WO2015046128A1 - 耐熱性樹脂膜およびその製造方法、加熱炉ならびに画像表示装置の製造方法 - Google Patents

耐熱性樹脂膜およびその製造方法、加熱炉ならびに画像表示装置の製造方法 Download PDF

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WO2015046128A1
WO2015046128A1 PCT/JP2014/075035 JP2014075035W WO2015046128A1 WO 2015046128 A1 WO2015046128 A1 WO 2015046128A1 JP 2014075035 W JP2014075035 W JP 2014075035W WO 2015046128 A1 WO2015046128 A1 WO 2015046128A1
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heating
resistant resin
resin film
temperature
heat
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PCT/JP2014/075035
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English (en)
French (fr)
Japanese (ja)
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宮崎大地
富川真佐夫
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東レ株式会社
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Priority to JP2014548218A priority Critical patent/JP6485043B2/ja
Priority to CN201480053341.3A priority patent/CN105579500B/zh
Priority to KR1020167003482A priority patent/KR102141355B1/ko
Priority to KR1020207008873A priority patent/KR102236562B1/ko
Publication of WO2015046128A1 publication Critical patent/WO2015046128A1/ja

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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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0209—Multistage baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0486—Operating the coating or treatment in a controlled atmosphere
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a heat resistant resin film and a manufacturing method thereof, a heating furnace, and a manufacturing method of an image display device.
  • Heat-resistant resins such as polyimide, polybenzoxazole, polybenzothiazole, and polybenzimidazole are used in various fields including semiconductor applications due to their excellent electrical insulation, heat resistance, and mechanical properties.
  • image display devices such as organic EL displays, electronic paper, and color filters to substrates has also expanded, and it is possible to manufacture a flexible image display device that is resistant to impact.
  • gas permeability such as oxygen and water vapor is high, and it is usual to use a gas barrier film such as a silicon nitride film in a laminated manner.
  • a vacuum process such as plasma enhanced chemical vapor deposition (PECVD) is often used. For this reason, it is preferable that the outgas from the heat resistant resin is as small as possible so that the film formation in the vacuum process does not become defective.
  • PECVD plasma enhanced chemical vapor deposition
  • a solution containing a precursor of a heat-resistant resin (hereinafter referred to as varnish) is usually applied to a support and is converted into a heat-resistant resin film by heating.
  • varnish a solution containing a precursor of a heat-resistant resin
  • a polyimide film can be obtained by coating a solution containing polyamic acid as a precursor on a support and heating at a temperature of 180 to 600 ° C.
  • the heating may be performed in one stage, or may be performed in multiple stages.
  • Patent Document 1 reports a method of heating in multiple stages.
  • This invention makes it a subject to solve the said problem. That is, it is an object to provide a heat-resistant resin film with little outgas and high mechanical properties. In addition, it is an object of the present invention to provide a method for producing a heat-resistant resin film with less outgassing without impairing the mechanical properties of the heat-resistant resin film even if the process of heating in an inert atmosphere is shortened.
  • One of the features of the present invention is a heat resistant resin film in which outgas generated during heating at 450 ° C. for 30 minutes in a helium stream is 0.01 to 4 ⁇ g / cm 2 .
  • One of the characteristics of the present invention is a method for producing a heat-resistant resin film comprising a step of applying a solution containing a precursor of a heat-resistant resin on a support, and a step of heating in multiple stages,
  • the step of heating in multiple stages is (A) a first heating step of heating at a temperature higher than 200 ° C. in an atmosphere having an oxygen concentration of 10% by volume or more, and (B) an atmosphere having an oxygen concentration of 3% by volume or less.
  • one of the features of the present invention is a temperature measuring unit for measuring the temperature in the furnace, a temperature adjusting unit for adjusting the temperature in the furnace, an oxygen concentration measuring unit for measuring the oxygen concentration in the furnace,
  • a heating furnace comprising: a gas flow rate adjustment unit that adjusts the flow rate of the heating atmosphere gas into the furnace; and a control unit that controls the temperature adjustment unit and the gas flow rate adjustment unit, wherein the control unit includes the The furnace that controls the gas flow rate adjusting unit according to the oxygen concentration in the furnace measured by the oxygen concentration measuring unit and that is measured by the temperature measuring unit after the oxygen concentration reaches a predetermined oxygen concentration It is a heating furnace which controls the said temperature adjustment part so that the inside temperature may become predetermined
  • FIG. 1 is a schematic view of a heating furnace 1.
  • One of the features of the present invention is a heat resistant resin film in which outgas generated during heating at 450 ° C. for 30 minutes in a helium stream is 0.01 to 4 ⁇ g / cm 2 .
  • the outgas generated during heating at 450 ° C. for 30 minutes under a helium stream here can be determined by measuring with the following apparatus and conditions.
  • Measuring device heating section “Small-4” (manufactured by Toray Research Center, Inc.), GC / MS “QP5050A (7)” (manufactured by Shimadzu Corporation) Heating conditions: Temperature is raised from room temperature at 10 ° C / min and held for 30 minutes after reaching 450 ° C. Measurement atmosphere: under helium air flow (50 mL / min).
  • the heat resistant resin film of the present invention needs to have an outgas of 0.01 to 4 ⁇ g / cm 2 measured while being held for 30 minutes after reaching 450 ° C. by the above method. If it is 4 ⁇ g / cm 2 or less, film formation defects in a vacuum process such as plasma enhanced chemical vapor deposition (PECVD) are reduced. More preferably, it is 2 ⁇ g / cm 2 or less, and further preferably 1 ⁇ g / cm 2 .
  • PECVD plasma enhanced chemical vapor deposition
  • the outgas generated from the heat-resistant resin film is accumulated at the interface with the glass, so that the peeling is facilitated.
  • the outgas of the heat resistant resin film is required to be 0.01 ⁇ g / cm 2 or more. More preferably, it is 0.02 ⁇ g / cm 2 or more, and further preferably 0.04 ⁇ g / cm 2 or more.
  • the heat resistant resin film of the present invention preferably has a maximum tensile stress of 200 MPa or more.
  • the maximum tensile stress here can be determined by measuring with the following equipment and conditions in accordance with Japanese Industrial Standards (JIS K 7127: 1999).
  • Measuring device Tensilon Universal Material Testing Machine “RTM-100” (Orientec Co., Ltd.) Measurement sample shape: Ribbon shape Measurement sample size: Length> 70 mm, width 10 mm Pulling speed: 50mm / min Distance between chucks at the start of the test: 50 mm Experimental temperature: 0 to 35 ° C Number of samples: 10 Calculation method of measurement results: Arithmetic average value of measured values of 10 samples If the maximum tensile stress is 200 MPa or more, it has appropriate mechanical characteristics as a substrate of an image display device such as an organic EL display, electronic paper, and a color filter. More preferably, it is 250 MPa or more. Further, it is preferably 800 MPa or less, more preferably 600 MPa or less. If it is 800 MPa or less, it has the flexibility as a flexible substrate.
