WO2021199798A1 - Stratifié à base d'un substrat inorganique/film plastique technique équipé d'un film protecteur, empilement stratifié, procédé de stockage de stratifié, et procédé de transport de stratifié - Google Patents

Stratifié à base d'un substrat inorganique/film plastique technique équipé d'un film protecteur, empilement stratifié, procédé de stockage de stratifié, et procédé de transport de stratifié Download PDF

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WO2021199798A1
WO2021199798A1 PCT/JP2021/006844 JP2021006844W WO2021199798A1 WO 2021199798 A1 WO2021199798 A1 WO 2021199798A1 JP 2021006844 W JP2021006844 W JP 2021006844W WO 2021199798 A1 WO2021199798 A1 WO 2021199798A1
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engineering plastic
inorganic substrate
plastic film
protective film
film
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PCT/JP2021/006844
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English (en)
Japanese (ja)
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全広 山下
奥山　哲雄
俊之 土屋
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東洋紡株式会社
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Priority to KR1020227029868A priority Critical patent/KR102665141B1/ko
Priority to KR1020237043849A priority patent/KR20240005118A/ko
Priority to JP2021526614A priority patent/JP6962506B1/ja
Priority to CN202180019216.0A priority patent/CN115243881A/zh
Publication of WO2021199798A1 publication Critical patent/WO2021199798A1/fr

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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
    • 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
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • 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
    • B32B17/10009—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 number, the constitution or treatment of glass sheets
    • B32B17/10018—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 number, the constitution or treatment of glass sheets comprising only one glass sheet
    • 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
    • B32B27/281—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 polyimides
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/04—4 layers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • 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
    • B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
    • B32B2379/08—Polyimides

Definitions

  • the present invention relates to a form, a storage method, and a transportation method for storing a laminate of an inorganic substrate and an engineering plastic film (hereinafter abbreviated as engineering plastic film).
  • engineering plastic films such as polyimide, aromatic polyamide, polyamideimide, polycarbonate, polyethylene naphthalate, and polyethylene terephthalate is being studied as a substrate material for manufacturing flexible electronic devices. Since such engineering plastic films are manufactured in the form of long rolls, it is generally accepted that a roll-to-roll manufacturing line is ideal for manufacturing flexible devices.
  • many conventional electronic devices such as display devices, sensor arrays, touch screens, and printed wiring boards use rigid rigid substrates such as glass substrates, semiconductor wafers, or glass fiber reinforced epoxy substrates.
  • the manufacturing equipment is also configured on the premise that such a rigid substrate is used.
  • a rigid inorganic substrate such as a glass substrate is used as a temporary support, and an engineering plastic film is temporarily attached to the temporary support.
  • a method of manufacturing a flexible electronic device is known in which the engineering plastic film on which the electronic device is formed is peeled off from the temporary support after handling and processing the electronic device on the engineering plastic film.
  • a rigid substrate such as a glass substrate is used as a temporary support, and a precursor of engineering plastic is applied to the temporary support in a solution state and dried. After forming the precursor film, a chemical reaction is caused to convert the precursor into an engineering plastic to obtain a laminate of a temporary support and an engineering plastic film, and similarly, an electronic device is formed on the engineering plastic film and then peeled off.
  • Patent Document 2 Patent Document 2
  • the rigid temporary support and the engineering plastic film layer which is finally peeled off and becomes the base material of the flexible electronic device are laminated. Since such a laminate can be handled as a rigid plate material, it can be handled in the same manner as a glass substrate by a device for manufacturing a liquid crystal display, a plasma display, an organic EL display, or the like using a conventional glass substrate.
  • the subject of the present invention is a form, a storage method, and a transportation method for storing the laminated body composed of the engineering plastic film and the rigid temporary support described above.
  • Rigid inorganic substrates such as conventional glass substrates are handled in the form of a stack of multiple sheets during storage or transportation.
