WO2023112685A1 - フレキシブルデバイス用基材・接着剤層一体型シート、及びフレキキシブルデバイスの製造方法 - Google Patents

フレキシブルデバイス用基材・接着剤層一体型シート、及びフレキキシブルデバイスの製造方法 Download PDF

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WO2023112685A1
WO2023112685A1 PCT/JP2022/044271 JP2022044271W WO2023112685A1 WO 2023112685 A1 WO2023112685 A1 WO 2023112685A1 JP 2022044271 W JP2022044271 W JP 2022044271W WO 2023112685 A1 WO2023112685 A1 WO 2023112685A1
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Prior art keywords
adhesive layer
flexible device
flexible
integrated sheet
mass
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PCT/JP2022/044271
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English (en)
French (fr)
Japanese (ja)
Inventor
小雪 坂井
憲司 徳久
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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Priority to EP22893975.7A priority Critical patent/EP4450579A4/en
Priority to CN202280007924.7A priority patent/CN116829668A/zh
Priority to JP2023515661A priority patent/JP7470863B2/ja
Priority to KR1020237012425A priority patent/KR102943975B1/ko
Priority to US18/203,389 priority patent/US20230295470A1/en
Publication of WO2023112685A1 publication Critical patent/WO2023112685A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/06—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin

Definitions

  • the present invention relates to a substrate/adhesive layer integrated sheet for a flexible device and a method for manufacturing a flexible device.
  • a flexible device such as a flexible display is an organic electroluminescence (organic EL) element, a liquid crystal panel, a micro light emitting diode (micro LED), a semiconductor element such as a transistor (these are collectively referred to as functional elements).
  • organic EL organic electroluminescence
  • micro LED micro light emitting diode
  • functional elements semiconductor elements such as a transistor
  • such a flexible device has a flexible film (back plate) as a supporting base material that supports the entire device in order to increase the strength of the device body and impart reliability. That is, the above functional element is immobilized on a flexible film to produce a flexible device.
  • a functional element usually has various functional layers (for example, a protective layer, a gas barrier layer (sealing layer), a polarizing plate, a hard coat layer, etc.) laminated on both sides thereof, and the entire laminate including the functional element are integrally arranged on a flexible film and fixed via a paste-like or film-like adhesive.
  • As flexible films polyethylene terephthalate films, polyimide films and the like are used.
  • Patent Literature 1 describes a device-sealing adhesive sheet having a first release film, a second release film, and an adhesive layer sandwiched therebetween.
  • This adhesive layer contains a compound having a cyclic ether group, and its storage modulus at 23° C. is adjusted to 9.5 ⁇ 10 5 Pa or more and 3.0 ⁇ 10 7 Pa or less. According to the technique described in Patent Document 1, even if the adhesive sheet is cut, the peelability of the release film from the adhesive layer is excellent, and the adhesive layer is said to be excellent in adhesiveness to the adherend.
  • an adhesive sheet used for bonding between layers of a flexible device is provided with a release film on both sides of an adhesive layer, and when used, the release films on both sides are peeled off, and both sides have adhesiveness.
  • Used as an adhesive film For example, when a functional element is provided on a flexible film that is the supporting substrate, the release film is peeled off from the adhesive sheet, the flexible film is attached to one side of the adhesive layer, and the functional element is attached to the other side.
  • a two-step process of bonding a laminate including an element is performed. In this case, depending on the combination of the flexible film and the adhesive layer, when the adhesive layer is cured, separation between the flexible film and the adhesive layer is likely to occur when the flexible film is folded. If peeling occurs between the flexible film and the adhesive layer, the reliability of the device is greatly reduced.
  • the present invention is formed by laminating a flexible film and an adhesive layer, has excellent adhesiveness (adhesiveness due to curing reaction) between the flexible film and the adhesive layer, and can be used as it is as a support substrate for a flexible device.
  • An object of the present invention is to provide a substrate-adhesive layer integrated sheet for a flexible device that can be laminated and adhered to a laminate containing
  • Another object of the present invention is to provide a flexible device manufacturing method that can simplify the flexible device manufacturing process and further improve the quality of the resulting flexible device.
  • a flexible film and an adhesive layer are laminated, and the absolute value of the difference between the surface free energy of the flexible film and the surface free energy of a cured layer formed by curing the adhesive layer is 30 dyn/cm or less. and a flexible device substrate/adhesive layer integrated sheet, wherein the cured layer has a storage elastic modulus of 5.0 GPa or less.
  • a method for producing a flexible device comprising forming a supporting substrate of the flexible device from the flexible device substrate/adhesive layer integrated sheet according to any one of [1] to [5].