  • an image display device such as an organic EL display, electronic paper, and a color filter. More preferably, it is 250 MPa or more. Further, it is preferably 800 MPa or
  • the heat-resistant resin in the present invention refers to a resin having no melting point or decomposition temperature below 300 ° C., and includes polyimide, polybenzoxazole, polybenzothiazole, polybenzimidazole, polyamide, polyethersulfone, polyetheretherketone, and the like. Including.
  • the heat resistant resin that can be preferably used in the present invention is polyimide, polybenzoxazole, polybenzimidazole, or polybenzothiazole, and more preferably polyimide.
  • the heat-resistant resin is polyimide
  • heat resistance outgas characteristics, glass transition temperature, etc.
  • toughness to the image display device after manufacture It is possible to have a mechanical property suitable for imparting.
  • Polyimide is a resin having a structure represented by the chemical formula (1).
  • X represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms
  • Y represents a divalent diamine residue having 2 or more carbon atoms
  • m represents a positive integer.
  • X is preferably a tetravalent hydrocarbon group having 2 to 80 carbon atoms.
  • X may be a tetravalent organic group having 2 to 80 carbon atoms containing hydrogen and carbon as essential components and containing one or more atoms selected from boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen.
  • Each atom of boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen is preferably independently in a range of 20 or less, more preferably in a range of 10 or less.
  • Examples of tetracarboxylic acids that give X include the following.
  • Examples of the aromatic tetracarboxylic acid include monocyclic aromatic tetracarboxylic acid compounds such as pyromellitic acid and 2,3,5,6-pyridinetetracarboxylic acid;
  • Various isomers of biphenyltetracarboxylic acid such as 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3 ′ -Biphenyltetracarboxylic acid, 3,3 ', 4,4'-benzophenone tetracarboxylic acid, 2,2', 3,3'-benzophenone tetracarboxylic acid, etc .;
  • Bis (dicarboxyphenyl) compounds such as 2,2-bis (3,4-dicarboxyphenyl) hexafluoro
  • aliphatic tetracarboxylic acid examples include a chain aliphatic tetracarboxylic acid compound such as butanetetracarboxylic acid; Alicyclic tetracarboxylic acid compounds such as cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, bicyclo [2.2.1. ] Heptanetetracarboxylic acid, bicyclo [3.3.1. ] Tetracarboxylic acid, bicyclo [3.1.1. ] Hept-2-enetetracarboxylic acid, bicyclo [2.2.2. ] Octane tetracarboxylic acid, adamatane tetracarboxylic acid and the like.
  • Alicyclic tetracarboxylic acid compounds such as cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanete
  • tetracarboxylic acids can be used as they are or in the form of acid anhydrides, active esters, and active amides. Two or more of these may be used.
  • X is mainly composed of a tetravalent tetracarboxylic acid residue represented by the chemical formula (2) or (3).
  • the main component means that 50 mol% or more of the total tetracarboxylic acid is used. More preferably, 80 mol% or more is used. If it is a polyamic acid obtained from these tetracarboxylic acids, even if it heats in air
  • silicon-containing tetracarboxylic acids such as dimethylsilanediphthalic acid and 1,3-bis (phthalic acid) tetramethyldisiloxane
  • adhesion to the support, oxygen plasma used for cleaning, etc. UV ozone Resistance to processing can be increased.
  • silicon-containing tetracarboxylic acids are preferably used in an amount of 1 to 30 mol% of the total tetracarboxylic acids.
  • part of the hydrogen contained in the tetracarboxylic acid residue is a hydrocarbon group having 1 to 10 carbon atoms such as a methyl group or an ethyl group, or a carbon group having 1 to 3 carbon atoms such as a trifluoromethyl group. It may be substituted with 10 fluoroalkyl groups, groups such as F, Cl, Br, and I. Furthermore, when substituted with an acidic group such as OH, COOH, SO 3 H, CONH 2 , or SO 2 NH 2 , the solubility of the resin in an aqueous alkali solution is improved, so that it is used as a photosensitive resin composition described later. Preferred in some cases.
  • Y is preferably a divalent hydrocarbon group having 2 to 80 carbon atoms.
  • Y may be a divalent organic group having 2 to 80 carbon atoms, which contains hydrogen and carbon as essential components and contains one or more atoms selected from boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen.
  • Each atom of boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen is preferably independently in a range of 20 or less, more preferably in a range of 10 or less.
  • Examples of diamines that give Y include the following.
  • Examples of the diamine compound containing an aromatic ring include monocyclic aromatic diamine compounds such as m-phenylenediamine, p-phenylenediamine, and 3,5-diaminobenzoic acid; Naphthalene or condensed polycyclic aromatic diamine compounds such as 1,5-naphthalenediamine, 2,6-naphthalenediamine, 9,10-anthracenediamine, 2,7-diaminofluorene, etc .; Bis (diaminophenyl) compounds or various derivatives thereof such as 4,4′-diaminobenzanilide, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3-carboxy-4,4′-diaminodiphenyl ether 3-sulfonic acid-4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl
  • aliphatic diamine compound examples include linear diamine compounds such as ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tetramethylhexanediamine, 1, 12- (4,9-dioxa) dodecanediamine, 1,8- (3,6-dioxa) octanediamine, 1,3-bis (3-aminopropyl) tetramethyldisiloxane and the like; Alicyclic diamine compounds such as cyclohexanediamine, 4,4′-methylenebis (cyclohexylamine), isophoronediamine and the like; Polyoxyethyleneamine, polyoxypropyleneamine, and their copolymer compounds known as Jeffamine (trade name, manufactured by Huntsman Corporation).
  • diamines can be used as they are or as the corresponding trimethylsilylated diamines. Two or more of these may be used.
  • Y is mainly composed of a divalent diamine residue represented by the chemical formula (4).
  • the main component means that 50 mol% or more of the entire diamine compound is used. More preferably, 80 mol% or more is used.
  • a polyamic acid obtained using p-phenylenediamine is less deteriorated even when heated in air. For this reason, in the method for producing a heat resistant resin film which is one of the features of the present invention, (A) a first heating step of heating at a temperature higher than 200 ° C. in an atmosphere having an oxygen concentration of 10% by volume or more, Further, it may be performed at a temperature higher than 300 ° C.
  • X in the chemical formula (1) is composed mainly of a tetravalent tetracarboxylic acid residue represented by the chemical formula (2) or (3), and Y is a divalent compound represented by the chemical formula (4).
  • the main component is a diamine residue.
  • the polyamic acid leading to the polyimide having such a structure is particularly less deteriorated even when heated in the air.
  • silicon-containing diamine such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane or 1,3-bis (4-anilino) tetramethyldisiloxane as the diamine component
  • adhesion to the support is achieved.
  • resistance to oxygen plasma used for cleaning and UV ozone treatment can be increased.
  • silicon-containing diamine compounds are preferably used in an amount of 1 to 30 mol% of the total diamine compound.
