WO2022224933A1 - 積層基板、積層体、積層体の製造方法、電子デバイス用部材付き積層体、電子デバイスの製造方法 - Google Patents

積層基板、積層体、積層体の製造方法、電子デバイス用部材付き積層体、電子デバイスの製造方法 Download PDF

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WO2022224933A1
WO2022224933A1 PCT/JP2022/018045 JP2022018045W WO2022224933A1 WO 2022224933 A1 WO2022224933 A1 WO 2022224933A1 JP 2022018045 W JP2022018045 W JP 2022018045W WO 2022224933 A1 WO2022224933 A1 WO 2022224933A1
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bis
resin layer
silicone resin
laminate
electronic device
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PCT/JP2022/018045
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English (en)
French (fr)
Japanese (ja)
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和夫 山田
周馬 川崎
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Ａｇｃ株式会社
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Priority to CN202280029474.1A priority Critical patent/CN117279780A/zh
Priority to KR1020237035218A priority patent/KR20240000475A/ko
Priority to JP2023515462A priority patent/JP7371813B2/ja
Publication of WO2022224933A1 publication Critical patent/WO2022224933A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10798—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing silicone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating

Definitions

  • the present invention relates to a laminated substrate, a laminated body, a method for manufacturing a laminated body, a laminated body with an electronic device member, and a method for manufacturing an electronic device.
  • Electronic devices such as solar cells (PV); liquid crystal panels (LCD); organic EL panels (OLED); receiving sensor panels that detect electromagnetic waves, X-rays, ultraviolet rays, visible light rays, infrared rays, etc.; is doing.
  • substrates such as polyimide resin substrates used in electronic devices are becoming thinner. If the strength of the substrate is insufficient due to the thinning, the handleability of the substrate decreases, and problems may occur in the process of forming electronic device members on the substrate (member forming process).
  • Patent Document 1 a technology has been proposed that uses a laminate in which a polyimide resin substrate is arranged on a support base (Patent Document 1). More specifically, in Patent Document 1, a polyimide varnish is applied on a thermosetting resin composition cured body layer to form a resin varnish cured film (corresponding to a polyimide film), and a resin varnish cured film is coated with It is disclosed that precision elements can be placed. With the technique of Patent Document 1, the resin varnish cured film can be easily peeled off from the thermosetting resin composition cured body layer and used as a polyimide resin substrate.
  • a glass substrate having a first surface and a second surface facing the first surface; and a silicone resin layer disposed on the second surface of the glass base material, Variation in surface roughness Ra of the surface of the silicone resin layer opposite to the glass substrate is 1.00 nm or less, A laminated substrate, wherein the thickness variation of the silicone resin layer is 1.5 ⁇ m or less.
  • a peelable protective film is arranged on the silicone resin layer.
  • a laminate comprising the laminated substrate according to any one of [1] to [3] and a polyimide film disposed on the silicone resin layer of the laminated substrate.
  • a polyimide varnish containing polyimide or its precursor and a solvent is applied, and the polyimide film is coated on the silicone resin layer. to form a laminate having the glass substrate, the silicone resin layer, and the polyimide film.
  • [7] forming an electronic device member on the polyimide film of the laminate according to [4]; A member forming step of obtaining a laminate with an electronic device member; and a separation step of obtaining an electronic device having the polyimide film and the electronic device member from the laminate with the electronic device member.
  • a polyimide varnish is applied on the surface of a silicone resin layer, and then peeled off from the silicone resin layer to produce a polyimide film, which can produce a polyimide film with little optical unevenness.
  • a polyimide film which can produce a polyimide film with little optical unevenness.
  • BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically one Embodiment of the laminated substrate of this invention.
  • BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically one Embodiment of the laminated body of this invention. It is a figure for demonstrating a member formation process. It is a figure for demonstrating a isolation
  • the terms used in the present invention have the following meanings.
  • the variation of the surface roughness Ra is measured by measuring the surface roughness Ra at any 10 points on the target surface (measurement area: vertical 940 ⁇ m ⁇ horizontal 700 ⁇ m), and the maximum and minimum values among the 10 measured values. is the difference between
  • the average value of surface roughness Ra is the arithmetic mean value of 10 measured values measured by the above procedure.
  • the surface roughness Ra is measured using, for example, a non-contact surface/layer profile measuring system "Vertscan R3300-lite” manufactured by Ryoka Systems Co., Ltd.
  • the variation in film thickness is the difference between the maximum and minimum values among the 10 measured values obtained by measuring the film thickness at any 10 locations on the object.
  • the average value of the film thickness is the arithmetic mean value of the 10 measured values obtained by measuring the variations in the film thickness.
  • the measurement range excludes a peripheral area of 3 mm from the edge of the silicone resin layer toward the center.
  • the film thickness is measured by, for example, a contact film thickness measurement device.
  • a numerical range expressed using " ⁇ ” means a range that includes the numerical values described before and after " ⁇ " as lower and upper limits.
  • FIG. 1 is a cross-sectional view schematically showing one embodiment of the laminated substrate of the present invention.
  • the laminated substrate 10 includes a glass substrate 12 having a first surface 12a and a second surface 12b facing the first surface 12a, and a silicone resin layer disposed on the second surface 12b of the glass substrate 12. 14.
  • polyimide varnish is applied onto the silicone resin layer 14 of the laminated substrate 10, and then a polyimide film is formed.
  • An electronic device member is formed on this polyimide film, and then the polyimide film (that is, an electronic device) on which the electronic device member is formed is separated. Thus, an electronic device is manufactured.
  • the variation in the surface roughness Ra of the surface 14a of the silicone resin layer 14 on the side opposite to the glass substrate 12 defined below is 1.00 nm or less.
  • the variation in the surface roughness Ra of the surface 14a of the silicone resin layer 14 opposite to the glass substrate 12 is 1.00 nm or less, it is formed on the silicone resin layer 14 of the laminated substrate 10 and then peeled off. , a polyimide film with little optical unevenness can be produced.
  • the variation in the surface roughness Ra of the surface 14a of the silicone resin layer 14 opposite to the glass substrate 12 is preferably 0.70 nm or less, more preferably 0.40 nm or less.
  • the lower limit of variation in the surface roughness Ra of the surface 14a of the silicone resin layer 14 opposite to the glass substrate 12 is 0.00 nm.
  • the thickness variation of the silicone resin layer 14 is 1.5 ⁇ m or less. If the variation in thickness of the silicone resin layer 14 is 1.5 ⁇ m or less, a polyimide film with little optical unevenness is manufactured by forming a polyimide film on the silicone resin layer 14 of the laminated substrate 10 and then peeling it off. can. Variation in the thickness of the silicone resin layer 14 is preferably 1.2 ⁇ m or less, more preferably 1.0 ⁇ m or less. The lower limit of variation in the film thickness of the silicone resin layer 14 is 0.0 ⁇ m.