  • a cushioning material such as a foamed polymer sheet or paper is sandwiched between the inorganic substrates so that the inorganic substrates can be easily taken out from the stack after storage or transportation.
  • Such a method is applicable to a glass substrate having sufficient surface hardness.
  • the hardness of the surface of the engineering plastic film is insufficient, so that when the laminated bodies are stacked, the engineering plastic film surface and the temporary support substrate surface of the laminated body rub against each other. , The soft engineering plastic film surface gets scratched. Furthermore, even when a cushioning material such as a foamed polymer sheet or paper is inserted, the surface of the engineering plastic film is liable to be scratched by foreign matter mixed in.
  • the method commonly used as a means for solving such a problem is a method of protecting the engineering plastic film surface with a protective film.
  • the protective film is a slightly adhesive film in which a weakly adhesive adhesive material is applied to one side of a relatively inexpensive polymer film such as polyethylene, polypropylene, or polyester.
  • An object to be solved by the present invention is to provide an appropriate form and method for storing or transporting a laminate composed of an engineering plastic film and a rigid temporary support. That is, the present invention provides an inorganic substrate / engineering plastic film laminate with a protective film that can be easily taken out individually even when stored in a stacked state for a long period of time, and the inorganic substrate / engineering plastic with a protective film. It is a provision of a stack in which film laminates are stacked, a method of storing an inorganic substrate / engineering plastic film laminate using a specific protective film, and a method of transporting an inorganic substrate / engineering plastic film laminate.
  • the present invention has the following configuration.
  • [1] In an inorganic substrate / engineering plastic film laminate with a protective film containing an inorganic substrate, an engineering plastic film, an adhesive layer of a protective film, and a protective film base material in this order.
  • Adhesive strength Fb by 90 degree peeling method between inorganic substrate and engineering plastic film The adhesive strength Fp of the engineering plastic film and the protective film by the 90 degree peeling method is Fp ⁇ Fb
  • the surface roughness Ra of the surface of the protective film base material opposite to the adhesive layer is in the range of 0.02 ⁇ m to 1.2 ⁇ m, which is an inorganic substrate / engineering plastic film with a protective film.
  • the dynamic friction coefficient between the surface of the protective film base material opposite to the adhesive layer and the surface of the inorganic substrate not facing the engineering plastic film is 0.02 to 0.25.
  • Inorganic substrate / engineering plastic film laminate with. [4] The protection according to any one of [1] to [3], wherein the adhesive strength Fb between the inorganic substrate and the engineering plastic film is in the range of 0.02 to 0.3 N / cm.
  • Inorganic substrate / engineering plastic film laminate with film [5] The protection according to any one of [1] to [4], wherein the adhesive strength Fp between the engineering plastic film and the protective film is in the range of 0.01 to 0.27 N / cm. Inorganic substrate / engineering plastic film laminate with film. [6] The inorganic substrate / engineering plastic film laminate with a protective film according to any one of [1] to [5], wherein the length of one side of the circumscribed circle of the inorganic substrate is 310 mm or more. [7] When the surface resistance of the surface of the protective film base material opposite to the adhesive material is placed in an environment of 23 ° C.
  • the air layer between the surface of the protective film and the surface of the inorganic substrate facing each other gradually moves out from the surface due to the weight of the laminate. It is discharged and becomes in close contact with the vacuum. This is the reason why it is difficult to take out the laminate individually when it is stored for a long period of time. If the size of the laminate is small, it does not pose a big problem, but assuming that it is handled by the display manufacturing apparatus, the size of the laminate is a glass plate having a maximum size of about 2 m ⁇ 3 m.
  • FIG. 1 is a schematic view showing a cross-sectional structure of an inorganic substrate / engineering plastic film laminate.
  • FIG. 2 is a schematic view showing a cross-sectional structure of the protective film.
  • FIG. 3 is a schematic view showing a cross-sectional structure of an inorganic substrate / engineering plastic film laminate with a protective film.
  • FIG. 4 is a schematic view showing a cross-sectional structure of a stack in which four inorganic substrates / engineering plastic film laminates with a protective film are stacked.