  • a numerical range represented by "-" means a range including the numerical values described before and after "-” as lower and upper limits.
  • the terms “upper” and “lower” of the laminated structure are used for the flexible film side as lower and the adhesive layer side as “upper” for convenience.
  • the flexible device substrate/adhesive layer integrated sheet of the present invention has a laminated structure of a flexible film and an adhesive layer that can be applied as a supporting substrate of a flexible device, and can be used as a supporting substrate of a flexible device as it is. , it can be attached to a laminate containing a functional element via the adhesive layer, and the adhesiveness (adhesiveness due to curing reaction) between the flexible film and the adhesive layer is also excellent. That is, the flexible device substrate/adhesive layer integrated sheet of the present invention contributes to the simplification of the manufacturing process of the flexible device, and also contributes to the improvement of the quality of the resulting flexible device. Moreover, according to the flexible device manufacturing method of the present invention, the manufacturing process of the flexible device can be simplified, and the quality of the obtained flexible device can be further improved.
  • FIG. 1 is a cross-sectional view schematically showing the laminated structure of the flexible device substrate/adhesive layer integrated sheet of the present invention.
  • the substrate/adhesive layer integrated sheet for flexible devices of the present invention (hereinafter also simply referred to as "the integrated sheet of the present invention") has a structure in which a flexible film and an adhesive layer are laminated.
  • the absolute value of the difference between the surface free energy of the flexible film and the surface free energy of the cured layer obtained by curing the adhesive layer is 30 dyn/cm or less.
  • the storage elastic modulus of the hardened layer is 5 GPa or less.
  • the integrated sheet of the present invention As a supporting substrate of a flexible device, the reliability (structural stability, etc.) of the flexible device can be further enhanced.
  • the flexible film and adhesive layer constituting the integrated sheet of the present invention will be described in order.
  • the flexible film that constitutes the integrated sheet of the present invention is not particularly limited in material, thickness, etc., as long as it has flexibility and can be used as a supporting substrate for flexible devices. That is, flexible films used in flexible devices can be widely applied.
  • the flexible film preferably has a storage modulus of 10 GPa or less, more preferably 7 GPa or less, and even more preferably 5 GPa or less.
  • the storage modulus is usually 0.01 GPa or more, preferably 0.05 GPa or more, and more preferably 0.1 GPa or more.
  • the storage modulus of the flexible film is measured by cutting the flexible film into a width of 5 mm, using a dynamic viscoelasticity measuring device RSA III (manufactured by TA Instruments), under tensile conditions of a chuck distance of 20 mm and a frequency of 10 Hz, from -20 ° C. It is the storage elastic modulus at 23°C when the temperature is raised to 150°C at a temperature increase rate of 5°C/min.
  • the term "storage elastic modulus” simply refers to the storage elastic modulus at room temperature (23°C).
  • Preferred materials for the flexible film include polyester resin, polyimide resin, acrylic resin (polymethyl methacrylate (PMMA) resin, etc.), polycarbonate resin, acrylonitrile/butadiene/styrene copolymer (ABS) resin, polyolefin resin (polypropylene resin, polyethylene resin, etc.), polyamide resin, polyurethane resin, polyvinyl alcohol (PVA) resin, polystyrene resin, polyphenylene sulfide (PPS) resin, polyetheretherketone (PEEK) resin, and the like.
  • Polyester resins and polyimide resins are particularly preferred.
  • Preferable examples of polyester resins include polyethylene terephthalate resin and polyethylene naphthalate resin.
  • the thickness of the flexible film is usually 1 to 1000 ⁇ m, preferably 5 to 800 ⁇ m, more preferably 5 to 400 ⁇ m, more preferably 5 to 200 ⁇ m, and more preferably 10 to 100 ⁇ m.
  • the thickness can be measured by a contact/linear gauge method (tabletop contact thickness measuring device).
  • the flexible film preferably has a surface free energy of 10 to 200 dyn/cm, more preferably 20 to 100 dyn/cm, and more preferably 30 to 80 dyn/cm at the contact surface with the adhesive layer thereon. It is preferably 35 to 75 dyn/cm, preferably 40 to 70 dyn/cm, preferably 45 to 65 dyn/cm, and also preferably 48 to 62 dyn/cm.
  • the "surface free energy” is a value obtained by using the Owens and Wendt method, and measures the contact angle of the surface of the measurement object with respect to pure water and diiodomethane (drop volume: 2 ⁇ L of pure water, 3 ⁇ L of diiodomethane , reading time: 30 seconds after dropping, measurement atmosphere: temperature 23° C., relative humidity 50%), and solving the simultaneous equations of the following formula 1.