  • each layer (the glass substrate 12 and the silicone resin layer 14) constituting the laminated substrate 10 will be described in detail, and then the method for manufacturing the laminated substrate 10 will be described in detail.
  • the glass substrate 12 is a member that supports and reinforces the polyimide film.
  • As the type of glass alkali-free borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide glasses containing silicon oxide as a main component are preferable.
  • As the oxide glass glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferable.
  • the glass substrate includes a glass substrate made of alkali-free borosilicate glass (trade name "AN100” manufactured by AGC Inc.).
  • the manufacturing method of the glass substrate is usually obtained by melting glass raw materials and forming the molten glass into a plate shape.
  • a molding method may be a general one, and examples thereof include a float method, a fusion method, and a slot down-draw method.
  • the shape (shape of the main surface) of the glass base material 12 is not particularly limited, but a rectangular shape is preferable.
  • Glass substrate 12 is preferably not flexible. Therefore, the thickness of the glass substrate 12 is preferably 0.3 mm or more, more preferably 0.5 mm or more. On the other hand, the thickness of the glass substrate 12 is preferably 1.0 mm or less.
  • the silicone resin layer 14 is a film for preventing peeling of the polyimide film placed on the silicone resin layer 14 .
  • a silicone resin layer 14 is arranged on the glass substrate 12 .
  • a silicone resin is a resin containing a specific organosiloxy unit, and is usually obtained by curing a curable silicone.
  • Curable silicones are classified into addition reaction silicones, condensation reaction silicones, ultraviolet curing silicones, and electron beam curing silicones according to their curing mechanism, and any of them can be used. Condensation reaction type silicone is particularly preferable as the silicone resin.
  • the condensation-reactive silicone includes a hydrolyzable organosilane compound that is a monomer or a mixture thereof (monomer mixture), or a partially hydrolyzed condensate (organopolysiloxane) obtained by partially hydrolyzing and condensing a monomer or a monomer mixture.
  • a silicone resin can be formed by proceeding a hydrolysis/condensation reaction (sol-gel reaction) using this condensation reaction type silicone.
  • the silicone resin layer 14 is preferably formed using a curable composition containing curable silicone.
  • the curable composition may contain, in addition to the curable silicone, a solvent, a platinum catalyst (when addition reaction silicone is used as the curable silicone), a leveling agent, a metal compound, and the like.
  • metal elements contained in metal compounds include 3d transition metals, 4d transition metals, lanthanide metals, bismuth (Bi), aluminum (Al), and tin (Sn).
  • the content of the metal compound is not particularly limited and is adjusted as appropriate.
  • the silicone resin layer 14 preferably has a hydroxy group. Hydroxy groups can appear when part of the Si--O--Si bonds forming the silicone resin of the silicone resin layer 14 are broken. Moreover, when condensation reaction type silicone is used, its hydroxy group can become the hydroxy group of the silicone resin layer 14 .
  • the average thickness of the silicone resin layer 14 is preferably 50.0 ⁇ m or less, more preferably 30.0 ⁇ m or less, and even more preferably 12.0 ⁇ m or less.
  • the average thickness of the silicone resin layer 14 is preferably more than 1 ⁇ m, and more preferably 6.0 ⁇ m or more from the viewpoint of more excellent foreign matter embedding properties.
  • the embedding property of foreign matter is excellent, protrusions due to foreign matter are less likely to occur in the silicone resin layer, and when the electronic device member is formed on the polyimide film, the risk of disconnection in the electronic device member due to the protrusions is suppressed. be done.
  • the voids formed when the protrusions are generated are observed as bubbles, the ability to embed foreign matter can be evaluated based on the presence or absence of the generation of bubbles.
  • the average value of the surface roughness Ra of the surface 14a of the silicone resin layer 14 is preferably 50.00 nm or less, more preferably 30.00 nm or less, even more preferably 15.00 nm or less, and particularly preferably 5.00 nm or less. If the average value of the surface roughness Ra of the surface 14a is within the above range, the surface roughness of the polyimide film produced by forming it on the silicone resin layer 14 of the laminated substrate 10 and then peeling it off is reduced.
  • the average value of the surface roughness Ra of the surface 14a of the silicone resin layer 14 is preferably 0.10 nm or more, more preferably 0.30 nm or more, in order to maintain a state of close contact with the polyimide film formed on the silicone resin layer 14. is more preferred.
  • the laminate substrate 10 may have a peelable protective film disposed on the silicone resin layer 14 .
  • the protective film is a film that protects the surface of the silicone resin layer 14 until the later-described polyimide varnish is applied on the silicone resin layer 14 .
  • Examples of materials that make up the protective film include polyimide resins, polyester resins (eg, polyethylene terephthalate, polyethylene naphthalate), polyolefin resins (eg, polyethylene, polypropylene), and polyurethane resins. Polyester resins are preferred, and polyethylene terephthalate is more preferred, as the material constituting the protective film.
  • the average thickness of the protective film is preferably 20 ⁇ m or more, more preferably 30 ⁇ m or more, and even more preferably 50 ⁇ m or more, in order to reduce the influence of external force.
  • the average thickness of the protective film is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, and even more preferably 100 ⁇ m or less.
  • the protective film may further have an adhesion layer on the surface on the silicone resin layer 14 side.
  • a known adhesive layer can be used as the adhesive layer.
  • adhesives constituting the adhesive layer include (meth)acrylic adhesives, silicone adhesives, and urethane adhesives.
  • the adhesion layer may be made of a resin, and examples of the resin include vinyl acetate resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, (meth)acrylic resin, and butyral resin. , polyurethane resins, and polystyrene elastomers.
  • the average value of the surface roughness Ra of the protective film is preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 15 nm or less, because the peeling force when the protective film is peeled off is reduced. Moreover, the average value of the surface roughness Ra of the protective film is preferably 0.1 nm or more, more preferably 0.5 nm or more, so that the protective film and the silicone resin layer can be maintained in close contact with each other.
  • a method for manufacturing the laminated substrate is not particularly limited, and includes known methods. Among them, in terms of better productivity, a transfer film having a temporary support and a precursor film that becomes a silicone resin layer after heat treatment disposed on the temporary support is prepared, and the precursor in the transfer film is prepared. A method of bonding a film to a predetermined position on a glass base material, and subjecting the resulting laminated body having the glass base material, the precursor film, and the temporary support to a heat treatment can be used. A silicone resin layer is formed by performing heat treatment.
  • the obtained laminate may be washed with an alkaline detergent.
  • the substrate may be rinsed with pure water, if necessary.