  • a glass plate As the inorganic substrate in the present invention, a glass plate, a semiconductor wafer, a metal plate, a ceramic plate, or the like can be used.
  • the glass plate include quartz glass, high silicate glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (Pylex (registered trademark)), borosilicate glass (non-alkali), and the like.
  • Borosilicate glass microsheet
  • aluminosilicate glass and the like are included.
  • Examples of the semiconductor wafer include silicon wafer, germanium, silicon-germanium, gallium-arsenic, aluminum-gallium-indium, nitrogen-phosphosphide-antimony, SiC, InP (indium phosphide), InGaAs, GaInNAs, LT, LN, ZnO. (Zinc oxide), CdTe (cadmium telluride), ZnSe (zinc selenide) and other wafers can be mentioned.
  • Examples of the metal plate include single element metals such as W, Mo, Pt, Fe, Ni, and Au, alloys such as inconel, monel, mnemonic, carbon copper, Fe—Ni based invar alloy, superinvar alloy, and various stainless steels. included.
  • a multilayer metal plate formed by adding another metal layer or a ceramic layer to these metals is also included.
  • a ceramic plate a single or composite sintered body such as alumina, magnesia, calcia, silicon nitride, boron nitride, aluminum nitride, and beryllium oxide can be used.
  • a ceramic substrate it is preferable to use a ceramic substrate whose surface is smoothed by glass glaze treatment.
  • the surface roughness of the inorganic substrate in the present invention is preferably in the range of 0.01 to 2 nm. At least, when the inorganic substrate is laminated with the engineering plastic, the surface roughness of the surface opposite to the engineering plastic film is preferably in the range of 0.01 to 2 nm. Further, the preferable range of the surface roughness is the range of 0.01 to 0.8 nm, and further preferably the range of 0.01 to 0.3 nm.
  • the size of the inorganic substrate is preferably such that the length of one side of the circumscribed circle is 310 mm or more when the inorganic substrate is rectangular.
  • the engineering plastic film in the present invention is a polymer compound film that retains a tensile strength of 49 MPa or more and a flexural modulus of 2.5 GPa or more even when exposed to an environment of 100 ° C. or higher for a long time, preferably 168 hours.
  • a film such as a polymer.
  • the polymer film having an imide bond include polyimide, polyamideimide, polyetherimide, polyimidebenzoxazole, and bismaleimide triazine.
  • aromatic polyimide, alicyclic polyimide, polyamideimide, polyetherimide and the like can be used as the polyimide film. More preferably, it refers to a polymer containing 50% or more of a polyimide skeleton.
  • a polyimide film is a green film (“precursor film”) in which a polyamic acid (polyimide precursor) solution obtained by reacting diamines and tetracarboxylic acids in a solvent is applied to a support for producing a polyimide film and dried.
  • polyamic acid film (Also referred to as "polyamic acid film”), and further obtained by subjecting the green film to a high-temperature heat treatment to carry out a dehydration ring-closing reaction on a support for producing a polyimide film or in a state of being peeled off from the support.
  • the diamines constituting the polyamic acid are not particularly limited, and aromatic diamines, aliphatic diamines, alicyclic diamines and the like usually used for polyimide synthesis can be used. From the viewpoint of heat resistance, aromatic diamines are preferable, and among aromatic diamines, aromatic diamines having a benzoxazole structure are more preferable. When aromatic diamines having a benzoxazole structure are used, it is possible to develop high bending elastic modulus, low coefficient of thermal expansion, and low linear expansion coefficient as well as high heat resistance.
  • the diamines may be used alone or in combination of two or more.
  • Polyimide resin is generally colored yellow to brown, but depending on the chemical structure, a colorless and highly transparent polyimide film can be obtained.
