WO2019117059A1 - 積層フィルム、離型フィルムおよび積層体 - Google Patents

積層フィルム、離型フィルムおよび積層体 Download PDF

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WO2019117059A1
WO2019117059A1 PCT/JP2018/045230 JP2018045230W WO2019117059A1 WO 2019117059 A1 WO2019117059 A1 WO 2019117059A1 JP 2018045230 W JP2018045230 W JP 2018045230W WO 2019117059 A1 WO2019117059 A1 WO 2019117059A1
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layer
film
laminated film
fluorine atom
laminated
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PCT/JP2018/045230
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English (en)
French (fr)
Japanese (ja)
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陽介 大関
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三菱ケミカル株式会社
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=66819211&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2019117059(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Priority to CN201880079992.8A priority Critical patent/CN111465639B/zh
Priority to KR1020237044895A priority patent/KR20240005214A/ko
Priority to KR1020207015538A priority patent/KR102639595B1/ko
Priority to CN202311249495.7A priority patent/CN117447743A/zh
Priority to JP2019559616A priority patent/JP7173045B2/ja
Publication of WO2019117059A1 publication Critical patent/WO2019117059A1/ja

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    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • 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
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • 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
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • 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
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/403—Adhesives in the form of films or foils characterised by release liners characterised by the structure of the release 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/405—Adhesives in the form of films or foils characterised by release liners characterised by the substrate of the release liner
    • 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
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • C09J2427/00—Presence of halogenated polymer
    • C09J2427/005—Presence of halogenated polymer in the release coating
    • 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
    • C09J2483/00—Presence of polysiloxane
    • 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
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/005—Presence of polysiloxane in the release coating

Definitions

  • the present invention relates to a laminated film, and more particularly to a laminated film having releasability.
  • silicone pressure-sensitive adhesive that is strongly adhesive has attracted attention.
  • the silicone pressure-sensitive adhesive is used in the form of a tape (film) as a pressure-sensitive adhesive layer, but before use, it is usually stored in a state where one or both sides are covered with a release film. It is used after peeling the mold film.
  • a strongly adhesive silicone pressure-sensitive adhesive adheres strongly to a widely used organosilicone-coated release film, and there is a problem that the release film becomes difficult to peel off during use.
  • a fluorinated silicone material having a fluorine substituent has been proposed as a method for expressing the releasability from a molded article formed by molding of a mold resin such as a silicone resin composition.
  • Patent Document 1 A fluorinated silicone material having a fluorine substituent has been proposed as a method for expressing the releasability from a molded article formed by molding of a mold resin such as a silicone resin composition.
  • the inventors of the present invention included fluorine atoms in each layer of a laminated film in which an A layer and a B layer were laminated in this order on at least one side of a polymer film.
  • the gist of the present invention is a laminated film in which an A layer and a B layer are laminated in this order on at least one surface of a polymer film, and both layers of the A layer and B layer contain fluorine atoms.
  • the gist of the present invention is a laminated film characterized by the fluorine atom content rate of B layer being more than the fluorine atom content rate of A layer.
  • the gist of the present invention is a laminated film in which an A layer and a B layer are laminated in this order on at least one surface of a polymer film, and the B layer contains a fluorine atom and is measured by the following method It is a laminated film characterized in that the normal peeling force at the time is 100 mN / cm or less. ⁇ Measurement of normal peeling force> A tape with a silicone pressure sensitive adhesive (3M Japan, No. 5413 tape, 50 mm width) is laminated to the surface of layer B of the laminated film, and a 180 ° peel test is carried out under the conditions of a peel speed of 0.3 m / min.
  • a laminated film having excellent releasability to a pressure-sensitive adhesive layer such as a silicone pressure-sensitive adhesive.
  • the laminated film of the present invention is a laminated film in which an A layer (undercoat layer) and a B layer (releasing layer) are laminated in this order on at least one side of a polymer film, as illustrated in FIG.
  • the laminated film of the present invention will be described below in the order of the polymer film, the A layer (undercoat layer) and the B layer (releasing layer).