  • the water may be drained with an air knife. After the air knife, the laminate may be dried by heating. Further, in the washing, the laminate may be washed with a brush.
  • the temperature of the alkaline detergent used for washing and the temperature of pure water used for rinsing are preferably 20° C. or higher, more preferably 40° C. or higher, from the viewpoint of detergency.
  • the heat treatment (annealing process) for forming the silicone resin layer is preferably carried out while applying pressure.
  • heat treatment and pressure treatment are preferably performed using an autoclave.
  • the heating temperature for heat treatment is preferably 50°C or higher, more preferably 55°C or higher, and even more preferably 60°C or higher.
  • the heating temperature for the heat treatment is preferably 350° C. or lower, more preferably 300° C. or lower, and even more preferably 250° C. or lower.
  • the heating time is preferably 10 minutes or longer, more preferably 20 minutes or longer.
  • the heating time is preferably 60 minutes or less, more preferably 40 minutes or less.
  • the pressure for the pressurization treatment is preferably 0.5 to 1.5 MPa, more preferably 0.8 to 1.0 MPa.
  • the heat treatment may be performed multiple times.
  • the heating conditions may be changed.
  • the heating temperature may be changed.
  • the first heat treatment may be performed under a temperature condition of less than 200° C.
  • the second heat treatment may be performed under a temperature condition of 200° C. or higher.
  • the presence or absence of pressure treatment may be changed.
  • the pressure treatment may be performed in combination with the first heat treatment, and the pressure treatment may not be performed in the second heat treatment.
  • the above heat treatment may be performed after the temporary support is peeled off, or the heat treatment may be performed while the temporary support is placed on the silicone resin layer. may be implemented. Further, when the heat treatment is performed a plurality of times, the temporary support may be peeled off between each heat treatment. For example, after performing the first heat treatment, the temporary support may be peeled off and the second heat treatment may be performed.
  • a notch portion may be formed in the temporary support to facilitate peeling.
  • a portion of the edge of the temporary support may be peeled off from the precursor film or silicone resin layer to form a folded portion, which may be used as the starting point of peeling.
  • a pull tape may be attached to the temporary support.
  • the temporary support is made larger than the precursor film or the silicone resin layer so that the temporary support protrudes, and the protruding portion of the temporary support is gripped to provide temporary support. You can peel the body.
  • 180 degree peeling is preferable because there is little possibility that the precursor film or the silicone resin layer will be damaged and become defective. Also, in order to prevent dust adhesion due to separation electrification, it is preferable to use an ionizer or humidify the separation environment.
  • Heating furnaces such as circulation furnaces and infrared furnaces can be used for heat treatment. It is preferable to evacuate the heating furnace in order to remove gas generated from the silicone resin layer during the heat treatment.
  • the cleanliness in the heating furnace is preferably class 10000 or less.
  • a surface treatment may be applied to the surface of the silicone resin layer of the laminated substrate.
  • Examples of surface treatment include corona treatment, atmospheric pressure plasma treatment, UV ozone treatment, and excimer UV treatment, with corona treatment and atmospheric pressure plasma treatment being preferred.
  • the water contact angle of the surface 14a of the silicone resin layer 14 after surface treatment is preferably 10 degrees or less, more preferably 5 degrees or less.
  • a structure having a glass substrate 12, a silicone resin layer 14, and a material to be supported in this order can be manufactured using the laminated substrate 10 described above. Materials other than the polyimide film 18 can also be laminated as the material to be supported.
  • supported materials include polyimide resin films, epoxy resin films, photosensitive resists, polyester resin films (e.g., polyethylene terephthalate, polyethylene naphthalate), polyolefin resin films (e.g., polyethylene, polypropylene), polyurethane resin films, and metals.
  • polyester resin films e.g., polyethylene terephthalate, polyethylene naphthalate
  • polyolefin resin films e.g., polyethylene, polypropylene
  • polyurethane resin films e.g., polyurethane resin films, and metals.
  • Foil e.g., copper foil, aluminum foil
  • sputtered film e.g., copper, titanium, aluminum, tungsten, silicon nitride, silicon oxide, amorphous silicon
  • TGV substrate thin glass substrate, thin glass substrate with sacrificial layer, ABF
  • sapphire substrates silicon substrates, TSV substrates, LED chips, display panels (eg, LCD, OLED, ⁇ -LED), artificial diamonds, interleaving paper, and the like.
  • the laminated body 16 having the glass base material 12, the silicone resin layer 14, and the polyimide film 18 shown in FIG.
  • the laminate 16 has a polyimide film 18 disposed on the silicone resin layer 14 of the laminate substrate 10 .
  • a polyimide varnish containing polyimide and a solvent is applied onto the silicone resin layer 14 of the laminate substrate 10 to form a polyimide film 18 on the silicone resin layer 14.
  • a method of forming a laminate having a glass substrate 12, a silicone resin layer 14, and a polyimide film 18 in this order will be described in detail below, and then the configuration of the polyimide film 18 will be described in detail.
  • polyimide varnish contains a polyimide or its precursor and a solvent.
  • a polyimide is usually obtained by polycondensing a tetracarboxylic dianhydride and a diamine, followed by imidization.
  • Polyimide preferably has solvent solubility.
  • the tetracarboxylic dianhydrides to be used include aromatic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides.
  • Diamines to be used include aromatic diamines and aliphatic diamines.
  • aromatic tetracarboxylic dianhydrides include pyromellitic anhydride (1,2,4,5-benzenetetracarboxylic dianhydride) and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride.
  • Aliphatic tetracarboxylic dianhydrides include cyclic or acyclic aliphatic tetracarboxylic dianhydrides
  • cycloaliphatic tetracarboxylic dianhydrides include, for example, 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, 1,1'-bicyclohexane-3,3',4,4'-tetracarboxylic acid-3,4,3',4'-dianhydride, carbonyl-4, 4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride
  • aromatic diamines include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,4-diaminotoluene, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′- dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ',5,5'-tetrachloro-4,4'-diaminobiphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4'-bis(4-aminophenyl)sulfide, 1, 3-bis[2-(4-aminophenoxyethoxy)]ethane, 9,9-bis(4-amin
  • aliphatic diamines include hexamethylenediamine, polyethylene glycol bis(3-aminopropyl) ether, polypropylene glycol bis(3-aminopropyl) ether, bis(aminomethyl) ether, bis(2-aminoethyl) ether, bis(3-aminopropyl) ether, bis[(2-aminomethoxy)ethyl]ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(3-aminoprotoxy)ethyl]ether, 1,2-bis(aminomethoxy)ethane, 1,2-bis(2-aminoethoxy)ethane, 1,2-bis[2-(aminomethoxy)ethoxy]ethane, 1,2-bis[2-(2 -aminoethoxy)ethoxy]ethane, ethylene glycol bis(3-aminopropyl) ether, diethylene glycol bis(3-aminopropy
  • polyimide examples include a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, wherein the structural unit A is represented by the following formula (a-1). and a structural unit (A-2) derived from a compound represented by the following formula (a-2), wherein the structural unit B is represented by the following formula (b-1 ) and a structural unit (B-2) derived from a compound represented by the following formula (b-2).