  • a part of hydrogen contained in the diamine compound is a hydrocarbon group having 1 to 10 carbon atoms such as a methyl group or an ethyl group, or a fluoroalkyl group having 1 to 10 carbon atoms such as a trifluoromethyl group.
  • F, Cl, Br, I and the like may be substituted.
  • an acidic group such as OH, COOH, SO 3 H, CONH 2 , or SO 2 NH 2
  • the solubility of the resin in an aqueous alkali solution is improved, so that it is used as a photosensitive resin composition described later. Preferred in some cases.
  • the weight average molecular weight of the precursor of the heat-resistant resin in the present invention is preferably adjusted to 100000 or less, more preferably 80000 or less, and still more preferably 50000 or less in terms of polystyrene using gel permeation chromatography. If it is this range, even if it is a high concentration varnish, it can suppress more that a viscosity increases. Further, the weight average molecular weight is preferably 2000 or more, more preferably 3000 or more, and further preferably 5000 or more. If the weight average molecular weight is 2000 or more, the viscosity when used as a varnish will not be excessively lowered, and better coating properties can be maintained.
  • m represents the number of repeating polyimide units, and may be in a range satisfying the weight average molecular weight of the heat resistant resin in the present invention.
  • m is preferably 5 or more, more preferably 10 or more. Moreover, it is preferably 500 or less, more preferably 200 or less.
  • the precursor of the heat-resistant resin in the present invention can be used as a varnish by further dissolving in a solvent.
  • a film containing a precursor of a heat resistant resin can be formed by applying such varnish on various supports.
  • a heat resistant resin film can be produced by converting the precursor of the heat resistant resin contained in the film into a heat resistant resin.
  • Solvents include aprotic polar solvents such as N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether and other ethers, acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, cyclohexanone and other ketones, ethyl acetate, propylene glycol monomethyl ether Esters such as acetate and ethyl lactate, toluene, Emissions, etc. aromatic hydrocarbons such as alone or mixture of two or more thereof may
  • the content of the solvent is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, preferably 2000 parts by mass or less, more preferably 1500 parts by mass with respect to 100 parts by mass of the heat-resistant resin precursor. It is as follows. If it is the range which satisfy
  • the solution containing the precursor of the heat-resistant resin in the present invention preferably contains at least one of (a) a photoacid generator, (b) a compound containing a phenolic hydroxyl group, and (c) a surfactant.
  • the varnish in the present invention can be made into a photosensitive resin composition by further containing (a) a photoacid generator.
  • a photoacid generator By containing the photoacid generator, an acid is generated in the light irradiation part, the solubility of the light irradiation part in the alkaline aqueous solution is increased, and a positive relief pattern in which the light irradiation part is dissolved can be obtained.
  • the acid generated in the light irradiation part accelerates the cross-linking reaction of the epoxy compound or the heat cross-linking agent, and the light irradiation part becomes insoluble.
  • the relief pattern can be obtained.
  • photoacid generators examples include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Two or more of these may be contained, and a highly sensitive photosensitive resin composition can be obtained.
  • the quinonediazide compound includes a polyhydroxy compound in which a sulfonic acid of quinonediazide is bonded with an ester, a polyamino compound in which a sulfonic acid of quinonediazide is bonded to a sulfonamide, and a sulfonic acid of quinonediazide in an ester bond and / or sulfone.
  • Examples include amide-bonded ones. It is preferable that 50 mol% or more of the total functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.
  • quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group.
  • the 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
  • the 5-naphthoquinonediazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.
  • a naphthoquinone diazide sulfonyl ester compound containing a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, or the 4-naphthoquinone diazide sulfonyl ester compound and the 5 -It may contain a naphthoquinonediazide sulfonyl ester compound.
  • sulfonium salts phosphonium salts, and diazonium salts are preferable because they moderately stabilize the acid component generated by exposure.
  • sulfonium salts are preferred.
  • it can also contain a sensitizer etc. as needed.
  • the content of the photoacid generator is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the precursor of the heat resistant resin from the viewpoint of increasing sensitivity.
  • the quinonediazide compound is preferably 3 to 40 parts by mass.
  • the total amount of sulfonium salt, phosphonium salt and diazonium salt is preferably 0.5 to 20 parts by mass.
  • the photosensitive resin composition in the present invention contains a thermal crosslinking agent represented by the following chemical formula (31) or a thermal crosslinking agent having a structure represented by the following chemical formula (32) (hereinafter also referred to as a thermal crosslinking agent). May be.
  • thermal cross-linking agents can cross-link the heat-resistant resin or its precursor and other additive components, and can increase the chemical resistance and hardness of the resulting heat-resistant resin film.
  • R 31 represents a divalent to tetravalent linking group.
  • R 32 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, Cl, Br, I or F.
  • R 33 and R 34 each independently represents CH 2 OR 36 (R 36 is hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms).
  • R 35 represents hydrogen, a methyl group or an ethyl group. s represents an integer of 0 to 2, and t represents an integer of 2 to 4.
  • the plurality of R 32 may be the same or different.
  • the plurality of R 33 and R 34 may be the same or different.
  • the plurality of R 35 may be the same or different. Examples of the linking group R 31 shown below.
  • R 41 to R 60 are hydrogen, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group in which part of hydrogen of these hydrocarbon groups is substituted with Cl, Br, I or F. Indicates.
  • R 37 represents hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms.
  • u represents 1 or 2
  • v represents 0 or 1.
  • u + v is 1 or 2.
  • R 33 and R 34 represent CH 2 OR 36 which is a thermally crosslinkable group.
  • R 36 is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, because the thermal crosslinking agent represented by the chemical formula (31) leaves moderate reactivity and is excellent in storage stability. preferable.
  • thermal crosslinking agent including the structure represented by the chemical formula (31) are shown below.
  • R 37 is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms. From the viewpoint of stability of the compound and storage stability in the photosensitive resin composition, R 37 is preferably a methyl group or an ethyl group, and the number of (CH 2 OR 37 ) groups contained in the compound is 8 or less. It is preferable.
  • thermal crosslinking agent containing a group represented by the chemical formula (32) are shown below.
  • the content of the thermal crosslinking agent is preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the heat-resistant resin precursor. If content of a thermal crosslinking agent is 10 mass parts or more and 100 mass parts or less, the intensity
  • the varnish in the present invention may further contain a thermal acid generator.
  • the thermal acid generator generates an acid by heating after development, which will be described later, and promotes a crosslinking reaction between the precursor of the heat resistant resin and the thermal crosslinking agent, and also promotes a curing reaction of the precursor of the heat resistant resin. For this reason, the chemical resistance of the resulting heat-resistant resin film is improved, and film loss can be reduced.
  • the acid generated from the thermal acid generator is preferably a strong acid.
  • the thermal acid generator is preferably an aliphatic sulfonic acid compound represented by the chemical formula (33) or (34), and may contain two or more of these.