  • polymer film As a polymer film to be a base material of the laminated film of the present invention, a film in which a polymer such as polyethylene, polypropylene, polyester, polystyrene, polycarbonate, polyether sulfone, polyamide, polyimide is formed in a film shape can be mentioned. . Further, as long as film formation is possible, it may be a mixture of these materials (polymer blend) or a composite of constituent units (copolymer).
  • the polymer film is not particularly limited as long as it is formed into a film, and may be a non-stretched film or a stretched film, but is preferably a stretched film stretched in a uniaxial direction or a biaxial direction. Among them, a biaxially stretched film is more preferable from the viewpoint of balance of mechanical properties and planarity.
  • the thickness of the polymer film constituting the laminated film in the present invention is not particularly limited as long as the film can be formed as a film, but is preferably 5 ⁇ m to 1000 ⁇ m, and more preferably 10 ⁇ m to 500 ⁇ m, More preferably, it is 15 ⁇ m or more or 200 ⁇ m or less.
  • polyester films are preferable because they are excellent in physical properties such as heat resistance, planarity, optical properties, strength and the like, and among them, biaxially stretched polyester films are particularly preferable.
  • the polyester film may be a single layer or a multilayer film (laminated film) having two or more layers having different properties.
  • the polyester used for the polyester film may be homopolyester or copolyester.
  • the homopolyester is preferably one obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol.
  • aromatic dicarboxylic acids include terephthalic acid and 2,6-naphthalenedicarboxylic acid
  • aliphatic glycols include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol and the like.
  • Examples of representative homopolyesters include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT) and the like.
  • examples of the dicarboxylic acid component of the copolyester include one or more of isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid and the like, and ethylene as a glycol component
  • glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, neopentyl glycol and the like can be mentioned.
  • polyethylene terephthalate in which 60 mol% or more, preferably 80 mol% or more is ethylene terephthalate units is preferable.
  • the surface of the polymer film is provided with antistatic properties, sealing properties of bleeding of the compound or oligomer onto the film surface (bleed, plate out), light transmittance of the film, or the after-mentioned
  • a subbing layer base coat layer may be provided in order to improve the adhesion to the A layer (undercoat layer).
  • the subbing layer may be formed by either an in-line coating method in which the subbing layer is formed simultaneously with the formation of the polymer film, or an off-line coating method in which the subbing layer is separately formed on the film having been formed.
  • the undercoat layer When the undercoat layer is provided, it may be formed on at least one side of the polymer film. When forming on both sides, the same undercoating layer may be formed on both sides, or different undercoating layers may be formed on each side.
  • the undercoat layer may be any of a layer formed of an organic substance, a layer formed of an inorganic film, and a layer formed of a mixture of an organic substance and an inorganic substance.
  • a layer (undercoat layer) In the present invention, an A layer (undercoat layer) is provided on at least one side of the polymer film.
  • the A layer usually contains a fluorine atom.
  • the adhesion between layer A and layer B described below is obtained, but when used as a release film, light releasability between layer B and the pressure-sensitive adhesive layer, which is an adherend, is expressed, and adhesion is achieved. It can make the body easy to peel off.
  • There is no limitation on the method of containing a fluorine atom in the layer A and it is sufficient if at least a compound containing a fluorine atom is contained in the layer A.
  • low molecular weight compounds containing a fluorine atom, resins containing a fluorine atom, and the like can be mentioned.
  • a resin containing a fluorine atom it is preferable to use a resin containing a fluorine atom, and in particular, the resin is preferably curable.
  • the peeling force with respect to a to-be-adhered body becomes small, and it can have light peelability.
  • the adherend adherend (adhesive) is also followed in the peeling direction at the time of peeling of the laminated film.
  • the layer A contains a material containing a fluorine atom, and the fluorine atom content (fraction of atoms) is preferably 50 ppm or more, more preferably 500 ppm or more as the whole layer A, from the viewpoint of adhesion and light removability. 1,000 ppm or more is more preferable, and 50,000 ppm or more is particularly preferable.