  • L is a single bond or a divalent linking group
  • each R is independently a hydrogen atom, a fluorine atom or a methyl group.
  • Structural unit A is a structural unit derived from tetracarboxylic dianhydride, represented by structural units (A-1) and formula (a-2) derived from the compound represented by formula (a-1) It contains a structural unit (A-2) derived from a compound.
  • the compound represented by formula (a-1) is norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2′′-norbornane-5,5′′,6,6′′-tetracarboxylic dianhydride It is a thing.
  • L is a single bond or a divalent linking group.
  • the divalent linking group is preferably a substituted or unsubstituted alkylene group, more preferably -CR 1 R 2 - (wherein R 1 and R 2 are each independently a hydrogen atom or a substituted or unsubstituted is a substituted alkyl group, or R 1 and R 2 are joined together to form a ring).
  • L is preferably selected from the group consisting of a single bond, a group represented by the following formula (L-1) and a group represented by the following formula (L-2).
  • the structural unit (A-2) is preferably a structural unit (A-2-1) derived from a compound represented by the following formula (a-2-1), represented by the following formula (a-2-2) At least one selected from the group consisting of a structural unit (A-2-2) derived from a compound derived from the following formula (a-2-3) and a structural unit (A-2-3) derived from a compound represented by and more preferably at least one selected from the group consisting of the structural unit (A-2-1) and the structural unit (A-2-2).
  • the compound represented by formula (a-2-1) is biphenyltetracarboxylic dianhydride, and specific examples thereof include 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2 , 3,3′,4′-biphenyltetracarboxylic dianhydride and 2,2′,3,3′-biphenyltetracarboxylic dianhydride.
  • the compound represented by formula (a-2-2) is 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride.
  • the compound represented by formula (a-2-3) is 4,4'-(hexafluoroisopropylidene)diphthalic anhydride.
  • the content of the structural unit (A-1) in the structural unit A is preferably 50 mol% or more, more preferably 55 mol% or more, still more preferably 60 mol% or more, and particularly preferably 75 mol% or more.
  • the content of the structural unit (A-1) in the structural unit A is preferably 95 mol % or less.
  • the content of the structural unit (A-2) in the structural unit A is preferably 50 mol% or less, more preferably 45 mol% or less, even more preferably 40 mol% or less, and particularly preferably 25 mol% or less.
  • the lower limit of the content of the structural unit (A-2) in the structural unit A is preferably 5 mol % or more.
  • the total content of the structural unit (A-1) and the structural unit (A-2) in the structural unit A is preferably 55 mol% or more, more preferably 60 mol% or more, further preferably 65 mol% or more, 80 mol % or more is particularly preferred.
  • the upper limit of the total content of the structural unit (A-1) and the structural unit (A-2) is not particularly limited, ie, it is 100 mol % or less.
  • Structural unit A may consist of only structural unit (A-1) and structural unit (A-2).
  • Structural unit A may contain structural units other than structural units (A-1) and (A-2).
  • the tetracarboxylic dianhydride that forms such a structural unit is not particularly limited, but an aromatic tetracarboxylic dianhydride such as pyromellitic dianhydride (where represented by formula (a-2) alicyclic tetracarboxylic dianhydrides such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride (however, , except for compounds represented by formula (a-1)); and aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride.
  • the aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more aromatic rings
  • the alicyclic tetracarboxylic dianhydride contains one or more alicyclic rings and is aromatic. It means a tetracarboxylic dianhydride containing no ring
  • an aliphatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing neither an aromatic ring nor an alicyclic ring.
  • Structural units arbitrarily included in structural unit A may be of one type or two or more types.
  • Structural unit B is a structural unit derived from a diamine, and is derived from a structural unit (B-1) derived from a compound represented by formula (b-1) and a compound represented by formula (b-2). It contains a structural unit (B-2) that The structural unit (B-1) improves mechanical properties and dimensional stability, and the structural unit (B-2) improves heat resistance.
  • the compound represented by formula (b-1) is 2,2'-bis(trifluoromethyl)benzidine.
  • each R is independently selected from the group consisting of a hydrogen atom, a fluorine atom and a methyl group, preferably a hydrogen atom.
  • Compounds represented by formula (b-2) include 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(3-fluoro-4-aminophenyl)fluorene, and 9,9-bis (3-methyl-4-aminophenyl)fluorene, etc., and 9,9-bis(4-aminophenyl)fluorene is preferred.
  • the content of the structural unit (B-1) in the structural unit B is preferably 20 mol% or more, more preferably 45 mol% or more, and even more preferably 50 mol% or more.
  • the content of the structural unit (B-1) in the structural unit B is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less.
  • the content of the structural unit (B-2) in the structural unit B is preferably 10 mol% or more, more preferably 15 mol% or more, and even more preferably 20 mol% or more.
  • the content of the structural unit (B-2) in the structural unit B is preferably 80 mol% or less, more preferably 55 mol% or less, even more preferably 50 mol% or less.
  • the total content of the structural unit (B-1) and the structural unit (B-2) in the structural unit B is preferably 30 mol% or more, more preferably 60 mol% or more, and even more preferably 70% or more.
  • the upper limit of the total content of the structural unit (B-1) and the structural unit (B-2) is not particularly limited, ie, it is 100 mol % or less.
  • the structural unit B may consist of only the structural unit (B-1) and the structural unit (B-2).
  • Structural unit B may contain structural units other than structural units (B-1) and (B-2).
  • the diamine that forms such a structural unit is not particularly limited, but the above aromatic diamine (excluding the compound represented by formula (b-1) and the compound represented by formula (b-2) ), cycloaliphatic diamines as described above, and aliphatic diamines as described above.
  • Structural units arbitrarily included in structural unit B that is, structural units other than structural units (B-1) and (B-2) may be of one type or two or more types.
  • Polyimide may have structural units derived from these.
  • 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis[3(3-aminophenoxy)phenyl ] Hexafluoropropane, 2,2′-bis[4(4-aminophenoxy)phenyl]hexafluoropropane, 2,2′-bis(3-aminophenyl)hexafluoropropane, 2,2′-bis(4- Aminophenyl)hexafluoropropane can suppress the formation of charge-transfer complexes between polyimide molecules by introducing bulky steric hindrance of fluorine atoms. Therefore, the polyimide may have repeating units derived from these in order to lower the yellow index (YI) of the polyimide film.