  • R 61 to R 63 may be the same or different and each represents an organic group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 20 carbon atoms. . Further, it may be an organic group having 1 to 20 carbon atoms containing hydrogen and carbon as essential components and containing one or more atoms selected from boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen.
  • the content of the thermal acid generator is preferably 0.5 parts by mass or more and preferably 10 parts by mass or less with respect to 100 parts by mass of the heat-resistant resin precursor from the viewpoint of further promoting the crosslinking reaction.
  • a compound containing a phenolic hydroxyl group may be contained for the purpose of supplementing the alkali developability of the photosensitive resin composition.
  • the compound containing a phenolic hydroxyl group include those having the following trade names (Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, manufactured by Honshu Chemical Industry Co., Ltd.) BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP- 4HBPA (Tetrakis P-DO-BPA), TrisP-HAP, TrisP-PA, TrisP-PHBA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, Bis
  • BIR-OC BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A
  • 1,4-dihydroxy Naphthalene 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-dihydroxyquinoline 2,6-dihydroxy Phosphorus, 2,3-dihydroxy quinoxaline, anthracene -1,2,10- triol, anthracene -1,8,9- triols, such as 8-quinolinol, and the like.
  • the resulting photosensitive resin composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. There is little film loss and development can be easily performed in a short time. Therefore, the sensitivity is easily improved.
  • the content of such a compound containing a phenolic hydroxyl group is preferably 3 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the precursor of the heat resistant resin.
  • the varnish in the present invention may contain an adhesion improving agent.
  • adhesion improvers vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane
  • Examples include silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, and aluminum chelating agents.
  • alkoxysilane-containing aromatic amine compounds, alkoxysilane-containing aromatic amide compounds and the like as shown below can be mentioned.
  • a compound obtained by reacting an aromatic amine compound and an alkoxy group-containing silicon compound can also be used.
  • examples of such compounds include compounds obtained by reacting an aromatic amine compound with an alkoxysilane compound containing a group that reacts with an amino group such as an epoxy group or a chloromethyl group.
  • the content of the adhesion improving agent is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the heat-resistant resin precursor.
  • the varnish in the present invention can contain inorganic particles for the purpose of improving heat resistance.
  • Inorganic particles used for such purposes include inorganic metal particles such as platinum, gold, palladium, silver, copper, nickel, zinc, aluminum, iron, cobalt, rhodium, ruthenium, tin, lead, bismuth, tungsten, and silicon oxide. (Silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, tungsten oxide, zirconium oxide, calcium carbonate, barium sulfate, and other metal oxide inorganic particles.
  • the shape of the inorganic particles is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, a flat shape, a lot shape, and a fiber shape.
  • the average particle size of the inorganic particles is preferably 1 nm to 100 nm, and more preferably 1 nm to 50 nm. More preferably, it is 1 nm or more and 30 nm or less.
  • the content of the inorganic particles is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 100 parts by mass or less, with respect to 100 parts by mass of the precursor of the heat resistant resin. More preferably, it is 80 mass parts or less, More preferably, it is 50 mass parts or less.
  • the content of the inorganic particles is 3 parts by mass or more, the heat resistance is sufficiently improved, and when the content is 100 parts by mass or less, the toughness of the fired film is hardly lowered.
  • the varnish in the present invention preferably contains (c) a surfactant in order to improve applicability.
  • a surfactant “Florard” (registered trademark) manufactured by Sumitomo 3M Co., Ltd., “Megafac” (registered trademark) manufactured by DIC Corporation, “sulfuron” (registered trademark) manufactured by Asahi Glass Co., Ltd., etc. Fluorosurfactant, Shin-Etsu Chemical Co., Ltd. KP341, Chisso Co., Ltd. DBE, Kyoeisha Chemical Co., Ltd.
  • Polyflow (registered trademark), “Granol” (registered trademark), Examples thereof include organic siloxane surfactants such as BYK manufactured by Chemie Corp. and acrylic polymer surfactants such as polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • the surfactant is preferably contained in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the heat-resistant resin precursor.
  • the precursor of the heat resistant resin can be polymerized by a known method.
  • a polyimide preferably used in the present invention tetracarboxylic acid or a corresponding acid dianhydride, active ester, active amide or the like as an acid component, and diamine or a corresponding trimethylsilylated diamine or the like as a diamine component in a reaction solvent.
  • a precursor polyamic acid By polymerizing, a precursor polyamic acid can be obtained.
  • the polyamic acid may be one in which a carboxyl group is esterified with a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms.
  • Reaction solvents include aprotic polar solvents such as N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, ethers such as diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate , Esters such as ethyl lactate, toluene, Can be used alone, or two or more such aromatic hydrocarbons such as Ren. Furthermore
  • a varnish can be obtained by dissolving a precursor of a heat resistant resin, and if necessary, a photoacid generator, a dissolution regulator, an adhesion improver, inorganic particles or a surfactant in a solvent.
  • a photoacid generator included in the heating temperature is preferably set in a range that does not impair the performance as the photosensitive resin composition, and is usually room temperature to 80 ° C.
  • each component is not particularly limited, and for example, there is a method of sequentially dissolving compounds having low solubility.
  • components that tend to generate bubbles when stirring and dissolving such as surfactants and some adhesion improvers, by dissolving other components and adding them last, poor dissolution of other components due to the generation of bubbles Can be prevented.
  • the obtained varnish is preferably filtered using a filter to remove foreign matters such as dust.
  • a filter to remove foreign matters such as dust.
  • the filter pore diameter include, but are not limited to, 10 ⁇ m, 3 ⁇ m, 1 ⁇ m, 0.5 ⁇ m, 0.2 ⁇ m, 0.1 ⁇ m, 0.07 ⁇ m, and 0.05 ⁇ m.
  • the material for the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), and polyethylene and nylon are preferable.
  • a method for producing a heat-resistant resin film which is one of the features of the present invention, includes a step of applying a solution containing a precursor of a heat-resistant resin on a support and a step of heating in multiple stages. And (B) oxygen in which the step of heating in the multi-stage is at least (A) heating at a temperature higher than 200 ° C. in an atmosphere having an oxygen concentration of 10% by volume or more.
  • a method for producing a heat-resistant resin film comprising a second heating step of heating at a temperature higher than that of the first heating step in an atmosphere having a concentration of 3% by volume or less in the above order.
  • a varnish containing a precursor of a heat resistant resin is applied on a support.
  • the support include a wafer substrate such as silicon and gallium arsenide, a glass substrate such as sapphire glass, soda-lime glass, and non-alkali glass, a metal substrate such as stainless steel and copper, a metal foil, and a ceramic substrate.
  • varnish coating methods include spin coating, slit coating, dip coating, spray coating, and printing, and these may be combined.
  • the support Prior to application, the support may be pretreated with the adhesion improving agent described above in advance.
  • a method of treating the surface of the support by a method such as spin coating, slit die coating, bar coating, dip coating, spray coating, or steam treatment. If necessary, a drying treatment under reduced pressure is performed, and then the reaction between the support and the adhesion improving agent can be advanced by heating at 50 ° C. to 300 ° C.