  • 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclopentanetetracarboxylic acid dianhydride, 1,2,4, as acid components used in the synthesis of the precursor 5-Cyclohexanetetracarboxylic acid dianhydride, bicyclo [2,2,1] heptane-2,3,5,6-tetracarboxylic acid dianhydride, bicyclo [2,2,2] octane-2,3,5 , 6-Tetracarboxylic acid dianhydride, 3,3', 4,4'-bicyclohexyltetracarboxylic acid dianhydride, 1,2,4-cyclohexanetricarboxylic acid anhydride and the like are exemplified, but are particularly preferable.
  • 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,3', 4,4'-bicyclohexyltetracarboxylic acid dianhydride It is a thing.
  • These aliphatic carboxylic acids may be used alone or in combination of two or more.
  • those containing unsaturated bonds such as bicyclo [2,2,2] octo-7-ene-2,3,5,6-tetracarboxylic dianhydride may be used in combination.
  • Examples of the diamine component used for the synthesis of the colorless transparent polyimide resin of the present invention or a precursor thereof are 1,3-phenylenediamine, 1,4-phenylenediamine, 2,4-diaminotoluene, 2,6.
  • NS Of these, particularly preferred are p-phenylenediamine, 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-bis (trifluoromethyl) benzidine, 2,2'-bis (trifluoro). Methyl) -4,4'-diaminodiphenyl ether, 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4' -Methylenebis (2-methylcyclohexylamine), 4,4'-methylenebis (2,6-dimethylcyclohexylamine).
  • the above amine components may be used alone or in combination of two or more.
  • the inorganic substrate and the engineering plastic film are laminated.
  • the adhesive strength between the inorganic substrate and the engineering plastic film laminate is preferably in the range of 0.02 to 1.0 N / cm, and more preferably in the range of 0.03 to 0.3 N / cm. This adhesive strength is an adhesive strength on the assumption that the inorganic substrate and the engineering plastic film will be peeled off in the future.
  • the laminate of the present invention can be classified into three types according to the production method.
  • (1) A method in which an engineering plastic film is prepared in advance and bonded to an inorganic substrate.
  • (2) A method in which a solution of an engineering plastic or a solution of an engineering plastic precursor is applied to an inorganic substrate and dried and, if necessary, a chemical reaction is carried out to form an engineering plastic film on the inorganic substrate.
  • (3) A method in which a film of an engineering plastic film precursor is prepared in advance, bonded to an inorganic substrate, and then subjected to a chemical reaction to form an engineering plastic film on the inorganic substrate.
  • a method of using an adhesive and a method of activating both or one surface of the engineering plastic film and the inorganic substrate by surface treatment and directly bonding them are used.
  • Specific examples of the latter include a method of treating the surface of the engineering plastic film with active energy rays, plasma, etc., a method of treating the surface of the inorganic substrate in the same manner, a method of chemically modifying the surface of the engineering plastic film with a coupling agent, and the like.
  • techniques such as mold release agent treatment and release layer formation can be combined in order to control the peel strength between the engineering plastic film and the inorganic plate.
  • a solution of a polyimide resin or a precursor of a polyimide resin can be used.
  • a solution in the state of isoimide or polyamic acid is applied to an inorganic substrate, and after drying, heating or a catalyst is allowed to act to obtain a polyimide film. Drying and heating may be performed in parallel.
  • a polyester film or the like is used.
  • An engineering plastic precursor preferably a polyimide precursor, is applied onto the film, dried, and chemically changed as necessary to first obtain a gel film.
  • the solvent may remain on the gel film. Since the gel film thus obtained has a certain degree of tackiness, it can be laminated by pressing it against an inorganic substrate.
  • the gel film may be interpreted as the B stage of the curable resin.
  • this method can form a curable resin such as an epoxy resin, a melamine resin, a phenol resin, or a BT resin as an empra film on an inorganic substrate, and in the present invention, the film of these curable resins is empla. It can also be handled as a film.
  • a curable resin such as an epoxy resin, a melamine resin, a phenol resin, or a BT resin
  • the adhesive strength Fb between the inorganic substrate and the engineering plastic film in the present invention is preferably in the range of 0.02 to 0.3 N / cm.