  • YI yellow index
  • a polyimide precursor means polyamic acid (so-called polyamic acid and/or polyamic acid ester) before imidization.
  • polyimide precursors include polyimide precursors containing 50 mol% or more of structural units represented by the following formula (1A) with respect to all structural units, and structural units represented by the following formula (1A). and a polyimide precursor containing 50 mol % or more of structural units represented by the following formula (2A) with respect to all structural units.
  • R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
  • R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.
  • polyimide precursors include polyimide precursors containing structural units represented by the following formula (3A), preferably 90 mol% or more, more preferably 95 mol% or more, based on all structural units, Polyimide precursor containing preferably 90 mol% or more, more preferably 95 mol% or more, of structural units represented by the following formula (3A) and structural units represented by the following formula (4A), based on all structural units body.
  • a 1 is a divalent group having an aromatic ring
  • R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 9 carbon atoms. It is a silyl group.
  • a 2 is a divalent group having an aromatic ring
  • R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 9 carbon atoms. It is a silyl group.
  • the structural unit represented by formula (1A) is a structural unit represented by formula (3A) in which A 1 is a group represented by formula (D-1) below.
  • the structural unit represented by formula (2A) is a structural unit represented by formula (4A) in which A 2 is a group represented by formula (D-1) below.
  • a 1 in formula (3A) and A 2 in formula (4A) other than the group represented by formula (D-1) are divalent groups having an aromatic ring having 6 to 40 carbon atoms. is preferred, and a group represented by the following formula (A-1) is more preferred.
  • n 0 to 3
  • Y 1 , Y 2 and Y 3 each independently represent one selected from the group consisting of a hydrogen atom, a methyl group and a trifluoromethyl group
  • Q and R each independently represent a direct bond
  • -NHCO-, -CONH-, -COO- and -OCO- one selected from the group consisting of groups represented by the formulas: -NHCO-, -CONH-, -COO- and -OCO-.
  • tetracarboxylic acid component that provides the structural unit represented by formula (1A) and the structural unit represented by formula (3A) include 1,2,3,4-cyclobutanetetracarboxylic acids.
  • Tetracarboxylic acids include tetracarboxylic acids and tetracarboxylic acid derivatives such as tetracarboxylic acid dianhydrides, tetracarboxylic acid silyl esters, tetracarboxylic acid esters, and tetracarboxylic acid chlorides.
  • trans-endo-endo-norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2′′-norbornane-5,5 ",6,6"-tetracarboxylic acids cis-endo-endo-norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2′′-norbornane-5,5′′,6,6′′-tetra
  • norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2′′-norbornane-5,5′′,6,6′′-tetracarboxylic acids such as carboxylic acids.
  • Examples of the diamine component that provides the structural unit represented by formula (1A) and the structural unit represented by formula (2A) include 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolysine). be.
  • the diamine component to be given has an aromatic ring, and when it has a plurality of aromatic rings, the aromatic rings are each independently linked by a direct bond, an amide bond, or an ester bond.
  • the linking position between the aromatic rings is not particularly limited, but bonding at the 4-position to the amino group or the linking group between the aromatic rings results in a linear structure, and the resulting polyimide may have low linear thermal expansion.
  • the aromatic ring may be substituted with a methyl group or a trifluoromethyl group.
  • a substitution position is not specifically limited.
  • Diamine components to be provided include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, benzidine, 3,3′-diamino-biphenyl, 2,2′-bis(trifluoromethyl)benzidine, 3,3′- Bis(trifluoromethyl)benzidine, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, N,N'-bis(4-aminophenyl)terephthalamide, N,N'-p-phenylenebis (p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis(4-aminophenyl) terephthalate, biphenyl-4,4'-dicarboxylic acid
  • a 1 or A 2 other than the diamine component that provides the structure of formula (D-1) or formula (A-1) of aromatic diamines can be used.
  • diamine components include, for example, 4,4′-oxydianiline, 3,4′-oxydianiline, 3,3′-oxydianiline, p-methylenebis(phenylenediamine), 1,3-bis( 4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4′-bis(4-aminophenoxy)biphenyl, 4,4 '-bis(3-aminophenoxy)biphenyl, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, bis(4- aminophenyl)sulfone, 3,3'-bis(trifluoromethyl)benzidine, 3,3'-bis((aminophenoxy)phenyl)propane, 2,2'-bis(3-amino-4
  • the solvent may be any solvent that dissolves the polyimide or its precursor, such as phenolic solvents (eg, m-cresol), amide solvents (eg, N-methyl-2-pyrrolidone, N,N-dimethylformamide , N,N-dimethylacetamide), lactone solvents (e.g., ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -crotonolactone, ⁇ -hexanolactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ - valerolactone, ⁇ -acetyl- ⁇ -butyrolactone, ⁇ -hexanolactone), sulfoxide solvents (e.g.
  • phenolic solvents eg, m-cresol
  • amide solvents eg, N-methyl-2-pyrrolidone, N,N-dimethylformamide , N,N-dimethylacetamide
  • ketone solvents e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone
  • esters system solvents eg, methyl acetate, ethyl acetate, butyl acetate, dimethyl carbonate.
  • the polyimide varnish preferably contains 5 to 40% by mass of polyimide resin or its precursor, more preferably 10 to 30% by mass.
  • the viscosity of the polyimide varnish is preferably 1 to 200 Pa ⁇ s, more preferably 5 to 150 Pa ⁇ s.
  • the method of applying the polyimide varnish on the silicone resin layer 14 side of the laminated substrate 10 is not particularly limited, and a known method can be used. Examples thereof include slit coating, curtain coating, spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing and gravure coating.
  • heat treatment (curing step) may be carried out, if necessary.
  • the temperature conditions are preferably 50 to 500.degree. C., more preferably 50 to 450.degree.
  • the heating time is preferably 10 to 300 minutes, more preferably 20 to 200 minutes. Further, the heat treatment may be performed multiple times. When the heat treatment is performed multiple times, the heating conditions may be changed.
  • the surface of the formed polyimide film may be polished in order to planarize the particles and protrusions.
  • the laminated substrate may be washed with an alkaline detergent before applying the polyimide varnish. Also, after cleaning with an alkaline detergent, the substrate may be rinsed with pure water, if necessary. Furthermore, after rinsing with pure water, if necessary, the water may be drained with an air knife. After the air knife, it may be dried by heating. Since contact with a brush may damage the surface of the silicone resin layer, it is preferable to wash without brushing.
  • the surface quality of the laminated substrate before applying the polyimide varnish may be inspected in the same way as the glass substrate.