  • the term "solid surface” used below refers to the surface to be measured (flexible film surface, cured layer surface obtained by curing an adhesive layer).
  • the formula (1) is the Fowkes -Owens formula, which divides the components of the surface free energy. is the sum of the dispersion components ⁇ s d (including Debye force and hydrogen bonding force) of .
  • the above equations (2a) and (2b) are equations obtained by combining Young's equation with the equation of the extended Fowkes model for the interfacial tension ⁇ sl at the interface between solid s and liquid l.
  • Formula (2a) is a relational expression for pure water
  • formula (2b) is a relational expression for diiodomethane.
  • the surface tension ⁇ l of pure water, the surface tension polar component ⁇ l p , and the surface tension dispersion component ⁇ l d are respectively 72.8 mN/m, 51.0 mN/m, and 21.8 mN/m, respectively. Since the surface tension ⁇ l , the surface tension polar component ⁇ l p , and the surface tension dispersion component ⁇ l d are respectively 50.8 mN/m, 2.3 mN/m, and 48.5 mN/m, respectively, the above formula ( 2a) and (2b) incorporate these values. In addition, "dyn/cm" is synonymous with "mN/m”.
  • the surface free energy of the surface of the flexible film measured above can be regarded as the surface free energy of the flexible film at the contact surface between the flexible film and the adhesive layer in the integrated sheet of the present invention.
  • the surface free energy of the surface of the cured layer obtained by curing the adhesive layer measured above is the surface free energy of the contact surface between the flexible film and the cured layer of the adhesive layer in the integrated sheet of the present invention. It can be regarded as the surface free energy of the hardened layer.
  • Pure water and diiodomethane have different polar components and dispersive components, so the surface tension differs as described above. This is because pure water and diiodomethane differ in the presence or absence of hydrogen bonding and in the difference in electronegativity, and accordingly the polarity greatly differs. In particular, in the case of water, hydrogen bonds such as —OH and —O— are strong, and the ratio of polar components is large.
  • the flexible film preferably has a linear expansion coefficient of 10 to 200 ppm/K, more preferably 20 to 150 ppm/K, further preferably 30 to 100 ppm/K, and 40 to 80 ppm/K. 50 to 80 ppm/K, preferably 55 to 75 ppm/K, and also preferably 58 to 72 ppm/K.
  • the coefficient of linear expansion is synonymous with the coefficient of linear thermal expansion.
  • TMA/SS6100 manufactured by Seiko Instruments Inc.
  • a measurement sample cut out from a flexible film was heated from -20°C to 220°C at a rate of 5°C/min. It is calculated from the elongation amount of
  • the term "linear expansion coefficient" simply means linear expansion coefficients in all directions.
  • the adhesive layer that constitutes the integrated sheet of the present invention is cured by a curing reaction to exhibit adhesive strength with an adherend. That is, the adhesive layer is a layer made of a curable composition.
  • the storage elastic modulus of the cured layer after curing reaction is 5.0 GPa or less.
  • the storage elastic modulus of the cured layer is preferably 4.5 GPa or less, more preferably 4.0 GPa or less, still more preferably 3.5 GPa or less, further preferably 3.0 GPa or less, further preferably 2.5 GPa or less, and 2 0.2 GPa or less is more preferable.
  • the storage elastic modulus of the cured layer is usually 0.5 GPa or more, preferably 0.7 GPa or more, preferably 0.8 GPa or more, and preferably 0.9 GPa or more. .
  • the storage elastic modulus of the cured layer is preferably 0.5 to 5.0 GPa, more preferably 0.7 to 5.0 GPa or less, still more preferably 0.8 to 4.5 GPa, and 0.8 to 4.0 GPa.
  • the storage modulus of the cured layer is determined as follows.
  • the adhesive layer is peeled off from the integrated sheet, and only this adhesive layer is laminated using a laminator at 70° C. to a thickness of 1 mm, and cured under conditions (i) or (ii) described later.
  • the obtained cured sample is cut into a width of 5 mm to obtain a measurement sample.
  • the measurement sample was measured using a dynamic viscoelasticity measuring device RSA III (manufactured by TA Instruments) under tension conditions with a chuck distance of 20 mm and a frequency of 10 Hz, from -20 ° C. to 150 ° C. at a heating rate of 5. The temperature is raised at a rate of °C/min, and the storage modulus at 23°C is determined.
  • the storage modulus of the cured layer depends on the chemical structure, type of functional group, functional group equivalent, and content of the curable compound that constitutes the adhesive layer (for example, the chemical structure and content of a compound having a cyclic ether group).