  • the upper limit is not particularly limited, but preferably less than 900,000 ppm, more preferably 800,000 ppm or less, and still more preferably 700,000 ppm or less.
  • the fluorine atom content ratio of the layer A is confirmed by performing, for example, depth direction analysis by sputter etching in the vicinity of the polymer film in the undercoat layer constituting the laminated film by X-ray photoelectron spectroscopy (XPS method) Can.
  • the fluorine atom content ratio of the layer A can also be quantified by using a material (fluorinated silicone etc.) known in advance as the fluorine atom content ratio as a reference. In the case of confirmation by the XPS method, the ratio of fluorine to all elements except hydrogen and helium was taken as the fluorine atom content ratio.
  • layer B releasing layer containing fluorine atoms can be uniformly coated on layer A by the coating method, and after coating or lamination.
  • the adhesion between layer A and layer B can also be enhanced.
  • resin used for A layer is resin containing only a fluorine atom, it mixes and uses resin (non-fluorinated resin) which does not contain a fluorine atom. It is also good.
  • the composition may have a fluorine atom content ratio inclined in the thickness direction.
  • a resin containing a fluorine atom used for this invention resin which contains a fluorine atom in the side chain part of resin frame
  • skeleton is mentioned.
  • the resin containing a fluorine atom include fluorine-containing hydrocarbon resins such as polytetrafluoroethylene in addition to fluorinated silicone resins, and various other resins subjected to a fluorination treatment.
  • a fluorinated silicone resin is preferred from the viewpoint of releasability.
  • the fluorinated silicone resin both curable and non-curable ones can be used without particular limitation. Among them, curable fluorinated silicone resins are preferable in that they form a stronger layer.
  • the fluorinated silicone resin may be a solvent type, a non-solvent type, or a mixture thereof.
  • the curable fluorinated silicone resin usually has a functional group such as an alkenyl group or a hydrosilyl group which can form a crosslinked structure upon reaction (curing).
  • the curable fluorinated silicone resin KP-911 and X-70-201S manufactured by Shin-Etsu Chemical Co., Ltd .; FS1265-300CS and FS1265-1000CS, FS1265-10000CS and BY24-900 manufactured by Toray Dow Corning Co., Ltd. , BY24-903, Syl-off 3062, Q2-7785 and the like.
  • the fluorine atom content ratio (atomic number fraction) of the fluorinated silicone resin is generally several thousand ppm to several tens percent.
  • Non-fluorinated resin examples include silicone resins, polyolefin resins, acrylic resins and the like, and among these, resins containing fluorine atoms, particularly fluorinated silicone resins From the viewpoint of compatibility, silicone resins are preferred (in the present invention, silicone resins containing no fluorine atom may be referred to as "non-fluorinated silicone resins"). Further, as the non-fluorinated resin, either a curable one or a non-curable one may be used, or both may be used in combination.
  • curable fluorinated silicone resin functional groups capable of forming a crosslinked structure upon reaction (curing), such as an alkenyl group or a hydrosilyl group, are also bonded to the non-curable fluorinated silicone resin.
  • the curable non-fluorinated silicone resin may be a solvent type or a non-solvent type.
  • Specific examples of the curable non-fluorinated silicone resin include KNS-3051, KNS-320A, KNS-316, KNS-3002, KNS-3300, X-62-1387, and KS-3656 manufactured by Shin-Etsu Chemical Co., Ltd.
  • a heavy release additive may be added to the curable non-fluorinated silicone resin, for example, KS-3800 manufactured by Shin-Etsu Chemical Co., Ltd .; SD7292 manufactured by Toray Dow Corning Co., Ltd., BY24 -4980 etc. can be mentioned.
  • the above-mentioned curable non-fluorinated silicones may be used alone or in combination of two or more different ones. Adjusting the curing reaction, adjusting the viscosity of the coating solution of layer A, and further enhancing the wettability and reactivity of layer B by mixing two or more curable non-fluorinated silicones. Can. At that time, the non-solvent type silicones may be mixed with each other, or the solvent type silicones may be mixed with each other, or the non-solvent type silicone and the solvent type silicone may be mixed. In particular, when the film thickness of the A layer is increased in order to obtain a lighter release film, the solid concentration of the coating solution forming the A layer tends to be high.