  • drying vacuum drying, heat drying, or a combination thereof can be used.
  • a method for drying under reduced pressure for example, a support body on which a coating film is formed is placed in a vacuum chamber, and the inside of the vacuum chamber is decompressed.
  • Heat drying is performed by using an apparatus such as a hot plate or an oven and treating with infrared rays or hot air.
  • a hot plate is used, the coating film is held directly on the plate or on a jig such as a proxy pin installed on the plate and dried by heating.
  • the material of the proxy pin there is a metal material such as aluminum or stainless steel, or a synthetic resin such as polyimide resin or “Teflon” (registered trademark). Any material can be used as long as it has heat resistance. .
  • the height of the proxy pin can be selected variously depending on the size of the support, the type of solvent used in the varnish, the drying method, etc., but is preferably about 0.1 to 10 mm.
  • the heating temperature varies depending on the type and purpose of the solvent used in the varnish, and it is preferably performed in the range of room temperature to 180 ° C. for 1 minute to several hours.
  • a pattern can be formed from the dried coating film by the method described below.
  • the coating film is exposed to actinic radiation through a mask having a desired pattern.
  • actinic radiation there are ultraviolet rays, visible rays, electron beams, X-rays and the like.
  • the exposed portion is dissolved in the developer.
  • it has negative photosensitivity the exposed area is cured and insolubilized in the developer.
  • a desired pattern is formed by removing an exposed portion in the case of a positive type and a non-exposed portion in the case of a negative type using a developer.
  • a developer in both positive and negative types, tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylamino acetate
  • An aqueous solution of an alkaline compound such as ethyl, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine is preferred.
  • these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added singly or in combination. Good.
  • polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lac
  • the above polar solvent not containing an alkaline aqueous solution alcohols, esters, ketones or the like can be used alone or in combination. After development, it is common to rinse with water.
  • alcohols such as ethanol and isopropyl alcohol
  • esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.
  • multistage heating which is a feature of the method for producing a heat resistant resin film of the present invention.
  • heating is performed in a range of 180 ° C. or more, and the coating film is made into a heat resistant resin film.
  • the heating process in the present invention requires heating in multiple stages, and at least (A) a first heating process for heating at a temperature higher than 200 ° C. in an atmosphere having an oxygen concentration of 10% by volume or more and (B) It is necessary to include, in the above order, the second heating step of heating at a temperature higher than that of the first heating step in an atmosphere having an oxygen concentration of 3% or less. The reason is as follows.
  • the varnish in the present invention contains a precursor other than a heat-resistant resin and a solvent, or when an unreacted monomer component is present, the component or its decomposition product remains in the heat-resistant resin film, Outgas characteristics may be degraded.
  • a compound containing a photoacid generator and a phenolic hydroxyl group is unlikely to cause outgassing because it does not have a bonding point with a heat resistant resin or a substrate, unlike a thermal crosslinking agent or an adhesion improver.
  • the surfactant is often a resin such as an acrylic polymer or polyoxyethylene alkyl ether.
  • the range of oxygen concentration in the first heating step is 10% by volume or more, more preferably 15% by volume or more. If the oxygen concentration range is 10% by volume or more, the components that cause outgassing can be oxidized by the oxidation reaction to promote decomposition and vaporization.
  • the oxygen concentration range in the first heating step is preferably 22% by volume or less. If the oxygen concentration range is 22% by volume or less, the first heating step can be performed in the atmosphere, and there is almost no need to introduce oxygen gas into the heating atmosphere.
  • the heating temperature in the first step needs to be equal to or higher than the temperature necessary to cure the precursor of the heat resistant resin. Specifically, a temperature higher than 200 ° C. is necessary. Moreover, it is preferable that the heating temperature in a 1st heating process is lower than the temperature which the heat resistant resin oxidizes. Specifically, it is preferably 420 ° C. or lower, more preferably 370 ° C. or lower, and further preferably 320 ° C. or lower.
  • the heating temperature in order to improve the mechanical properties of the heat resistant resin film, it is preferable to increase the heating temperature.
  • the heating temperature is increased in an atmosphere where oxygen molecules are present, oxidation of the heat resistant resin and decomposition due to the oxidation occur, and it becomes difficult to obtain good physical properties. Therefore, by heating in an atmosphere having a low oxygen concentration in the second heating step, the mechanical characteristics can be improved while suppressing oxidation and decomposition of the heat resistant resin.
  • the range of the oxygen concentration in the second heating step is 3% by volume or less, more preferably 1% by volume or less, and still more preferably 0.1% by volume or less. If the oxygen concentration range is 3% by volume or less, the resin can be prevented from deteriorating even if the heating temperature in the second step is 300 ° C. or higher. Further, the oxygen concentration range in the second heating step is preferably 0.000001% by volume or more, more preferably 0.00001% by volume or more, and further preferably 0.0001% by volume or more. If the range of oxygen concentration is 0.000001 volume% or more, it can prevent that the usage-amount of inert gas increases extremely and a burden is applied to a vacuum pump.
  • the heating temperature in the second step needs to be higher than the maximum temperature of the first heating step, specifically 300 ° C or higher, more preferably 350 ° C or higher, more preferably 400 ° C or higher. is there. On the other hand, it is preferable that the heating temperature in a 2nd heating process does not exceed the decomposition temperature of resin, specifically 600 degreeC or less is preferable and 550 degreeC or less is more preferable.
  • the step of heating in multiple steps in the method for producing a heat resistant resin film of the present invention may include three or more heating steps.
  • the heating is preferably performed at a temperature lower than that of the first heating step in an atmosphere having an oxygen concentration higher than that of the first heating step.
  • an additional step is provided after the second heating step, it is preferable that heating is performed at a temperature higher than that of the second heating step in an atmosphere having an oxygen concentration equal to or lower than that of the second heating step.
  • any of the methods described in the above-mentioned heat drying can be suitably used. That is, it is preferable to use an apparatus such as a hot plate or an oven and treat with hot air or infrared rays.
  • Cooling includes a method in which heating by the apparatus is stopped and natural cooling is performed, or a cooling unit provided in the apparatus is forcibly cooled.
  • room temperature When taking out manually after cooling, it is preferable to cool to room temperature. However, if it is not limited to this, it may be taken out at a temperature higher than room temperature. However, it is preferable to carry out within a range in which the physical properties of the heat resistant resin film are not greatly reduced.
  • the atmosphere in the apparatus at the time of cooling is preferably a state in which the atmosphere immediately after the end of the heating process is maintained.
  • the atmosphere in the apparatus may be replaced with air when the temperature in the apparatus is cooled to a predetermined temperature or lower. Also in this case, it is preferable to determine the temperature to be substituted with the atmosphere within a range in which the physical properties of the heat resistant resin film are not greatly reduced.