  • the laminate 16 has a glass substrate 12, a silicone resin layer 14, and a polyimide film 18, as shown in FIG.
  • the structures of the glass substrate 12 and the silicone resin layer 14 are as described above.
  • the polyimide film 18 is arranged on the silicone resin layer 14 .
  • the average thickness of the polyimide film 18 is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more. From the viewpoint of flexibility, the thickness is preferably 1 mm or less, more preferably 0.2 mm or less.
  • the thickness variation of the polyimide film 18 is preferably 0.5 ⁇ m or less, more preferably 0.2 ⁇ m or less. A lower limit is 0 ⁇ m.
  • the polyimide film 18 may be a single film or a multi-layer film of two or more layers.
  • the surface of the polyimide film 18 is preferably smooth in order to form high-definition wiring of electronic devices on the polyimide film 18 .
  • the average value of the surface roughness Ra of the polyimide film 18 is preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 10 nm or less.
  • a lower limit is 0 nm.
  • the thermal expansion coefficient of the polyimide film 18 is preferably smaller than that of the glass substrate 12 because warping of the laminate 16 after heating or cooling can be suppressed.
  • the difference in thermal expansion coefficient between the polyimide film 18 and the glass substrate 12 is preferably 0 to 90 ⁇ 10 -6 /°C, more preferably 0 to 30 ⁇ 10 -6 /°C.
  • the area of the polyimide film 18 is not particularly limited, it is preferably 300 cm 2 or more from the viewpoint of productivity of electronic devices.
  • the yellow index (YI) of the polyimide film 18 is preferably small.
  • YI of the polyimide film 18 is preferably 10.0 or less, more preferably 5.0 or less, still more preferably 3.5 or less, and particularly preferably 1.5 or less. 0 is mentioned as a lower limit. YI is measured according to JIS K7361-1.
  • the light transmittance of the polyimide film 18 in the visible light region is preferably 80% or more.
  • the upper limit includes less than 100%.
  • the laminate may have a gas barrier film on the polyimide film 18.
  • the polyimide film 18 When the polyimide film 18 is a laminated film, it may have a gas barrier film between two or more layers.
  • gas barrier films include inorganic material films such as silicon oxide films and silicon nitride films.
  • the gas barrier film may be a multilayer film in which an organic material layer such as a thermoplastic resin or an organic silicon compound and an inorganic material layer such as silicon oxide or silicon nitride are laminated.
  • the film formation method is not particularly limited, and includes known methods. For example, methods such as plasma CVD and sputtering can be used.
  • the laminated body 16 can be used for various purposes, for example, it can be used for manufacturing electronic parts such as a display device panel, a PV, a thin-film secondary battery, a semiconductor wafer having a circuit formed on its surface, and a reception sensor panel, which will be described later. mentioned.
  • the laminate may be exposed to high temperature conditions (eg, 450° C. or higher) (eg, 20 minutes or longer) in the atmosphere.
  • Display device panels include LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, micro LED display panel, MEMS shutter panel, and the like.
  • Receiving sensor panels include electromagnetic wave receiving sensor panels, X-ray receiving sensor panels, ultraviolet light receiving sensor panels, visible light receiving sensor panels, and infrared light receiving sensor panels.
  • the substrate used for the receiving sensor panel may be reinforced with a reinforcing sheet made of resin or the like.
  • the electronic device manufacturing method includes forming an electronic device member 20 on the surface of the polyimide film 18 of the laminate 16 opposite to the silicone resin layer 14 side, and and a separation step of obtaining an electronic device 24 having the polyimide film 18 and the electronic device member 20 from the electronic device member-attached laminate 22 .
  • the process of forming the electronic device member 20 is referred to as the "member forming process”
  • the process of separating the electronic device 24 and the glass substrate 26 with the silicone resin layer is referred to as the "separating process”.
  • the materials and procedures used in each step are detailed below.
  • the member forming step is a step of forming an electronic device member on the polyimide film 18 of the laminate 16 . More specifically, as shown in FIG. 3, an electronic device member 20 is formed on the surface of the polyimide film 18 opposite to the silicone resin layer 14 side to obtain a laminate 22 with an electronic device member.
  • the laminate 22 with the electronic device member includes the laminate 16 and the electronic device member 20 arranged on the polyimide film 18 in the laminate 16 .
  • the electronic device member 20 is a member that constitutes at least part of an electronic device formed on the polyimide film 18 of the laminate 16 .
  • the electronic device member 20 is used for a display device panel, a solar cell, a thin-film secondary battery, or an electronic component such as a semiconductor wafer having a circuit formed on its surface, a receiving sensor panel, or the like.
  • Members e.g., members for display devices such as LTPS, members for solar cells, members for thin-film secondary batteries, circuits for electronic components, and members for receiving sensors).
  • the solar cell member described in paragraph [0192] of the book, the thin film secondary battery member described in the same paragraph [0193], and the electronic component circuit described in the same paragraph [0194] can be mentioned.
  • the method for producing the laminate 22 with the electronic device member described above is not particularly limited, and an electronic device forming the member 20;
  • the electronic device member 20 is not all of the members finally formed on the polyimide film 18 (hereinafter referred to as “all members”), but may be a part of all members (hereinafter referred to as “partial members”). good.
  • the substrate with partial members peeled off from the silicone resin layer 14 can also be made into a substrate with all members (corresponding to an electronic device to be described later) in subsequent steps.
  • Another electronic device member may be formed on the peeled surface of the substrate with all members peeled off from the silicone resin layer 14 . Furthermore, the electronic device members 20 of the two laminates 22 with electronic device members are opposed to each other, and the two are bonded together to assemble a laminate with all members, and then, from the laminate with all members, two silicone An electronic device can also be manufactured by peeling the resin layer-coated glass substrate.
  • a transparent electrode is formed to form an organic EL structure on the surface of the polyimide film 18 of the laminate 16 opposite to the silicone resin layer 14 side
  • various layer formation such as vapor deposition of a hole injection layer, hole transport layer, light emitting layer, electron transport layer, etc. on the surface on which the transparent electrode is formed, formation of a back electrode, sealing using a sealing plate, etc. and processing are performed.
  • Specific examples of these layer formations and treatments include film formation treatment, vapor deposition treatment, sealing plate adhesion treatment, and the like.
  • the electronic device member 20 is separated from the laminate 22 with the electronic device member obtained in the member forming step using the interface between the silicone resin layer 14 and the polyimide film 18 as a release surface. is separated into the laminated polyimide film 18 and the glass substrate 26 with the silicone resin layer to obtain the electronic device 24 including the electronic device member 20 and the polyimide film 18 .
  • the remaining components can also be formed on the polyimide film 18 after separation.
  • the method for separating the polyimide film 18 and the silicone resin layer 14 is not particularly limited.