  • the viscosity of the coating solution may be increased, which may cause problems such as deterioration of the coat appearance and increase in thickness unevenness. Therefore, by mixing the non-solvent type silicone and the solvent type silicone, the viscosity of the coating solution can be reduced, and an A layer having a good coat appearance and a small thickness deviation can be formed.
  • the "solvent-free silicone” is a silicone having a viscosity that can be applied without dilution in a solvent, is composed of short polysiloxane chains, and is a silicone having a relatively low molecular weight.
  • the viscosity of the solvent-free silicone is preferably less than 1000 mPa ⁇ s alone when it is 100% concentration, and more preferably 50 mPa ⁇ s or more or 900 mPa ⁇ s or less, and more preferably 80 mPa ⁇ s or more or 800 mPa ⁇ s. It is further preferred that
  • solvent-type silicone is a silicone having a viscosity high enough to be coated unless diluted with a solvent, and is a silicone having a relatively high molecular weight.
  • the viscosity of the solvent type silicone is preferably 1000 mPa ⁇ s or more when made into a 30% toluene solution, and more preferably 2000 mPa ⁇ s or more and 20000 mPa ⁇ s or less, and more preferably 3000 mPa ⁇ s or more or 18000 mPa ⁇ s or less It is further preferred that
  • the controllability of the curing reaction can be improved, and sufficient flexibility is also imparted to the A layer, and The storage stability of the laminate laminated with the pressure-sensitive adhesive layer also becomes good.
  • the non-curable non-fluorinated silicone resin it is possible to use the non-fluorinated silicone resin listed above without specifically limiting the silicone resin having no reactive functional group.
  • organopolysiloxanes represented by the following general formula (I) are preferable.
  • the mass mixing ratio of the curable silicone resin (total of fluorinated and non-fluorinated) and non-curable non-fluorinated silicone resin is preferably in the range of 1: 1000 to 1000: 1, 1: 100 to It is more preferably in the range of 100: 1, and still more preferably in the range of 1:50 to 50: 1. Particularly preferred is in the range of 1:20 to 20: 1, and preferably 1: 1 to 20: 1.
  • the film thickness of the layer A is preferably 10 nm to 100 ⁇ m, more preferably 20 nm to 10 ⁇ m, and still more preferably 50 nm to 1 ⁇ m.
  • a particularly preferable range is 80 nm or more and 800 nm or less.
  • B layer (release layer) ⁇ Configuration of layer B>
  • a resin containing a fluorine atom similar to that described in the above-mentioned A layer (undercoat layer) can be used in the same manner.
  • a fluorinated silicone resin is preferable, and in particular, a curable fluorinated silicone resin is preferable.
  • a curable fluorinated silicone resin for the B layer (releasing layer) a releasing film having stable releasability with respect to the silicone pressure-sensitive adhesive layer can be obtained.
  • the layer B may be formed of a curable fluorinated silicone resin alone, or a mixture of a plurality of materials may be used, such as mixing with a curable non-fluorinated silicone resin.
  • the coating solution for forming the layer B particularly preferably contains a fluorine-containing solvent containing a fluorine atom for the purpose of enhancing the wettability to the layer A.
  • the thickness of the layer B is too thin, the effects of the present invention may be difficult to obtain, while if it is too thick, it may be difficult to obtain an increase in the effect commensurate with the increase in the amount of material used. . 5 nm or more is preferable, as for the minimum of the film thickness of B layer, 10 nm or more is more preferable, and 20 nm or more is especially preferable. Moreover, 50 micrometers or less are preferable, as for the upper limit, 1 micrometer or less is more preferable, and 500 nm or less is especially preferable.
  • the B layer (releasing layer) is formed on the A layer (undercoat layer).