  • the "cured layer” means a cured layer obtained by curing reaction of the adhesive layer.
  • the cured layer is a cured layer obtained by subjecting the adhesive layer to a curing reaction under the following conditions (i) or (ii) depending on the type of curing agent. is.
  • the curing agent is a photocationic polymerization initiator: A hardened layer obtained by irradiating ultraviolet rays under the irradiation conditions of 1000 mJ/cm 2 at 25° C. using a mercury lamp.
  • the curing agent is a latent curing agent or a thermal cationic polymerization initiator: Hardened layer obtained by heat treatment at 150° C. for 1 hour.
  • Both the thickness of the adhesive layer and the cured layer formed by curing the adhesive layer are usually 1 to 100 ⁇ m, preferably 2 to 80 ⁇ m, more preferably 5 to 50 ⁇ m, and 8 to 40 ⁇ m. is also preferred, and 10 to 30 ⁇ m is also preferred.
  • the cured layer obtained by curing the adhesive layer preferably has a surface free energy of 10 to 200 dyn/cm, more preferably 15 to 120 dyn/cm, on the contact surface with the flexible film underneath. , preferably 20 to 90 dyn/cm, more preferably 20 to 80 dyn/cm, more preferably 25 to 75 dyn/cm, and more preferably 28 to 70 dyn/cm.
  • the storage modulus of the cured layer depends on the chemical structure, type of functional group, functional group equivalent, and content of the curable compound that constitutes the adhesive layer (for example, the chemical structure and content of a compound having a cyclic ether group).
  • the integrated sheet of the present invention is the absolute value of the difference between the surface free energy of the flexible film and the surface free energy of the cured layer formed by curing the adhesive layer (hereinafter also simply referred to as "interlayer surface free energy difference". ) is 30 dyn/cm or less.
  • the interlayer surface free energy difference is more preferably 28 dyn/cm or less.
  • the interlayer surface free energy difference is usually 1 dyn/cm or more, preferably 2 dyn/cm or more, preferably 4 dyn/cm or more, and preferably 6 dyn/cm or more.
  • the interlayer surface free energy difference is preferably 1 to 30 dyn/cm, preferably 2 to 28 dyn/cm, preferably 4 to 28 dyn/cm, preferably 6 to 28 dyn/cm, and 7 to It is also preferred to be 27 dyn/cm.
  • the cured layer obtained by curing the adhesive layer preferably has a linear expansion coefficient of 10 to 200 ppm/K, more preferably 20 to 150 ppm/K, and even more preferably 25 to 100 ppm/K, from the viewpoint of thermal stability. , preferably 30 to 80 ppm/K, preferably 40 to 80 ppm/K, preferably 45 to 75 ppm/K, preferably 46 to 70 ppm/K, 47 to 65 ppm/K It is also preferable that The coefficient of linear expansion of the hardened layer is determined as follows. The adhesive layer is peeled off from the integrated sheet, and this adhesive layer alone is laminated using a laminator at 70° C.
  • a prismatic test piece having a length of 5 mm, a width of 5 mm, and a thickness of 1 mm is cut out from the obtained cured sample and used as a measurement sample.
  • the measurement sample was heated from -20 ° C. to 220 ° C. at a rate of 5 ° C./min using a thermomechanical analyzer TMA/SS6100 (manufactured by Seiko Instruments Inc.). Calculate the coefficient of linear expansion from the amount of elongation.
  • the absolute value of the difference between the linear expansion coefficient of the flexible film and the linear expansion coefficient of the cured layer obtained by curing the adhesive layer is a thermal From the viewpoint of stability, it is preferably 30 ppm/K or less, more preferably 25 ppm/K or less, and even more preferably 20 ppm/K or less. It is preferable that the difference between the coefficients of linear expansion between layers is as small as possible (it is particularly preferable that the difference between the coefficients of linear expansion between layers is 0 ppm/K), but it is usually 1 ppm/K or more.
  • the interlayer linear expansion coefficient difference is preferably 1 to 30 ppm/K, preferably 1 to 25 ppm/K, more preferably 2 to 20 ppm/K, and more preferably 2 to 18 ppm/K.
  • the component composition of the adhesive layer is not particularly limited as long as it satisfies the requirements specified in the present invention.
  • a preferred form of the adhesive layer includes a form containing a compound having a cyclic ether group and a curing agent for this compound.
  • the adhesive layer usually contains a polymer component (film component) apart from the compound having a cyclic ether group.
  • other components may be contained as necessary for adjustment of surface free energy, elastic modulus, coefficient of linear expansion, and the like. The constituent components of the adhesive layer will be described.