  • the separation can be performed by spraying a mixed fluid of water and compressed air.
  • a laser lift-off method may be used.
  • the laminate 22 with the electronic device member is placed on a surface plate so that the glass substrate 12 is on the upper side and the electronic device member 20 side is on the lower side.
  • the electronic device member 20 side is vacuum-sucked on the surface plate, and in this state, a knife-like object is first penetrated into the interface between the polyimide film 18 and the glass substrate 12 .
  • the glass substrate 12 side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are sequentially raised from the vicinity of the place where the blade-like object is inserted. Then, the glass substrate 26 with the silicone resin layer can be easily peeled off.
  • the polyimide film 18 and the silicone resin layer 14 are peeled off, if the electronic device member 20 is prepared for each of a plurality of cells, the electronic device 24 having the polyimide film 18 and the electronic device member 20 is separated from each cell. After cutting into pieces, the polyimide film 18 and the silicone resin layer 14 may be peeled off for each of the cut cells. Examples of the method of cutting into cells include a method of cutting with a laser beam and a method of cutting with a cutting machine such as a dicing saw.
  • the above-described electronic device manufacturing method is suitable for manufacturing the display device described in paragraph [0210] of US Patent Application Publication No. 2018/0178492, for example, and the electronic device 24 is, for example, [0211].
  • a region of the laminate in which the electronic device member is not arranged may be cut and removed.
  • a protective film may be attached to the surface of the electronic device member 20 of the separated electronic device 24 opposite to the polyimide film 18 side.
  • a protective film may be attached to the surface of the polyimide film 18 of the separated electronic device 24 on the side opposite to the electronic device member 20 side.
  • the surface of the polyimide film 18 may be subjected to surface treatment, if necessary.
  • Surface treatments include, for example, corona treatment, atmospheric pressure plasma treatment, UV ozone treatment, and excimer UV treatment.
  • the water contact angle of the surface of the polyimide film 18 after the surface treatment is preferably 10 degrees or less, more preferably 5 degrees or less.
  • the glass substrate 26 with the silicone resin layer separated from the laminate 22 with the electronic device member may be recycled as a glass raw material.
  • the surface of the silicone resin layer 14 of the separated glass substrate 26 with a silicone resin layer may be washed and further surface-modified to be used again as a laminated substrate for forming a polyimide film.
  • the silicone resin layer 14 of the separated glass substrate 26 with a silicone resin layer may be removed and reused as the glass substrate.
  • Methods for removing the silicone resin layer include a method of dissolving the silicone resin layer in a solvent and a method of mechanically grinding or polishing the silicone resin layer.
  • the average number of OX groups is a numerical value representing the average number of OX groups (X is a hydrogen atom or a hydrocarbon group) bonded to one Si atom.
  • the M unit means a monofunctional organosiloxy unit represented by (R) 3 SiO 1/2 .
  • a T unit means a trifunctional organosiloxy unit represented by RSiO 3/2 (R represents a hydrogen atom or an organic group).
  • curable composition 1 (Preparation of curable composition 1) A curable silicone (20 g), a zirconium octoate compound (“Orgatics ZC-200”, manufactured by Matsumoto Fine Chemicals Co., Ltd.) (0.16 g) as a metal compound, and cerium (III) 2-ethylhexanoate (Alfa Aesar) (metal content 12%) (0.17 g), and Isoper G (manufactured by TonenGeneral Sekiyu Co., Ltd.) (19.7 g) as a solvent. A curable composition 1 was obtained by filtering using.
  • curable silicone 2 was obtained by mixing an organohydrogensiloxane and an alkenyl group-containing siloxane.
  • the composition of the curable silicone 2 is such that the molar ratio of M units, D units and T units is 9:59:32, the molar ratio of organic methyl groups to phenyl groups is 44:56, all alkenyl groups and all silicon atoms. was 0.7 and the average number of OX groups was 0.1.
  • Example 1> (Preparation of a laminated substrate consisting of a glass base material and a silicone resin layer)
  • a PET film manufactured by Toyobo Co., Ltd., Cosmoshine A4160, thickness 50 ⁇ m
  • This film has a flat surface and an uneven surface, and the prepared curable composition 1 was applied on the flat surface side and heated at 140° C. for 10 minutes using a hot plate to form a silicone resin layer.
  • a glass substrate “AN100” glass substrate having a size of 200 mm ⁇ 200 mm and a thickness of 0.5 mm was washed with pure water, A PET film (size: 190 mm ⁇ 190 mm) on which a silicone resin layer was formed was laminated to prepare a laminate in which the glass substrate, the silicone resin layer, and the PET film were arranged in this order.
  • the obtained laminate was placed in an autoclave and heated at 60°C and 1 MPa for 30 minutes. Thereafter, the PET film was peeled off, and the obtained laminate was placed in an oven preheated to 250° C. and annealed for 30 minutes to produce a laminated substrate comprising a glass substrate and a silicone resin layer (annealing step). .
  • the thickness of the silicone resin layer after annealing was measured at arbitrary 10 locations using a film thickness measurement system ("F20" manufactured by Filmetrics Co., Ltd.). As for the measurement range, a peripheral area of 3 mm was excluded from the edge of the silicone resin layer toward the center. The average film thickness of 10 measured values was 7.2 ⁇ m. The maximum film thickness of the silicone resin layer was 7.4 ⁇ m, and the minimum film thickness was 7.1 ⁇ m. Also, the difference between the maximum value and the minimum value of the film thickness was taken as the film thickness variation. The film thickness variation was 0.3 ⁇ m.
  • the surface roughness (Ra) of the silicone resin layer after the annealing treatment was measured at 10 arbitrary locations using a non-contact surface/layer cross-sectional shape measurement system ("Vertscan R3300-lite” manufactured by Ryoka Systems Co., Ltd.). As for the measurement range, a peripheral area of 3 mm was excluded from the edge of the silicone resin layer toward the center. One measurement area was 940 ⁇ m long ⁇ 700 ⁇ m wide. The average surface roughness of 10 measured values was 0.81 nm. The surface roughness had a maximum value of 0.87 nm and a minimum value of 0.72 nm. Also, the difference between the maximum value and the minimum value of surface roughness was defined as surface roughness variation. The surface roughness variation was 0.15 nm.
  • a silicon nitride film (SiN film) having a thickness of 50 nm was formed on the surface of the colorless polyimide film of the laminate obtained in the above (Production of laminate) using a plasma CVD apparatus.
  • a plasma CVD apparatus using an inert gas oven, a laminate having a glass substrate, a silicone resin layer, a colorless polyimide film, and a silicon nitride film in this order was heated in a nitrogen atmosphere at 400° C. for 1 hour (heat resistance test).