  • the material suitable for the layer B is the same as that described in the description of the layer A, but from the viewpoint of adhesion and light removability, the fluorine atom content ratio per unit volume contained in the layer B is It is necessary to include more than A layer.
  • the lower limit of the fluorine atom content ratio (atomic number fraction) contained in the layer B measured by the SIMS method or the like is preferably 3,000 ppm or more, more preferably 5,000 ppm or more, 10,000 ppm or more is more preferable, and 20,000 ppm or more is particularly preferable.
  • the upper limit is not particularly limited, but is preferably 900,000 ppm or less, more preferably 800,000 ppm or less, and particularly preferably 700,000 ppm or less.
  • the fluorine atom content ratio of the layer B can be confirmed by, for example, the surface of the release layer of the laminated film by secondary ion mass spectrometry (SIMS method) or X-ray photoelectron spectroscopy (XPS method).
  • the fluorine atom content ratio of the layer B can also be quantified by using a material (fluorinated silicone etc.) known in advance as the fluorine atom content ratio as a reference. In the case of confirmation by the XPS method, the ratio of fluorine to all elements except hydrogen and helium was taken as the fluorine atom content ratio.
  • the fluorine atom content ratio in the layer has a sloped structure in the thickness direction in one lamination step (tilted composition
  • a resin containing fluorine atoms and a resin not containing fluorine atoms are diluted in a solvent to form a coating solution, and the coating solution is coated on at least one surface of a polymer film and dried to obtain a resin containing fluorine atoms.
  • the surface side in the layer is a layer B and the side of a polymer film is an layer A, and if they have substantially the same structure, they are included in the present invention.
  • the layer A and the layer B into a sloped structure, it is also expected to improve the adhesion of the interface between the layer A and the polymer film and the interface between the layer A and the layer B.
  • the fluorine atom content ratio of the B layer surface can be increased, the light releasability may be further improved while suppressing the content of the resin containing a fluorine atom in the entire laminated film to a low level.
  • the content ratio is the silicone which is the base material of each layer It is preferable to have a specific relationship with the content ratio of methyl siloxane ion (CH 3 SiO 2 ⁇ ) of the resin. That is, the ratio ([F ⁇ ] / [CH 3 SiO 2 ⁇ ]) of the fluorine ion content ratio to the methyl siloxane ion content ratio contained in the B layer calculated by SIMS method etc. (hereinafter, “fluorine atom content ratio” Is abbreviated to be greater than the fluorine atom content ratio of the A layer.
  • the fluorine atom content ratio of each of the layer A and the layer B is preferably 1 or more and 1,000 or less in the layer A and 3 or more and 5,000 or less in the layer B.
  • the lower limit of the fluorine atom content ratio of the layer B is preferably 5 or more, more preferably 10 or more, and still more preferably 20 or more. Further, the upper limit thereof is preferably 3,000 or less, and more preferably 1,000 or less.
  • the fluorine atom content ratio of the layer B is preferably 1.1 times or more, more preferably 1.5 times or more, of the fluorine atom content ratio of the layer A from the viewpoint of light removability with the silicone pressure-sensitive adhesive layer. It is more preferably 2 times or more, particularly preferably 3 times or more, and most preferably 5 times or more.
  • the upper limit is not particularly limited, but it is preferably 1000 times or less, more preferably 100 times or less from the viewpoint of the adhesion between layer A and layer B.
  • the fluorine atom content ratio (atomic number fraction) in the layer B is 1 of the fluorine atom content ratio (atomic number fraction) in the layer A from the viewpoint of light removability with the silicone pressure-sensitive adhesive layer.
  • the ratio is preferably 1 or more, more preferably 1.5 or more, still more preferably 2 or more, particularly preferably 3 or more, and most preferably 5 or more.
  • the upper limit is not particularly limited, but it is preferably 1000 times or less, more preferably 100 times or less from the viewpoint of the adhesion between layer A and layer B.
  • fluorine atom content ratio (atomic number fraction) means the ratio of fluorine atoms to the layer concerned.