  • the above compound having a cyclic ether group is a compound having at least one (preferably 2 to 20, more preferably 2 to 10) cyclic ether groups in the molecule.
  • a compound having a cyclic ether group is a polymer, it is classified as a compound having a cyclic ether group rather than being classified as the polymer component.
  • Common epoxy resins are therefore classified as compounds with cyclic ether groups.
  • a phenoxy resin which will be described later, is not included in the compound having a cyclic ether group. That is, the phenoxy resin described later is a polymer component.
  • a compound having a cyclic ether group preferably has a molecular weight of 100 to 3,000, more preferably 200 to 1,500.
  • the compound having a cyclic ether group preferably has a cyclic ether equivalent weight of 100 to 3000 g/eq, more preferably 200 to 1500 g/eq.
  • Cyclic ether equivalent weight refers to the number of grams (g/eq) of a compound containing one gram equivalent of a cyclic ether group.
  • the number of ring-constituting atoms of the cyclic ether group is preferably 3 or 4.
  • the cyclic ether group include an oxirane group (epoxy group), an oxetane group (oxetanyl group), a tetrahydrofuryl group, and a tetrahydropyranyl group.
  • an oxirane group or an oxetane group is preferable, and an oxirane group is more preferable. That is, the compound having a cyclic ether group is particularly preferably an epoxy resin.
  • the skeletons of epoxy resins include phenol novolak type, ortho-cresol novolak type, cresol novolak type, dicyclopentadiene type, biphenyl type, fluorene bisphenol type, triazine type, naphthol type, naphthalenediol type, triphenylmethane type, and tetraphenyl type. , bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, trimethylolmethane type and the like.
  • the triphenylmethane type, bisphenol A type, cresol novolac type, and ortho-cresol novolac type are preferable from the viewpoint of obtaining a film-like adhesive having a low crystallinity of the resin and a good appearance.
  • the content of the compound having a cyclic ether group in the solid content (components other than the solvent) of the adhesive layer is preferably 10 to 70% by mass, preferably 15 to 65% by mass, more preferably 20 to 60% by mass. , 22 to 55% by mass is more preferable.
  • curing agent examples include amines, acid anhydrides, polyhydric phenols, cationic polymerization initiators (preferably photocationic polymerization initiators), compounds having a cyclic ether group (epoxy resin etc.) can be widely used.
  • cationic polymerization initiators preferably photocationic polymerization initiators
  • compounds having a cyclic ether group epoxy resin etc.
  • the curing agent is preferably a photo cationic polymerization initiator or a latent curing agent.
  • latent curing agents include dicyandiamide compounds, imidazole compounds, curing catalyst complex polyhydric phenol compounds, hydrazide compounds, boron trifluoride-amine complexes, amine imide compounds, polyamine salts, modified products thereof, and microcapsule-type products. can be mentioned. These may be used individually by 1 type, or may be used in combination of 2 or more type. It is more preferable to use an imidazole compound from the viewpoint of having better latent potential (property of exhibiting curability by heating and having excellent stability at room temperature) and faster curing speed.
  • the content of the curing agent in the adhesive layer may be appropriately set according to the type of curing agent and the mode of reaction. For example, it may be 0.5 to 30 parts by mass, may be 1 to 20 parts by mass, may be 1 to 15 parts by mass, or may be 2 to 10 parts by mass with respect to 100 parts by mass of the compound having a cyclic ether group. It is also preferable to use parts, and it is also preferable to use 3 to 8 parts by mass.
  • polymer component suppresses film tackiness at room temperature (25°C) (the property that the film state easily changes even with a slight temperature change), and imparts sufficient adhesiveness and film-forming properties (film-forming properties). Any ingredient is acceptable.
  • Natural rubber butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, polybutadiene resin, polycarbonate resin, thermoplastic Polyimide resins, polyamide resins such as 6-nylon and 6,6-nylon, phenoxy resins, (meth)acrylic resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamideimide resins, polyurethane resins, fluorine resins, and the like. . These polymer components may be used alone or in combination of two or more.
  • a phenoxy resin is preferable as a polymer component because it has a similar structure to a compound having a cyclic ether group and thus has good compatibility.
  • a phenoxy resin can be obtained by a conventional method. For example, it can be obtained by reacting a bisphenol or biphenol compound with an epihalohydrin such as epichlorohydrin, or by reacting a liquid epoxy resin with a bisphenol or biphenol compound.
  • (meth)acrylic resin examples include copolymers containing (meth)acrylic acid or (meth)acrylic acid ester components as polymer constituents.
  • (Meth)acrylic resin constituents include, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, glycidyl methacrylate, glycidyl acrylate and the like.