  • This furnace is A temperature measurement unit for measuring the temperature in the furnace; A temperature adjusting unit for adjusting the temperature in the furnace; An oxygen concentration measuring unit for measuring the oxygen concentration in the furnace; A gas flow rate adjusting unit for adjusting the flow rate of the heating atmosphere gas into the furnace; A control unit for controlling the temperature adjusting unit and the gas flow rate adjusting unit;
  • a heating furnace comprising: The controller is While controlling the gas flow rate adjustment unit according to the oxygen concentration in the furnace measured by the oxygen concentration measurement unit, The temperature adjusting unit is controlled so that the temperature in the furnace measured by the temperature measuring unit after the oxygen concentration reaches a predetermined oxygen concentration becomes a predetermined temperature.
  • FIG. 1 is a schematic view of a heating furnace 10 which is an embodiment of the heating of the present invention.
  • Gas supply pipes 41 and 51 and an exhaust pipe 61 are connected to the furnace body 11 for arranging the heated body.
  • the gas supply pipes 41 and 51 are provided with gas flow rate adjusting units, respectively, and a purge on / off valve 42 and 52, a purge flow rate adjusting valve 43 and 53, a running on / off valve 44 and 54, and a running flow rate adjusting valve, respectively. 45 and 55.
  • the exhaust pipe 61 is also provided with an exhaust opening / closing valve 62 and an exhaust flow rate adjusting valve 63.
  • the purge on-off valve is opened particularly when the atmosphere in the furnace 12 filled with a gas different from the supply gas is rapidly replaced with the supply gas. For this reason, it is necessary that a sufficiently large gas flow rate is set by the purge flow rate adjusting valve so that the inside of the furnace 12 can be replaced with the supply gas.
  • the running on-off valve is opened particularly when supplying gas in order to maintain the atmosphere in the furnace 12. For this reason, it is sufficient that the gas flow rate capable of maintaining the atmosphere in the furnace 12 is set by the running flow rate adjustment valve, and usually a gas flow rate lower than the flow rate set by the purge flow rate control valve is set.
  • the furnace body 11 is provided with a temperature measuring unit 22 and a heating unit 23.
  • the temperature measuring unit 22 and the heating unit 23 are connected to the temperature adjusting unit 21 through an electrical connection indicated by a broken line. Further, the temperature adjustment unit 21 is electrically connected to the control unit 71.
  • the heating furnace 10 is provided with an oxygen concentration measuring unit for measuring the oxygen concentration, and includes an oxygen concentration meter 31 and a gas sampling port 32 for collecting the gas in the furnace 12.
  • the oxygen concentration meter 31 is also connected to the control unit 71 via an electrical connection indicated by a broken line.
  • a user interface 81 that can set a program in advance for automatically executing the heating process under a predetermined condition is provided, which is also electrically connected to the control unit 71.
  • the gas flow rate adjusting unit is also connected to the control unit 71 via an electrical connection, and the on / off valves 42, 44, 52, 54, and 62 are opened and closed electrically from the control unit 71. Controlled by signal.
  • the furnace body 11 is provided with an opening / closing door for taking in and out the heated body.
  • the control unit 71 controls at least the temperature adjustment unit 21 and the gas flow rate adjustment unit. Specifically, the gas flow rate adjusting unit is controlled in accordance with the oxygen concentration in the furnace 12 measured by the oxygen concentration measuring unit, and the temperature measuring unit after the oxygen concentration in the furnace 12 reaches a predetermined oxygen concentration. The temperature adjusting unit 21 is controlled so that the temperature in the furnace 12 measured in step 1 becomes a predetermined temperature.
  • control unit 71 can control the temperature adjusting unit 21 and the gas flow rate adjusting unit so as to continuously perform the multi-step heating process. For example, at least a first heating step in which heating is performed at a first temperature in a first oxygen concentration atmosphere and a second heating step in which heating is performed at a second temperature in a second oxygen concentration atmosphere.
  • control unit 71 can control the gas flow rate adjusting unit and the temperature adjusting unit 21 so as to continuously perform the first heating process and the second heating process.
  • the heat-resistant resin film of the present invention is manufactured using the heating furnace 10
  • the function of each part will also be described.
  • a two-step heating process is performed, and the first heating process and the second heating process are performed in the atmosphere (oxygen concentration 21 vol%) and nitrogen (oxygen concentration 0.01 vol% or less), respectively. I will do it.
  • the gas supply pipes 41 and 51 are connected to nitrogen and air supply lines, respectively. Subsequently, a coating film obtained by applying and drying a solution containing the above-described precursor of the heat-resistant resin film on the substrate is placed in the furnace body 11. A heating process program is set via the user interface 81.
  • the first heating step is started. If the inside of the furnace 12 does not have the same oxygen concentration as the atmosphere, it is detected by the oximeter 31 and a signal is sent from the control unit 71 to the purge opening / closing valve 52 to open the valve and purge the atmosphere into the furnace 12. To do. When the inside of the furnace 12 is filled with the atmosphere and the oximeter 31 detects this, the purge on-off valve 52 is closed by the signal from the control unit 71 and the supply of the atmosphere is stopped. During the first heating step, the purge on-off valve 42 and the running on-off valve 44 provided in the gas supply pipe 41 for supplying nitrogen are both closed.
  • a signal is sent from the control unit 71 to the temperature adjustment unit 21, and the temperature rise is started according to a preset program.
  • the temperature measuring unit 22 always monitors the temperature in the furnace 12 and the temperature adjusting unit 21 controls the heating unit 23 so that heating can be performed as programmed. Since outgas is generated from the coating film during the first heating step, the atmosphere is always supplied from the gas supply pipe 51 for supplying air to the furnace 12, and the outgas from the coating film is exhausted together with the atmosphere in the furnace 12. It is preferable to discharge from 61. Therefore, it is preferable that the running on-off valve 54 of the gas supply pipe 51 is open during heating.
  • the running flow rate adjustment valve 55 and the exhaust flow rate adjustment valve 63 are adjusted so that the atmosphere in the furnace 12 is always positive. When the pressure in the furnace 12 is negative, outside air may enter the furnace 12 through a gap between the doors.
  • the oxygen concentration meter 31 can always monitor the oxygen concentration in the furnace 12. If a decrease in oxygen concentration is detected, a signal is sent from the control unit 71 to the gas flow rate adjustment unit, and the purge on-off valve 52 is opened to purge the atmosphere. If the oxygen concentration in the furnace 12 returns to a predetermined concentration and the oximeter 31 can detect it, a signal is sent from the control unit 71 to the gas flow rate adjustment unit, and the purge on-off valve 52 is closed to stop the purge of the atmosphere. .
  • the running on / off valve 54 may be closed while the purge on / off valve 52 is opened to purge the atmosphere. However, when the purge on-off valve 52 is closed to stop the purge of the atmosphere, it is preferable that the running on-off valve 54 is opened to continuously supply air.
  • a signal is sent from the control unit 71 to the gas flow rate adjustment unit in order to reduce the oxygen concentration in the furnace 12 to a predetermined concentration.