  • each of layer A and layer B is substantially composed of silicone resin (including fluorinated, non-fluorinated and curable, non-curable), the above-mentioned “fluorine atom content ratio” and With respect to the “fluorine atom content ratio (atomic number fraction)”, the ratio of the layer A to the layer B is a similar value.
  • the fluorine atom content ratio of the layer B By setting the fluorine atom content ratio of the layer B to the above range, sufficient adhesion is obtained between the layer A and the layer B, and good peelability between the layer B and the silicone pressure-sensitive adhesive layer is expressed. Can. Further, when the fluorine atom content ratio and / or the fluorine atom content ratio of the layer B is higher than that of the layer A, sufficient adhesion between the layer A and the layer B can be obtained, and the layer B and the silicone pressure-sensitive adhesive layer are good. Peelability can be stably expressed.
  • the fluorine atom content ratio or fluorine atom content ratio of the layer A or layer B can be calculated by structural analysis of the coating agent by nuclear magnetic resonance spectrum (NMR) method, or secondary ion may be formed after layer formation. It can be quantified by mass spectrometry (SIMS method) or X-ray electron spectroscopy (XPS method). In the measurement by the SIMS method or the XPS method, the fluorine atom content ratio of each layer can also be quantified on the basis of a material (fluorinated silicone etc.) in which the fluorine atom content ratio is known in advance.
  • NMR nuclear magnetic resonance spectrum
  • XPS method X-ray electron spectroscopy
  • the fluorine atom content ratio per unit volume divided by the volume of the layer A may be the fluorine atom content ratio of each of the A layer and the B layer.
  • the coating solution having the curable non-fluorinated silicone resin and the curable fluorinated silicone resin contain a crosslinking agent, a catalyst, and a reaction initiator (reaction accelerator) .
  • a crosslinking agent and a catalyst may be contained from the beginning.
  • a crosslinking agent be included to react with reactive functional groups contained in the resin to form a crosslinked structure.
  • the crosslinking agent include vinyl siloxane and organosiloxane having a hydrosiloxane moiety.
  • Specific examples of the crosslinking agent include SP7297, 7560, 3062A, 3062B, 3062C, 3062D, etc. manufactured by Toray Dow Corning.
  • the crosslinking agent may contain a site having a fluorine substituent, or a silane coupling agent having a fluorinated substituent may be used.
  • a catalyst that accelerates the addition type reaction be contained, and among them, a platinum catalyst is preferably contained.
  • platinum catalysts include chloroplatinic acid, alcohol solutions of chloroplatinic acid, complexes of chloroplatinic acid and olefin, platinum-based compounds such as complexes of chloroplatinic acid and alkenyl siloxane, platinum black, platinum-supported silica, platinum-supported activated carbon Is illustrated.
  • the platinum catalyst may be used alone or in combination of two or more.
  • catalysts include CAT PL-50T manufactured by Shin-Etsu Chemical Co., Ltd., SRX 212 manufactured by Toray Dow Corning Co., Ltd., SRX 212 P, NC-25, FS XK-3077 and the like.
  • Examples of other additives that can be added to layer A and layer B include (meth) acrylic acid alkyl esters having 1 to 20 carbon atoms in the ester group, acrylic resins, olefin resins, and the like. Among them, silane coupling agents having a fluorinated substituent are preferable.
  • the normal-state peeling force of the laminated film of the present invention is preferably 100 mN / cm or less.
  • the lower the normal-state peeling power the smaller the force required for peeling from the pressure-sensitive adhesive layer. Therefore, the release film is peeled from the laminate on which the pressure-sensitive adhesive layer is laminated, and defects such as peeling failure in the production process such as sticking the pressure-sensitive adhesive layer to various members and deformation of the pressure-sensitive adhesive layer are suppressed.