  • Examples 2 to 6 Examples 9 to 13> An evaluation sample was prepared in the same manner as in Example 1 except that the curable composition, release film, and annealing conditions shown in Table 1 were used.
  • Example 7> Preparation of a laminated substrate consisting of a glass base material and a silicone resin layer
  • a glass substrate "AN100” glass substrate
  • the curable composition 1 was applied using a coater.
  • a silicone resin layer was formed by heating at 140° C. for 10 minutes using a hot plate.
  • a laminated substrate composed of a glass substrate and a silicone resin layer was placed in an oven preheated to 250° C. and annealed for 30 minutes (annealing step).
  • the thickness of the silicone resin layer at any 10 locations after annealing was measured using a film thickness measurement system ("F20" manufactured by Filmetrics Co., Ltd.) (the measurement range was from the edge to the center of the silicone resin layer. except for a peripheral area of 3 mm towards ).
  • the average film thickness of 10 measured values was 7.0 ⁇ m.
  • the maximum film thickness was 9.5 ⁇ m and the minimum film thickness was 6.8 ⁇ m.
  • the film thickness variation which is the difference between the maximum value and the minimum value of the film thickness, was 2.7 ⁇ m.
  • the surface roughness (Ra) of the silicone resin layer after the annealing treatment was measured at 10 arbitrary locations using a non-contact surface/layer cross-sectional shape measurement system ("Vertscan R3300-lite" manufactured by Ryoka Systems Co., Ltd.). As for the measurement range, a peripheral area of 3 mm was excluded from the edge of the silicone resin layer toward the center. One measurement area was 940 ⁇ m ⁇ 700 ⁇ m. The average surface roughness of 10 measured values was 0.42 nm. The maximum surface roughness was 0.47 nm and the minimum was 0.40 nm. Moreover, the surface roughness variation, which is the difference between the maximum value and the minimum value of surface roughness, was 0.07 nm.
  • a silicon nitride film (SiN film) having a thickness of 50 nm was formed on the surface of the colorless polyimide film of the laminate obtained in the above (Production of laminate) using a plasma CVD apparatus.
  • an inert gas oven was used to heat a laminate having a glass substrate, a silicone resin layer, a colorless polyimide film and a silicon nitride film in this order at 400° C. for 1 hour in a nitrogen atmosphere.
  • Example 8 Example 14, Example 15> An evaluation sample was prepared in the same manner as in Example 7 except that the curable composition, the method for forming the silicone resin layer, and the annealing conditions shown in Table 1 were used.
  • Table 2 shows the results of the unevenness evaluation.
  • the "Average” column in the “Thickness [ ⁇ m] of the silicone resin layer” column represents the arithmetic mean value of the measured values of 10 thicknesses of the silicone resin layer
  • the "Maximum” column represents the 10 films. The maximum of the thickness measurements is presented
  • the "minimum” column represents the minimum of the 10 thickness measurements
  • the "variance” column represents the difference between the maximum and minimum values.
  • the "average” column in the “silicone resin layer surface roughness Ra [nm]” column represents the arithmetic mean value of the measured values of 10 surface roughnesses of the silicone resin layer
  • the "maximum” column represents 10 represents the maximum value among the measured values of surface roughness
  • the column “minimum” represents the minimum value among the measured values of ten surface roughness
  • the column “dispersion” represents the difference between the maximum and minimum values. represent the difference.
  • silicon nitride, silicon oxide, and amorphous silicon were formed in this order by plasma CVD.
  • low-concentration boron was implanted into the amorphous silicon layer by an ion doping device, and heat treatment and dehydrogenation treatment were performed.
  • the amorphous silicon layer was crystallized by a laser annealing apparatus.
  • low-concentration phosphorus was implanted into the amorphous silicon layer using an etching and ion doping apparatus using photolithography to form N-type and P-type TFT areas.
  • a silicon oxide film is formed by a plasma CVD method to form a gate insulating film, a molybdenum film is formed by a sputtering method, and a photolithography method is used.
  • a gate electrode was formed by etching.
  • a source area and a drain area were formed by implanting high-concentration boron and phosphorus into desired areas of the N-type and P-type, respectively, using a photolithography method and an ion doping apparatus.
  • an interlayer insulating film is formed by forming a silicon oxide film by a plasma CVD method, an aluminum film is formed by a sputtering method, and a TFT electrode is formed by etching using a photolithography method. formed.
  • a passivation layer was formed by film formation of silicon nitride by a plasma CVD method.
  • an ultraviolet curable resin was applied to the side of the polyimide film opposite to the glass substrate side, and a planarizing layer and contact holes were formed by photolithography.
  • a film of indium tin oxide was formed by a sputtering method, and a pixel electrode was formed by etching using a photolithography method.
  • 4,4′,4′′-tris(3-methylphenylphenylamino)triphenylamine as a hole injection layer and a hole transport layer were formed on the opposite side of the polyimide film from the glass substrate side.
  • a structure having an organic EL structure on a polyimide film (hereinafter referred to as panel A) is a laminate with an electronic device member.
  • the sealing body side of Panel A was vacuum-adsorbed to a surface plate, and a stainless steel knife with a thickness of 0.1 mm was inserted into the interface between the polyimide film and the glass substrate at the corners of Panel A to remove the polyimide film. and the interface with the glass substrate triggered the peeling. Then, after the surface of the glass substrate of panel A was sucked by a vacuum suction pad, the suction pad was raised. Here, the cutting tool was inserted while spraying a neutralizing fluid onto the interface from an ionizer (manufactured by Keyence Corporation).
  • the vacuum suction pad was lifted up while continuously spraying the anti-static fluid from the ionizer toward the formed gap and pouring water onto the separation front.
  • the glass substrate with the silicone resin layer could be peeled off, leaving only the polyimide film with the organic EL structure formed on the surface plate.
  • the separated polyimide film is cut using a laser cutter or a scribe-break method to divide into a plurality of cells, and then the polyimide film on which the organic EL structure is formed and the counter substrate are assembled to form a module.
  • An organic EL display device was manufactured by carrying out the steps.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
PCT/JP2022/018045 2021-04-22 2022-04-18 積層基板、積層体、積層体の製造方法、電子デバイス用部材付き積層体、電子デバイスの製造方法 WO2022224933A1 (ja)

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KR1020237035218A KR20240000475A (ko) 2021-04-22 2022-04-18 적층 기판, 적층체, 적층체의 제조 방법, 전자 디바이스용 부재가 부착된 적층체, 전자 디바이스의 제조 방법
JP2023515462A JP7371813B2 (ja) 2021-04-22 2022-04-18 積層基板、積層体、積層体の製造方法、電子デバイス用部材付き積層体、電子デバイスの製造方法

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