  • the adhesive strength does not necessarily have to be in this range, but in the present invention, it can be particularly effective in weak adhesion, that is, in a laminate premised on peeling the engineering plastic film from the inorganic substrate in a subsequent step.
  • the engineering plastic film surface of the laminate of the engineering plastic film and the inorganic substrate is covered with a protective film.
  • the protective film in the present invention is composed of at least a protective film base material and an adhesive layer.
  • As the protective film base material in addition to PET film, PEN film, polyethylene film, polypropylene film, nylon film, etc., heat-resistant super engineering plastics such as PPS film, PEEK film, aromatic polyamide film, polyimide film, polyimide benzasole film, etc.
  • a film can be used.
  • the adhesive material of the protective film is not particularly limited, and known materials such as acrylic type, silicone type, urethane type, rubber type, and polyester type can be used. From the viewpoint of handleability, an acrylic resin, a silicone resin, and a urethane resin are preferable.
  • the acrylic resin is obtained by polymerizing a monomer such as a (meth) acrylic acid alkyl ester. Specific examples of the monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, and t-butyl (meth).
  • n-hexyl (meth) acrylate 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and other alkyl ( Meta) acrylate compounds can be mentioned. A plurality of these can be copolymerized if necessary.
  • the surface roughness Ra of the protective film base material in the present invention is preferably 0.02 ⁇ m or more, preferably 0.025 ⁇ m or more, more preferably 0.03 ⁇ m or more on the surface opposite to the adhesive layer, and the upper limit is 1.2 ⁇ m.
  • the range of preferably 0.6 ⁇ m or less, more preferably 0.3 ⁇ m or less is further preferable.
  • a method of controlling the surface roughness of the protective film base material within a predetermined range a method of adding inorganic particles to the raw material resin at the time of producing the film of the protective film base material to control the surface roughness can be exemplified.
  • the inorganic particles a predetermined amount of known inorganic particles such as silica, alumina, calcia, magnesia, calcium carbonate, magnesium carbonate, calcium phosphate, magnesium phosphate, barium sulfate, talc, and kaolin may be added.
  • the amount added is not uniform depending on the draw ratio at the time of producing the base film, the final thickness of the base film, the particle size distribution of the added inorganic particles, etc., but is generally 500 ppm by mass ratio to the mass of the base film resin.
  • the upper limit is in the range of 10% mass or less, preferably 3% by mass or less, still more preferably 10000 ppm or less.
  • a method of controlling the surface roughness of the protective film base material within a predetermined range a method of polishing or grinding the surface of the film base material to obtain a predetermined surface roughness can be exemplified.
  • a method of controlling the surface roughness of the protective film base material within a predetermined range a method of casting a film raw material on a support base material prepared in advance so as to have a predetermined surface roughness to obtain a protective film base material is exemplified. can.
  • a method of controlling the surface roughness of the protective film base material by pressing an embossed roller or the like processed into a predetermined surface shape can be exemplified.
  • the adhesive strength Fp of the engineering plastic film and the protective film in the present invention by the 90-degree peeling method is preferably in the range of 0.01 to 0.27 N / cm. Further, in the present invention, the adhesive strength Fb of the inorganic substrate and the engineering plastic film by the 90-degree peeling method and the adhesive strength Fp of the engineering plastic film and the protective film are determined. Fp ⁇ Fb It is preferable that there is a relationship of. That is, when the protective film is peeled from the engineering plastic film, it is preferable to set the adhesive force between the layers so that the engineering plastic film does not peel off from the inorganic substrate. Since the adhesive has a peeling speed dependence depending on the type of the pressure-sensitive adhesive, the adhesive strength between the layers differs depending on the peeling speed.
  • the peeling speed at the time of peeling is preferably as high as possible, but is preferably at least 50 mm / min, preferably 100 mm / min or less.