  • the (meth)acrylic resin has a (meth)acrylic acid ester having a cyclic skeleton as a constituent component (e.g., (meth)acrylic acid cycloalkyl ester, (meth)acrylic acid benzyl ester, isobornyl (meth)acrylate, dicyclopenta Nil (meth)acrylate, dicyclopentenyl (meth)acrylate and dicyclopentenyloxyethyl (meth)acrylate) components.
  • a (meth)acrylic acid ester having a cyclic skeleton as a constituent component e.g., (meth)acrylic acid cycloalkyl ester, (meth)acrylic acid benzyl ester, isobornyl (meth)acrylate, dicyclopenta Nil (meth)acrylate, dicyclopentenyl (meth)acrylate and dicyclopentenyloxyethyl (meth)acrylate
  • imide (meth)acrylate components (meth)acrylic acid alkyl esters in which the alkyl group has 1 to 18 carbon atoms (e.g., methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate) and butyl (meth)acrylate) components. It may also be a copolymer with vinyl acetate, (meth)acrylonitrile, styrene, or the like.
  • a (meth)acrylic resin having a hydroxyl group is preferable from the viewpoint of compatibility with a compound having a cyclic ether group.
  • the weight average molecular weight of the polymer component is usually 10,000 or more. Although there is no particular upper limit, 5,000,000 or less is practical.
  • the weight average molecular weight of the polymer component is a value determined by GPC [Gel Permeation Chromatography] in terms of polystyrene.
  • the glass transition temperature (Tg) of the polymer component is preferably 100°C or lower, more preferably 90°C or lower.
  • the Tg of the polymer component is preferably ⁇ 30° C. or higher, preferably ⁇ 10° C. or higher, preferably 0° C. or higher, preferably 10° C. or higher, preferably 20° C. or higher, and preferably 30° C. or higher. C. or higher, 40.degree. C. or higher, 50.degree. C. or higher, or 60.degree. C. or higher.
  • the Tg of the polymer component is preferably ⁇ 30 to 100° C., preferably ⁇ 10 to 100° C., preferably 0 to 100° C., preferably 10 to 90° C., and at 20 to 90° C.
  • the Tg of the polymer component is the peak top temperature of tan ⁇ in dynamic viscoelasticity measurement.
  • Tg can be determined as follows. A solution obtained by dissolving a polymer component is applied onto a release film and dried by heating to form a film (polymer film) comprising the polymer component on the release film. The release film is peeled off and removed from the polymer film, and the polymer film is measured using a dynamic viscoelasticity measuring device (trade name: Rheogel-E4000F, manufactured by UBM), with a measurement temperature range of 20 to 300 ° C. Measured at a speed of 5°C/min and a frequency of 1 Hz. The obtained tan ⁇ peak top temperature (the temperature at which tan ⁇ shows the maximum) is defined as Tg.
  • the content of the polymer component in the adhesive layer may be, for example, 10 to 300 parts by mass, and may be 20 to 200 parts by mass, with respect to 100 parts by mass of the compound having a cyclic ether group. It may be up to 180 parts by mass, preferably 60 to 160 parts by mass, preferably 70 to 140 parts by mass, and more preferably 80 to 130 parts by mass.
  • the adhesive layer may contain an inorganic filler.
  • inorganic fillers include silica, clay, gypsum, calcium carbonate, barium sulfate, alumina (aluminum oxide), beryllium oxide, magnesium oxide, silicon carbide, silicon nitride, aluminum nitride, ceramics such as boron nitride, aluminum, copper , silver, gold, nickel, chromium, lead, tin, zinc, palladium, solder and other metals or alloys, carbon nanotubes, graphene and other carbons, and various inorganic powders.
  • the inorganic filler may be subjected to surface treatment or surface modification, and examples of such surface treatment or surface modification include silane coupling agents, phosphoric acid or phosphoric acid compounds, and surfactants.
  • surface treatment or surface modification include silane coupling agents, phosphoric acid or phosphoric acid compounds, and surfactants.
  • the shape of the inorganic filler includes flakes, needles, filaments, spheres, and scales, and spherical particles are preferred from the viewpoint of high filling and fluidity.
  • the content of the inorganic filler in the adhesive layer is preferably 70% by mass or less, more preferably 60% by mass or less, and also preferably 50% by mass or less. , 40% by mass or less.
  • the content of the inorganic filler in the adhesive layer may be 1% by mass or more, may be 2% by mass or more, or may be 4% by mass or more. is also preferred.
  • the content of the inorganic filler in the adhesive layer can be 1 to 70% by mass, and can be 2 to 60% by mass. It can be 50% by mass, and preferably 4 to 40% by mass.
