un film mince de résine qui absorbe les faisceaux lumineux ayant une longueur d'onde spécifique, permettant ainsi d'appliquer un procédé de décollement laser. La présente invention concerne par conséquent une composition de formation d'un substrat pour dispositifs flexibles, qui contient un polyimide, des particules de dioxyde de titane présentant un diamètre de particule de 3 nm à 200 nm, des particules de dioxyde de silicium présentant un diamètre moyen de particule de 100 nm ou moins tel que calculé à partir de la surface spécifique déterminée par un procédé d'adsorption d'azote, et un solvant organique ; et un film mince de résine qui est formé à partir de cette composition de formation d'un substrat pour dispositifs flexibles.
PCT/JP2017/000147 2016-01-08 2017-01-05 Composition permettant de former un substrat pour dispositifs flexibles WO2017119450A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201780005922.3A CN108473764B (zh) 2016-01-08 2017-01-05 柔性器件基板形成用组合物
JP2017560407A JP6905213B2 (ja) 2016-01-08 2017-01-05 フレキシブルデバイス基板形成用組成物
KR1020187018920A KR20180102081A (ko) 2016-01-08 2017-01-05 플렉서블 디바이스 기판 형성용 조성물

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2016002614 2016-01-08
JP2016-002614 2016-01-08
JP2016-228050 2016-11-24
JP2016228050 2016-11-24

Publications (1)

Publication Number Publication Date
WO2017119450A1 true WO2017119450A1 (fr) 2017-07-13

Family

ID=59274112

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/000147 WO2017119450A1 (fr) 2016-01-08 2017-01-05 Composition permettant de former un substrat pour dispositifs flexibles

Country Status (5)

Country Link
JP (1) JP6905213B2 (fr)
KR (1) KR20180102081A (fr)
CN (1) CN108473764B (fr)
TW (1) TWI775739B (fr)
WO (1) WO2017119450A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190125208A (ko) 2018-04-27 2019-11-06 스미또모 가가꾸 가부시키가이샤 광학 필름

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI645973B (zh) * 2017-12-15 2019-01-01 律勝科技股份有限公司 聚醯亞胺薄化軟性基板及其製造方法
KR102245533B1 (ko) * 2020-11-02 2021-04-28 주식회사 지게차코리아 운송수단용 림 및 이의 제조방법

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009540092A (ja) * 2006-06-15 2009-11-19 クローダ インターナショナル パブリック リミティド カンパニー Ｕｖ吸収性組成物
JP2010037425A (ja) * 2008-08-05 2010-02-18 Jsr Corp 樹脂組成物、光学膜及び光学用部材
WO2013125193A1 (fr) * 2012-02-23 2013-08-29 日立化成デュポンマイクロシステムズ株式会社 Composition de résine, film de résine polyamide mettant en œuvre celle-ci, substrat d'affichage et procédé de fabrication
JP2015078254A (ja) * 2013-10-15 2015-04-23 東レ株式会社 樹脂組成物、それを用いたポリイミド樹脂膜、それを含むカラーフィルタ、ｔｆｔ基板、表示デバイスおよびそれらの製造方法
WO2015152178A1 (fr) * 2014-03-31 2015-10-08 日産化学工業株式会社 Procédé de production de film mince de résine et composition permettant de former ledit film mince de résine
WO2016147958A1 (fr) * 2015-03-13 2016-09-22 旭化成株式会社 Composition de résine à base de précurseur de polyimide
WO2016158990A1 (fr) * 2015-03-31 2016-10-06 日産化学工業株式会社 Composition pour la formation d'une couche anti-adhésive, et couche anti-adhésive
WO2016167296A1 (fr) * 2015-04-17 2016-10-20 旭化成株式会社 Composition de résine, film de résine polyimide, et leur procédé de production