  • both the purge on-off valve 52 and the running on-off valve 54 of the gas supply pipe 51 are closed, and the supply of air is stopped.
  • the purge opening / closing valve 42 of the gas supply pipe 41 is opened to supply nitrogen into the furnace 12. The supply of nitrogen is continued until the inside of the furnace 12 becomes a predetermined oxygen concentration or less, and the start of the second heating step is often in a standby state.
  • the oxygen concentration meter 31 detects that the oxygen concentration in the furnace 12 has become equal to or lower than a predetermined oxygen concentration
  • the signal is sent to the control unit 71, and the purge opening / closing valve 42 of the gas supply pipe 41 is sent from the control unit 71. Closed.
  • a signal for starting the second heating step is sent from the control unit 71 to the temperature adjusting unit 21 to start heating.
  • the oxygen concentration in the furnace 12 can always be monitored by the oxygen concentration meter 31. If an increase in oxygen concentration is detected, a signal is sent from the control unit 71 to the gas flow rate adjustment unit, and the purge on-off valve 42 is opened to purge nitrogen. When the oxygen concentration in the furnace 12 returns to a predetermined concentration or less and the oximeter 31 detects this, a signal is sent from the control unit 71 to the gas flow rate adjustment unit, and the purge on-off valve 42 is closed to purge nitrogen. Stop.
  • cooling of the furnace 12 begins.
  • a signal is sent from the control unit 71 to the temperature adjustment unit 21 and heating in the heating unit 23 is stopped according to the signal, cooling starts naturally.
  • a heating furnace in which a cooling unit (not shown) electrically connected to the temperature adjusting unit 21 is provided in the furnace body 11 may be used. Due to the action of the cooling section, the temperature in the furnace 12 can be forcibly lowered.
  • the temperature measuring unit 22 detects that the temperature in the furnace 12 has become equal to or lower than a predetermined temperature according to the program set in the user interface 81.
  • the signal is transmitted to the control unit 71 via the temperature adjustment unit 21.
  • a signal is sent from the control unit 71 to the gas flow rate adjusting unit, the purge on-off valve 42 and the running on-off valve 44 provided in the gas supply pipe 41 are closed, and the supply of nitrogen to the furnace 12 is stopped.
  • the purge opening / closing valve 52 provided in the gas supply pipe 51 is opened, and the supply of air to the furnace 12 is started.
  • the temperature and oxygen concentration in the furnace 12 are monitored by the temperature measuring unit 22 and the oxygen concentration meter 31, and the temperature in the furnace 12 has dropped below a predetermined temperature set by the program. All of the steps are completed when the atmosphere of 12 reaches almost the same oxygen concentration as the atmosphere. After that, the coating film is taken out from the open / close door provided in the furnace body 11. During the heating process, it is preferable that the open / close door is in a locked state, and a mechanism in which the lock is released when all the processes are completed and the heated object can be taken out is preferable.
  • the gas flow rate adjustment unit is controlled by the control unit 71 and automatically opens and closes the on-off valves 42, 44, 52, 54 and 62 according to a program set in advance via the user interface 81. It is a mechanism to do.
  • the flow rate adjusting valves 43, 45, 53, 55 and 63 may be adjusted in advance and not changed during the heating process, or may be automatically adjusted.
  • the oxygen concentration meter 31 it is necessary to keep the oxygen concentration meter 31 in operation in order to monitor the oxygen concentration during heating.
  • the heat-resistant resin film obtained by the present invention includes a surface protective film and an interlayer insulating film of a semiconductor element, an insulating layer and a spacer layer of an organic electroluminescence element (organic EL element), a planarization film of a thin film transistor substrate, and an insulating film of an organic transistor. It is suitably used for a layer, a flexible printed circuit board, a flexible display substrate, a flexible electronic paper substrate, a flexible solar cell substrate, a flexible color filter substrate, and the like. Especially for image display devices such as organic EL, electronic paper, and color filters, heat resistance (outgas characteristics, glass transition temperature, etc.) to the temperature of the manufacturing process and toughness are imparted to the image display device after manufacture. Since the heat-resistant resin film has mechanical properties suitable for the above, it can be preferably used as those substrates.
  • a method of using the heat resistant resin film obtained by the production method of the present invention as a substrate of an image display device will be described.
  • a heat resistant resin film is produced on a support such as a glass substrate by the production method of the present invention.
  • pixel driving elements or colored pixels are formed on the heat resistant resin film.
  • a TFT which is an image driving element
  • a first electrode which is an image driving element
  • an organic EL light emitting element a second electrode
  • a sealing film are sequentially formed.
  • colored pixels such as red, green, and blue are formed.
  • a gas barrier film may be provided between the heat resistant resin film and the pixel driving element or the colored pixel.
  • the gas barrier film By providing the gas barrier film, it is possible to prevent moisture and oxygen from passing through the heat resistant resin film from the outside of the image display device and causing deterioration of the pixel driving element and the colored pixel.
  • a single film of inorganic films such as a silicon oxide film (SiOx), a silicon nitrogen film (SiNy), a silicon oxynitride film (SiOxNy), or a laminate of a plurality of types of inorganic films is used.
  • the gas barrier film is formed by using a method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD).
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • a film in which these inorganic films and organic films such as polyvinyl alcohol are alternately laminated can be used.
  • peeling is performed at the interface between the support and the heat resistant resin film to obtain an image display device including the heat resistant resin film.
  • Examples of the method of peeling at the interface between the support and the heat-resistant resin film include a method using a laser, a mechanical peeling method, and a method of etching the support. In the method using a laser, peeling can be performed without damaging the image display element by irradiating the support such as a glass substrate from the side where the image display element is not formed. Moreover, you may provide the primer layer for making it easy to peel between a support body and a heat resistant resin film.
  • Measuring device Tensilon Universal Material Testing Machine “RTM-100” (Orientec Co., Ltd.) Measurement sample shape: Ribbon shape Measurement sample size: Length> 70 mm, width 10 mm Pulling speed: 50mm / min Distance between chucks at the start of the test: 50 mm Experimental temperature: 0 to 35 ° C Number of samples: 10 Calculation method of measurement results: An arithmetic average value of measured values of 10 samples was obtained.
  • Measuring device heating section “Small-4” (manufactured by Toray Research Center), GC / MS “QP5050A (7)” (manufactured by Shimadzu Corporation) Heating condition: Temperature is raised from room temperature at 10 ° C./min and held for 30 minutes after reaching 450 ° C. Measurement atmosphere: under a helium stream (50 mL / min).
  • thermometer and a stirring rod with stirring blades were set in a 200 mL four-necked flask.
  • 90 g of NMP was added under a dry nitrogen stream, and the temperature was raised to 60 ° C.
  • 5.407 g (50.00 mmol) of p-PDA was added with stirring, and washed with 15 g of NMP.
  • 14.49 g (49.25 mmol) of BPDA was added and washed with 15 g of NMP.