  • the adhesive layer may contain a silane coupling agent in addition to the inorganic filler.
  • the silane coupling agent has at least one hydrolyzable group such as an alkoxy group or an aryloxy group bonded to a silicon atom. good.
  • the alkyl group is preferably substituted with an amino group, an alkoxy group, an epoxy group or a (meth)acryloyloxy group, such as an amino group (preferably a phenylamino group), an alkoxy group (preferably a glycidyloxy group), (meth)acryloyl Those substituted with an oxy group are more preferred.
  • Silane coupling agents include, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane.
  • Silane 3-glycidyloxypropylmethyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N-phenyl-3-aminopropyltri methoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane and the like.
  • the adhesive layer may further contain an organic solvent, an ion trapping agent (ion trapping agent), a curing catalyst, a viscosity modifier, an antioxidant, a flame retardant, a coloring agent, and the like.
  • an ion trapping agent ion trapping agent
  • a curing catalyst e.g., a styrene-butadiene-styrene-styrene-styl dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dime-butadion trapping agent, ethylene glycol dime-styrene-styrene-styrene-styrene-styrene-s
  • the total content of the compound having a cyclic ether group, the curing agent thereof, and the polymer component in the adhesive layer can be, for example, 30% by mass or more, preferably 40% by mass or more. 50% by mass or more is more preferable.
  • the ratio may be 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.
  • the integrated sheet of the present invention is formed by preparing a composition (varnish) by mixing each constituent component of the adhesive layer, coating this composition on a flexible film, and drying it as necessary. can do.
  • a composition (varnish) obtained by mixing each component of the adhesive layer usually contains an organic solvent.
  • the coating method a known method can be appropriately employed, and examples thereof include methods using a roll knife coater, gravure coater, die coater, reverse coater, and the like. Drying is sufficient so long as the organic solvent can be removed to form an adhesive layer without substantially causing a curing reaction.
  • the integrated sheet of the present invention may be composed of a flexible film and an adhesive layer, and the above-described release-treated base film is attached to the surface of the adhesive layer opposite to the flexible film side. It may be in a different form. A protective film or the like may be provided on the surface of the flexible film opposite to the adhesive layer. Further, the integrated sheet of the present invention may be in the form of being cut into an appropriate size, or may be in the form of being wound into a roll.
  • the integrated sheet of the present invention is stored under temperature conditions of 10°C or less before use (before the curing reaction). preferably.
  • the flexible film constituting the integrated sheet is used as a support base material (back plate) that supports the entire flexible device, and the adhesive layer of the integrated sheet is composed of the support base material and the adhesive layer thereon. It can function as a layer for bonding a laminate containing a functional element (a laminate of a functional element and various functional layers arranged on one side or both sides thereof). Therefore, in the method for producing the flexible device of the present invention, the supporting substrate of the flexible device is formed from the integrated sheet of the present invention, that is, the adhesive layer side of the integrated sheet of the present invention and the functional element are combined. It includes a step of laminating the laminate including the adhesive layer and causing a curing reaction of the adhesive layer.
  • the conditions for this curing reaction can be appropriately set in consideration of the type of curing agent, the heat resistance of the functional element, and the like.
  • the adhesive layer can be sufficiently cured by irradiating ultraviolet rays of 100 to 3000 mJ/cm 2 using a mercury lamp or the like.
  • the adhesive layer can be sufficiently cured by heating at a temperature of 150° C. or higher for 1 hour or longer.
  • room temperature means 25° C.
  • MEK is methyl ethyl ketone
  • PET is polyethylene terephthalate
  • UV ultraviolet light.
  • % and “parts” are based on mass unless otherwise specified.
  • Example 1 In a 1000 mL separable flask, 50 parts by mass of 828 (bisphenol A liquid epoxy resin, manufactured by Mitsubishi Chemical Corporation) as a compound having a cyclic ether group, YP-50 as a polymer component (phenoxy resin, Tg 84 ° C., Nippon Steel Chemical & Material Co., Ltd.) and 30 parts by mass of MEK were heated and stirred at a temperature of 110° C. for 2 hours to obtain a resin varnish.
  • 828 bisphenol A liquid epoxy resin, manufactured by Mitsubishi Chemical Corporation
  • YP-50 as a polymer component
  • MEK phenoxy resin, Tg 84 ° C., Nippon Steel Chemical & Material Co., Ltd.
  • this resin varnish is transferred to an 800 mL planetary mixer, 2 parts by mass of WPI-113 (UV cationic polymerization initiator, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) is added as a curing agent, and stirred and mixed at room temperature for 1 hour. , vacuum defoaming to obtain a mixed varnish.