  • the adhesive strengths Fp and Fb are based on the 90 degree peeling method, even when the peeling strength between the engineering plastic film and the protective film and the peeling strength between the inorganic substrate and the engineering plastic film are both 180 degrees peeled, the peeling strength is 180 degrees. It is preferable that Fp ⁇ Fb.
  • the coefficient of kinetic friction between the surface of the protective film base material opposite to the pressure-sensitive adhesive layer and the surface of the inorganic substrate not facing the engineering plastic film is 0.02 to 0. It is in the range of 25.
  • the dynamic friction coefficient is realized by controlling the surface roughness of the surface of the protective film base material opposite to the adhesive layer and the surface of the inorganic substrate not facing the engineering plastic film within the above range. can.
  • a plurality of the above-mentioned laminates preferably 4 or more, and more preferably 10 or more can be stacked to form a stack.
  • the laminate since the coefficient of kinetic friction between the surface opposite to the adhesive of the protective film base material that comes into contact with the stack and the inorganic substrate is within a predetermined range, the laminate can be easily taken out from the stack individually. Is possible.
  • the surface resistance of the surface of the protective film base material opposite to the adhesive material is 1 ⁇ 10 6 to 1 ⁇ 10 10 [ ⁇ ] is preferable. That is, it is preferable that the surface of the protective film has conductivity to the extent that it is not unnecessarily charged.
  • the protective film surface is charged, when the laminated bodies are stacked to form a stack, the protective film surface and the inorganic substrate surface are in close contact with each other due to static electricity, making it difficult to take out the laminated bodies individually. There is.
  • the laminated body can be stored in the stacked state thus obtained.
  • the stack of the present invention is stored so that the inorganic substrate of the stack is in the horizontal direction, is stored in the vertical direction, or is stored at an angle of about 75 to 89 degrees, which is close to vertical. It is also possible to correspond to.
  • the laminated body can be transported in the stacked state thus obtained.
  • the stack of the present invention is held and transported so that the inorganic substrate of the stack is in the horizontal direction, and when the stack is held and transported so as to be in the vertical direction, the stack is almost vertical and tilted at about 75 to 89 degrees. It is possible to handle any case where the product is kept in a state and transported.
  • ⁇ Adhesive strength> The adhesive strength between the engineering plastic film and the inorganic substrate and the adhesive strength between the protective film and the engineering plastic film (before heating) were measured under the following conditions according to the 90-degree peeling method described in JIS K 6854-1. Similarly, the adhesive strength after heating at 120 ° C. for 1 hour was also measured.
  • Tensile tester "Autograph (registered trademark) AG-IS” manufactured by Shimadzu Corporation Measurement temperature: Room temperature Peeling speed: 50 mm / min Atmosphere: Atmosphere Measurement sample width: 10 mm ⁇ Surface resistance>
  • the resistance measuring cell 16008B manufactured by Agilent Technologies was attached to the milliohm meter 4338B manufactured by Agilent Technologies, and the measurement was performed by a method compliant with IEC 62633-1-2.
  • the engineering plastic film F1 a polyimide film UPIREX 25S manufactured by Ube Industries, Ltd. was used. First, one side of the engineering plastic film was subjected to atmospheric pressure plasma treatment using nitrogen gas.
  • the inorganic substrate a glass plate OA10G manufactured by Nippon Electric Glass having a thickness of 370 mm ⁇ 470 mm and a thickness of 0.7 mm was used. First, the surface of the glass plate is cleaned by UV / ozone treatment, then the glass plate is placed in a clean chamber together with a hot plate, the glass plate is supported by a support base, and then the inside of the chamber is replaced with clean dry nitrogen to be inorganic.
  • a petri dish filled with a silane coupling agent (3-aminopropyltrimethoxysilane) is placed so that the liquid level is located 200 mm below the substrate, the petri dish is heated to 100 ° C. on a hot plate, and the lower surface of the inorganic substrate is silane.
  • a silane coupling agent (3-aminopropyltrimethoxysilane)
  • the petri dish is heated to 100 ° C. on a hot plate
  • the lower surface of the inorganic substrate is silane.