  • the laminate film of the present invention can suppress the above problems and have low releasability even if it is a pressure-sensitive adhesive layer having strong adhesiveness such as a silicone pressure-sensitive adhesive. Moreover, it is possible to prevent the phenomenon in which the release film on the unintended side peels off in a laminate having release films on both sides of the pressure-sensitive adhesive layer as the release film. From this point of view, the normal peel force is preferably 70 mN / cm or less, more preferably 40 mN / cm or less, particularly preferably 35 mN / cm or less, and most preferably 30 mN / cm or less. preferable.
  • the lower limit is not particularly limited, but it is preferably 1 mN / cm or more, more preferably 3 mN / cm or more, from the viewpoint of storage stability of a laminate obtained by laminating a laminate film and an adhesive layer.
  • normal-state peeling force shall be measured by the method as described in the Example mentioned later.
  • the laminate film of the present invention may have a configuration in which an A layer is provided on one side or both sides of a polymer film, and a B layer is provided on the A layer. Also, if necessary, another layer may be interposed between the polymer film and the A layer, or between the A layer and the B layer. Other layers may include an antistatic layer having antistatic properties, an oligomer sealing layer for sealing a compound on the film surface and bleeding of an oligomer (bleed, plate out), and the like.
  • the layers such as the antistatic layer and the oligomer sealing layer may be formed either by in-line coating, which is simultaneously formed with a polymer film, or off-line coating, which is separately formed on the formed polymer film. Can be adopted.
  • the total thickness of the laminated film in the present invention is preferably 5 ⁇ m or more and 1250 ⁇ m or less, more preferably 10 ⁇ m or more and 500 ⁇ m or less, and still more preferably 10 to 200 ⁇ m or less.
  • the method for producing a polyester film will be described by way of example.
  • a method for producing the polyester film used in the present invention it is preferable to use a polyester raw material such as the above-mentioned polyethylene terephthalate, and to solidify the molten sheet extruded from the die by cooling with a cooling roll to obtain an unstretched sheet.
  • a polyester raw material such as the above-mentioned polyethylene terephthalate
  • a cooling roll to obtain an unstretched sheet.
  • the obtained unstretched sheet can be used as it is, but at least uniaxial stretching is preferable, and biaxial stretching is more preferable.
  • when using as a release film when laminating
  • the stretching conditions are also not particularly limited, and for example, the unstretched sheet is stretched 2 to 6 times at 70 to 145 ° C.
  • layer A and layer B Formation of layer A (undercoat layer) and layer B (release layer)
  • the method for forming layer A and layer B is not limited, and may be formed by coextrusion or the like. Is preferred.
  • the number of times of application of the layer A and the layer B may be one, or two or more. In the case of forming the layer A and the layer B by setting the number of times of application twice or more, different coating solutions may be applied. However, it is necessary that at least one of the coating solutions contains a fluorine atom.
  • the coating method may be in-line coating or off-line coating, and, for example, a coating method as shown in "Coating method" (Yuji Harazaki, published by Tsuji Shoten, 1979) can be used.
  • a coating head air doctor coater, blade coater, rod coater, knife coater, squeeze coater, impregnating coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, cast coater, spray coater, curtain coater, calendar coater And extrusion coaters and the like.
  • the coating solution for forming the layer B preferably contains a fluorine solvent having a fluorine atom for the purpose of enhancing the wettability to the layer A.
  • alcohols such as ethanol and (iso) propyl alcohol, methyl acetate, ethyl acetate, ethyl acetate (iso) propyl, acetate (iso) butyl acetate, esters of acetate (iso) pentyl acetate, ethyl lactate, ethyl benzoate and the like , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol, diisobutyl ketone, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc.
  • Glycols N-methyl-2-pyrrolidone, N, N-dimethylformamide, tetrahydrofuran, acetonitrile and the like.
  • nonpolar solvents include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane and octane, hydrocarbons having a branched structure such as isohexane, isooctane and isononane, cyclohexane and cyclo Examples thereof include alicyclic hydrocarbons such as heptane and cyclooctane, and dioxane.
  • fluorine solvent hydrofluoroethers, metaxylene hexafluoride, tridecafluorooctane and the like can be mentioned.