  • WPI-113 UV cationic polymerization initiator, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • the obtained mixed varnish is applied to a 20 ⁇ m thick PET film (flexible film, storage elastic modulus 5 GPa at 23° C.), dried by heating at 130° C. for 10 minutes, and has an adhesive layer of 300 mm long and 200 mm wide.
  • a monolithic sheet having a thickness of 20 ⁇ m was obtained.
  • Example 2 An integrated sheet was obtained in the same manner as in Example 1, except that 2 parts by mass of 2E4MZ (imidazole-based thermosetting agent, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was used as the curing agent.
  • 2E4MZ imidazole-based thermosetting agent, manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • Example 3 An integrated sheet was obtained in the same manner as in Example 1, except that 1 part by mass of KBM-402 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the mixed varnish.
  • KBM-402 silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 4 An integrated sheet was obtained in the same manner as in Example 2, except that 1 part by mass of KBM-402 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the mixed varnish.
  • KBM-402 silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 5 An integrated sheet was obtained in the same manner as in Example 1, except that 10 parts by mass of SIRMEK50WT%-M01 (silica slurry filler, manufactured by CIK Nanotech) was added to the mixed varnish.
  • Example 6 In Example 2, 80 parts by mass of SIRMEK50WT%-M01 (silica slurry filler, manufactured by CIK Nanotech) and 1 part by mass of KBM-402 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to the mixed varnish. An integrated sheet was obtained in the same manner as in Example 2, except for the above.
  • Example 7 An integrated sheet was obtained in the same manner as in Example 1, except that the compound having a cyclic ether group was replaced with 50 parts by mass of EPPN-501H (triphenylmethane type epoxy resin, manufactured by Nippon Kayaku Co., Ltd.). rice field.
  • EPPN-501H triphenylmethane type epoxy resin, manufactured by Nippon Kayaku Co., Ltd.
  • Example 8 In Example 2, the compound having a cyclic ether group was 25 parts by mass of 828 (bisphenol A type liquid epoxy resin, manufactured by Mitsubishi Chemical Corporation) and 25 parts by mass of EPPN-501H (triphenylmethane type epoxy resin, manufactured by Nippon Kayaku Co., Ltd.). An integrated sheet was obtained in the same manner as in Example 2, except that a mixture of parts was used.
  • 828 bisphenol A type liquid epoxy resin, manufactured by Mitsubishi Chemical Corporation
  • EPPN-501H triphenylmethane type epoxy resin, manufactured by Nippon Kayaku Co., Ltd.
  • Example 1 An integrated sheet was obtained in the same manner as in Example 1, except that 300 parts by mass of SIRMEK50WT%-M01 (silica slurry filler, manufactured by CIK Nanotech) was added to the mixed varnish.
  • SIRMEK50WT%-M01 sica slurry filler, manufactured by CIK Nanotech
  • Example 2 An integrated sheet was obtained in the same manner as in Example 4, except that 450 parts by mass of SIRMEK50WT%-M01 (silica slurry filler, manufactured by CIK Nanotech) was added to the mixed varnish.
  • SIRMEK50WT%-M01 silicon slurry filler, manufactured by CIK Nanotech
  • Example 6 In Example 1, the polymer component was replaced with YX7200B35 (phenoxy resin, Tg 150 ° C., manufactured by Mitsubishi Chemical Co., Ltd.) 50 parts by mass, and the curing agent was SI-B3 (thermal cationic polymerization initiator, manufactured by Sanshin Chemical Industry Co., Ltd.) 2 parts by mass. An integrated sheet was obtained in the same manner as in Example 1, except that
  • the compounding amount of each component of the adhesive is expressed in parts by mass.
  • the adhesive layer breaks due to repeated bending, and the adhesive layer Fold marks or peeling between the adhesive layer and the flexible film were likely to occur, and the bending resistance was poor (Comparative Examples 1, 2, 4 to 6).
  • the interlayer surface free energy difference was larger than that specified in the present invention, the bending resistance was also inferior (Comparative Example 3).
  • all of the integrated sheets of Examples 1 to 8, which satisfy the requirements of the present invention exhibited excellent flex resistance. It can be seen that the application of the integrated sheet of the present invention as a support base material for a flexible device contributes to a reduction in man-hours and an improvement in the reliability of the flexible device.

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PCT/JP2022/044271 2021-12-16 2022-11-30 フレキシブルデバイス用基材・接着剤層一体型シート、及びフレキキシブルデバイスの製造方法 Ceased WO2023112685A1 (ja)

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