  • After exposing to the coupling agent steam for 3 minutes remove it from the chamber, place it in a clean bench, and place it on a hot plate whose temperature has been adjusted to 120 ° C. so that the side opposite to the exposed surface of the inorganic substrate is in contact with the hot plate.
  • the heat treatment was carried out for 1 minute to obtain a glass plate treated with a silane coupling agent.
  • silane coupling agent-treated surface of the glass plate was brought into close contact with the atmospheric pressure plasma-treated surface of the engineering plastic film obtained earlier with a roll laminator, and heat treatment was performed at 150 ° C. for 30 minutes in a clean oven. , An engineering plastic film / inorganic substrate laminate L1 was obtained.
  • engineering plastic film F2 Polyimide film made by Toray DuPont Kapton 100H
  • F3 Toyobo Polyimide Film Xenomax 38LR
  • F4 Kuraray liquid crystal polymer film Vecstar CTQ-25 The same operation was carried out except for the change to, to obtain the laminated bodies L2 to L4 of the engineering plastic film / inorganic substrate.
  • stirring was continued for another 20 hours while adjusting the temperature inside the container to be in the range of 25 ° C. ⁇ 5 ° C. using an oil bath to obtain a polyamic acid solution.
  • the obtained polyamic acid solution was applied to one side of a glass plate OA10G manufactured by Nippon Electric Glass having a thickness of 370 mm ⁇ 470 mm and a thickness of 0.7 mm using a bar coater, and applied at 70 ° C. for 7.5 minutes and at 120 ° C. for 7 minutes. After drying for 5. minutes, the mixture was further heated in an inert oven under a nitrogen atmosphere at 300 ° C. for 20 minutes.
  • the polyamic acid was converted to polyimide to obtain an engineering plastic film / inorganic substrate laminate L6 composed of a polyimide film to be an engineering plastic film F6 and a glass plate.
  • Table 1 shows the adhesive strength Fa between the engineering plastic film and the glass plate of the obtained laminated body, the surface roughness Ra of the surface opposite to the laminated surface of the glass plate with the engineering plastic film, and the like.
  • the resin film layer was peeled off from the laminate L6 produced by the same method to obtain an engineering plastic film F6.
  • This polyamic acid solution was applied to a non-slip material surface of a polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd.) using a comma coater with a die coater so that the final film thickness was 20 ⁇ m. This was dried at 110 ° C. for 10 minutes.
  • the polyamic acid film that has obtained self-support after drying is peeled off from the A4100 film that has been used as a support, passed through a pin tenter having a pin sheet on which pins are arranged, and the film end is gripped by inserting it into the pins, and the film does not break.
  • the pin sheet spacing is adjusted so as to prevent unnecessary slack, and the film is conveyed, and heated at 200 ° C. for 3 minutes, 250 ° C. for 3 minutes, and 300 ° C. for 6 minutes to carry out the imidization reaction. I made it progress. Then, the film was cooled to room temperature in 2 minutes, and the portions of the film having poor flatness were cut off with a slitter and wound into a roll to obtain an engineering plastic film (polyimide film) F7 having a width of 450 mm. Using the obtained engineering plastic film F7, the engineering plastic film / inorganic substrate laminate L7 was obtained in the same manner as in the production of the engineering plastic film / inorganic substrate laminate L1.
  • Protective films P1 to P6 were produced by using the polyester (PET) film and polypropylene (PP) film shown in Table 2 as the base film of the protective film and applying the adhesive shown in Table 2 as well.
  • the surface roughness in Table 2 indicates the surface roughness on the side opposite to the pressure-sensitive adhesive layer of the protective film base material.
  • the adhesive strength Fb of the inorganic substrate (glass plate) and the engineering plastic film by the 90 degree peeling method and the adhesive strength Fp of the engineering plastic film and the protective film by the 90 degree peeling method are obtained.