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101831175A (zh) * 2010-04-01 2010-09-15 辽宁科技大学 一种无色透明的聚酰亚胺纳米复合材料膜及其制备方法
JP2014114429A (ja) 2012-01-12 2014-06-26 New Japan Chem Co Ltd 溶剤可溶性ポリイミド樹脂
JP5845918B2 (ja) 2012-01-20 2016-01-20 宇部興産株式会社 ポリイミド前駆体及びポリイミド
WO2013161970A1 (fr) * 2012-04-27 2013-10-31 宇部興産株式会社 Composition de type solution d'acide polyamique, et polyimide
TWI495404B (zh) * 2013-06-21 2015-08-01 Chi Mei Corp 軟性基板用組成物及軟性基板
KR102119426B1 (ko) * 2013-06-26 2020-06-08 도레이 카부시키가이샤 폴리이미드 전구체, 폴리이미드, 그것을 사용한 플렉시블 기판, 컬러 필터와 그 제조 방법, 및 플렉시블 표시 디바이스
CN105137636A (zh) * 2015-09-10 2015-12-09 京东方科技集团股份有限公司 一种显示基板及其制作方法和显示面板
CN105111475A (zh) * 2015-09-16 2015-12-02 苏州华辉材料科技有限公司 无色透明的聚酰亚胺纳米复合材料膜及其制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009540092A (ja) * 2006-06-15 2009-11-19 クローダ インターナショナル パブリック リミティド カンパニー Ｕｖ吸収性組成物
JP2010037425A (ja) * 2008-08-05 2010-02-18 Jsr Corp 樹脂組成物、光学膜及び光学用部材
WO2013125193A1 (fr) * 2012-02-23 2013-08-29 日立化成デュポンマイクロシステムズ株式会社 Composition de résine, film de résine polyamide mettant en œuvre celle-ci, substrat d'affichage et procédé de fabrication
JP2015078254A (ja) * 2013-10-15 2015-04-23 東レ株式会社 樹脂組成物、それを用いたポリイミド樹脂膜、それを含むカラーフィルタ、ｔｆｔ基板、表示デバイスおよびそれらの製造方法
WO2015152178A1 (fr) * 2014-03-31 2015-10-08 日産化学工業株式会社 Procédé de production de film mince de résine et composition permettant de former ledit film mince de résine
WO2016147958A1 (fr) * 2015-03-13 2016-09-22 旭化成株式会社 Composition de résine à base de précurseur de polyimide
WO2016158990A1 (fr) * 2015-03-31 2016-10-06 日産化学工業株式会社 Composition pour la formation d'une couche anti-adhésive, et couche anti-adhésive
WO2016167296A1 (fr) * 2015-04-17 2016-10-20 旭化成株式会社 Composition de résine, film de résine polyimide, et leur procédé de production

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190125208A (ko) 2018-04-27 2019-11-06 스미또모 가가꾸 가부시키가이샤 광학 필름
KR20200017447A (ko) 2018-04-27 2020-02-18 스미또모 가가꾸 가부시키가이샤 광학 필름

Also Published As

Publication number Publication date
JPWO2017119450A1 (ja) 2018-10-25
KR20180102081A (ko) 2018-09-14
CN108473764B (zh) 2021-09-28
JP6905213B2 (ja) 2021-07-21
TWI775739B (zh) 2022-09-01
CN108473764A (zh) 2018-08-31
TW201739838A (zh) 2017-11-16

Similar Documents

Publication Publication Date Title
JP6631804B2 (ja) 樹脂薄膜の製造方法および樹脂薄膜形成用組成物
JP7011231B2 (ja) フレキシブルデバイス基板形成用組成物
JP6990354B2 (ja) 樹脂薄膜形成用組成物
JP7231887B2 (ja) ハイブリッド樹脂組成物
JP7116366B2 (ja) フレキシブルデバイス用基板の製造方法
JP7011230B2 (ja) フレキシブルデバイス基板形成用組成物
JP6905213B2 (ja) フレキシブルデバイス基板形成用組成物
KR20220075327A (ko) 폴리이미드 수지 조성물, 폴리이미드 바니시 및 폴리이미드 필름

Legal Events

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

Ref document number: 17735987

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017560407

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20187018920

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: 17735987

Country of ref document: EP

Kind code of ref document: A1