  • Synthesis example 2 A thermometer and a stirring rod with stirring blades were set in a 200 mL four-necked flask. Next, 90 g of NMP was added under a dry nitrogen stream, and the temperature was raised to 40 ° C. After raising the temperature, 10.01 g (50.00 mmol) of DAE was added while stirring and washed with 15 g of NMP. After confirming that DAE was dissolved, 10.74 g (49.25 mmol) of PMDA was added and washed with 15 g of NMP. Cooled after 4 hours.
  • Synthesis Example 3 A thermometer and a stirring rod with stirring blades were set in a 200 mL four-necked flask. Next, 90 g of NMP was added under a dry nitrogen stream, and the temperature was raised to 60 ° C. After the temperature was raised, 5.407 g (50.00 mmol) of p-PDA was added with stirring, and washed with 15 g of NMP. After confirming that p-PDA was dissolved, 15.28 g (49.25 mmol) of ODPA was added and washed with 15 g of NMP.
  • Synthesis Example 4 A thermometer and a stirring rod with stirring blades were set in a 200 mL four-necked flask. Next, 90 g of NMP was charged under a dry nitrogen stream and cooled to 10 ° C. or lower. After cooling, 10.81 g (50.00 mmol) of HAB and 13.22 g (150.0 mmol) of glycidyl methyl ether were added with stirring, and washed with 15 g of NMP. Subsequently, 10.15 g (50.00 mmol) of TPC diluted with 15 g of NMP was added dropwise. After completion of dropping, the mixture was stirred overnight at room temperature.
  • Synthesis Example 5 A thermometer and a stirring rod with stirring blades were set in a 200 mL four-necked flask. Next, 90 g of NMP was added under a dry nitrogen stream, and the temperature was raised to 60 ° C. After the temperature was raised, 6.488 g (60.00 mmol) of p-PDA was added with stirring and washed with 15 g of NMP. After confirming that p-PDA was dissolved, 7.061 g (24.00 mmol) of BPDA and 7.525 g (34.50 mmol) of PMDA were added and washed with 15 g of NMP. Cooled after 4 hours. After cooling, 0.100 g of a surfactant d was added to make a varnish.
  • Synthesis Example 6 Synthesis of photoacid generator a A 1000 mL four-necked flask was equipped with a thermometer and a stirring rod with stirring blades. Next, in a dry nitrogen stream, 15.31 g (50.00 mmol) of 1,1,1-tris (4-hydroxyphenyl) ethane and 20.15 g (75.00 mmol) of 5-naphthoquinone diazide sulfonyl chloride were added to 1,4 -Dissolved in 450 g dioxane and brought to room temperature.
  • Example 1 The resin solution obtained in Synthesis Example 1 was subjected to pressure filtration using a 1 ⁇ m filter to remove foreign matters. Spin coating was performed on a 6-inch glass substrate using a coating and developing apparatus Mark-7 (manufactured by Tokyo Electron Ltd.) so that the film thickness after pre-baking was 15 ⁇ m, and then pre-baking was performed at 140 ° C. for 5 minutes. . The pre-baked film was heated using a gas oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) according to the following first condition, and then heated according to the following second condition to produce a heat resistant resin film on the glass substrate. . The heating under the first condition and the heating under the second condition were performed continuously.
  • a gas oven IH-21CD manufactured by Koyo Thermo Systems Co., Ltd.
  • Second step Heated at 400 ° C. for 30 minutes in a nitrogen atmosphere with an oxygen concentration of less than 20 ppm.
  • the temperature was raised from room temperature, and the rate of temperature rise was 5 ° C./min.
  • the temperature was raised from the maximum heating temperature of the first step, and the rate of temperature rise was 5 ° C./min.
  • Examples 2 to 10c, Comparative Examples 1 to 12 As shown in Table 1, a pre-baked film was prepared in the same manner as in Example 1 using the resin solutions obtained in Synthesis Examples 1 to 5. However, Examples 6 to 9 and Comparative Examples 6 to 9 were used with the additives shown in Table 1 added. Subsequently, a heat resistant resin film was produced in the same manner as in Example 1 except that the maximum heating temperature and the heating atmosphere in the first step and the second step were changed to the conditions shown in Table 1. However, for Comparative Example 12, the following third step was added.
  • Third step Heated at 450 ° C. for 30 minutes in an air atmosphere. However, in the third step, the temperature was raised from room temperature, and the rate of temperature rise was 5 ° C./min.
  • Tables 1 and 2 show the measurement results of the maximum tensile elongation, maximum tensile stress, and outgas of the heat resistant resin films obtained in Examples 1 to 10c and Comparative Examples 1 to 12.
  • Example 11 A gas barrier film made of a laminate of SiO 2 and Si 3 N 4 was formed on the heat resistant resin film obtained in Example 10a by CVD. Subsequently, a TFT was formed, and an insulating film made of Si 3 N 4 was formed so as to cover the TFT. Next, after forming a contact hole in the insulating film, a wiring connected to the TFT through the contact hole was formed.
  • a flattening film was formed.
  • a first electrode made of ITO was formed on the obtained flattened film by being connected to the wiring.
  • a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed.
  • pattern processing was performed by wet etching using an ITO etchant.
  • the resist pattern was stripped using a resist stripping solution (mixed solution of monoethanolamine and diethylene glycol monobutyl ether).
  • the substrate after peeling was washed with water and dehydrated by heating to obtain an electrode substrate with a planarizing film.
  • an insulating film having a shape covering the periphery of the first electrode was formed.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus.
  • a second electrode made of Al / Mg was formed on the entire surface above the substrate.
  • a sealing film made of a laminate of SiO 2 and Si 3 N 4 was formed by CVD.
  • the glass substrate was irradiated with a laser (wavelength: 308 nm) from the side where the heat resistant resin film was not formed, and peeling was performed at the interface with the heat resistant resin film.
  • Comparative Example 13 On the heat-resistant resin film obtained in Comparative Example 10, a gas barrier film was formed by CVD in the same manner as in Example 11. Continued to form the TFT, but due to the cause of outgassing of the heat-resistant resin film, the adhesion between the heat-resistant resin film and the gas barrier film was reduced and peeling occurred. could not.
  • the obtained heat-resistant resin film includes a surface protective film and an interlayer insulating film of a semiconductor element, an insulating layer and a spacer layer of an organic electroluminescence element (organic EL element), a flattening film of a thin film transistor substrate, an insulating layer of an organic transistor, a flexible It can be suitably used for printed circuit boards, flexible display substrates, flexible electronic paper substrates, flexible solar cell substrates, flexible color filter substrates, and the like.

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TW202112837A (zh) 2019-09-26 2021-04-01 日商富士軟片股份有限公司 導熱層的製造方法、積層體的製造方法及半導體器件的製造方法
CN115685681A (zh) * 2021-07-27 2023-02-03 吉林奥来德光电材料股份有限公司 树脂组合物、树脂膜及显示器件

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