  • Fp ⁇ Fb It is shown that the engineering plastic film is not peeled off from the inorganic substrate (glass plate) together with the protective film when the protective film is peeled off in the case of.
  • the inorganic substrate / engineering plastic film laminate with the protective film of the present invention is excellent in handleability and transportability, and can be handled while the engineering plastic film surface is protected by the protective film, and the engineering plastic film surface is protected.
  • the protective film can be peeled off without any problem.
  • INDUSTRIAL APPLICABILITY The present invention can be usefully used for manufacturing a flexible device or the like by peeling an engineering plastic film from an inorganic substrate after microfabrication of the engineering plastic film using such a laminate.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Ceramic Engineering (AREA)
  • Laminated Bodies (AREA)
  • Packages (AREA)
  • Packaging Of Annular Or Rod-Shaped Articles, Wearing Apparel, Cassettes, Or The Like (AREA)

Abstract

Selon la présente invention, une protection est assurée, par un film protecteur, à un stratifié à base de plastique technique/substrat inorganique qui est utilisé dans un procédé de production visant à obtenir un dispositif électronique flexible et comprenant les étapes consistant à faire supporter de manière temporaire un film plastique technique par un substrat inorganique, soumettre le film plastique technique à une microfabrication de façon à préparer un dispositif électronique, puis retirer celui-ci du substrat inorganique.　Ce stratifié à base d'un substrat inorganique/film plastique technique qui est équipé d'un film protecteur comprend successivement un substrat inorganique, un film plastique technique, une couche adhésive autocollante pour un film protecteur, et un matériau de base de film protecteur. Le stratifié à base d'un substrat inorganique/film plastique technique qui est équipé d'un film protecteur présente une aptitude à la conservation, une aptitude à la manipulation et une aptitude au transport souhaitables, grâce à la combinaison d'une force adhésive Fb entre le substrat inorganique et le film plastique technique comme mesuré par un essai de pelage à 90 degrés, et d'une force adhésive Fp entre le film plastique technique et le film protecteur comme mesuré par un essai de pelage à 90 degrés, telles à satisfaire la relation Fp < Fb, ainsi que grâce au réglage dans une plage de 0,02 à 1,2 µm de la rugosité de surface Ra d'une surface du matériau de base du film protecteur sur la face opposée à la couche autocollante.
PCT/JP2021/006844 2020-03-31 2021-02-24 Stratifié à base d'un substrat inorganique/film plastique technique équipé d'un film protecteur, empilement stratifié, procédé de stockage de stratifié, et procédé de transport de stratifié WO2021199798A1 (fr)

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KR1020227029868A KR102665141B1 (ko) 2020-03-31 2021-02-24 보호 필름을 갖는 무기 기판/엔지니어링 플라스틱 필름 적층체, 적층체의 스택, 적층체의 보관 방법 및 적층체의 수송 방법
KR1020237043849A KR20240005118A (ko) 2020-03-31 2021-02-24 보호 필름을 갖는 무기 기판/엔지니어링 플라스틱 필름 적층체, 적층체의 스택, 적층체의 보관 방법 및 적층체의 수송 방법
JP2021526614A JP6962506B1 (ja) 2020-03-31 2021-02-24 保護フィルム付きの無機基板／エンジニアリングプラスチックフィルム積層体、積層体のスタック、積層体の保管方法、および積層体の輸送方法
CN202180019216.0A CN115243881A (zh) 2020-03-31 2021-02-24 带保护膜的无机基板/工程塑料膜层叠体、层叠体组、层叠体的保管方法及层叠体的运输方法

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WO2023074536A1 (fr) * 2021-10-27 2023-05-04 東洋紡株式会社 Stratifié muni d'un film protecteur de substrat inorganique et de film polymère thermorésistant

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KR20220154099A (ko) 2022-11-21
TW202204145A (zh) 2022-02-01
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CN115243881A (zh) 2022-10-25
TWI811636B (zh) 2023-08-11
KR102665141B1 (ko) 2024-05-10
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