  • a method for forming these layers there is exemplified a method of preparing a coating liquid having a fluorine atom content ratio corresponding to each layer after coating and drying as a coating liquid, and using the same. it can.
  • a curable non-fluorinated silicone resin is mixed with a predetermined amount of a fluorinated material to prepare a coating solution having a composition corresponding to the A layer / B layer, and then applied and dried. It is possible to form an A layer and / or a B layer containing a desired fluorine atom.
  • This method is preferable because a release film having a predetermined fluorine atom content ratio A layer / B layer can be produced more easily.
  • the layer A and the layer B can be formed by coating and drying the layer A and then coating and drying the layer B.
  • the layer B is coated following the coating of the layer A. Then, it can be formed by a wet coating method in which drying is performed thereafter, which can also be expected to shorten the production process and improve energy efficiency.
  • layer A is formed by applying a mixture of a curable fluorinated silicone resin and a curable non-fluorinated silicone resin, and then a solution comprising a curable fluorinated silicone resin as a main component as layer B
  • a non-fluorinated resin can be previously formed by coating and then a fluorinated layer can be formed by a dry process such as carbon tetrafluoride (CF 4 ) plasma treatment.
  • CF 4 carbon tetrafluoride
  • both A layer and B layer may be in-line coating, or only A layer may be in-line coating
  • the layer B may be coated off-line.
  • both the layer A and the layer B are provided by off-line coating, even if they are continuously formed in one "substrate film unwinding-rewinding step", a plurality of "substrate film unwinding--"
  • the former may be sequentially formed through the winding process, but the former is a particularly preferable method because the manufacturing process becomes simple and the manufacturing cost can be reduced.
  • the amount of heat applied to the film at the time of forming the A layer lower than the amount of heat applied at the time of forming the B layer, it is possible to suppress the deterioration of film planarity at the time of forming the B layer, and also the occurrence of coating unevenness of the B layer. It is preferable because it can be effectively prevented.
  • the laminated film of the present invention has excellent releasability, it can be provided, for example, as a laminated film-attached pressure-sensitive adhesive sheet having a configuration formed by laminating the laminated film and the adhesive layer.
  • the laminated film of the present invention has excellent releasability even for a silicone adhesive having strong adhesiveness, for example, a structure formed by laminating the laminate film and an adhesive layer made of a silicone adhesive.
  • the method of using the laminated film is not limited to such a method of use.
  • the print is excellent in water resistance, water repellency, oil resistance, oil repellency, antifogging, antifouling, chemical resistance, corrosion resistance, etc.
  • Substrates, optical member protective films, films for construction materials, films for agriculture, highly water repellent films, films for packaging, cosmetic films, surface protective films and the like can be mentioned.
  • an adhesive layer, an adhesive layer, a heat seal layer, etc. may be provided on the polymer film on the side opposite to the side having the A layer and the B layer. .
  • a silicone adhesive As a silicone adhesive, an addition reaction type, a peroxide curing type, or a condensation reaction type silicone adhesive etc. are mentioned, for example. Among them, from the viewpoint of being curable in a low temperature and short time, an addition reaction type silicone pressure sensitive adhesive is preferably used. These addition reaction type silicone pressure sensitive adhesives are cured when forming the pressure sensitive adhesive layer on the support.
  • the silicone adhesive may contain a catalyst such as a platinum catalyst.
  • the above-mentioned addition reaction type silicone pressure-sensitive adhesive is coated on a support after stirring the silicone resin solution diluted with a solvent such as toluene, if necessary, uniformly by adding a catalyst such as a platinum catalyst.
  • a crosslinker, an additive for controlling adhesion, or the like may be added to the addition reaction type silicone pressure-sensitive adhesive, or the support may be subjected to a primer treatment before the formation of the pressure-sensitive adhesive layer. It is also good.
  • silicone resins used for the addition reaction type silicone adhesive include SD4580PSA, SD4584PSA, SD4585PSA, SD4587LPSA, SD4560PSA, SD4570PSA, SD4600FCPSA, SD4593PSA, DC7651ADHESIVE, DC7652ADHESIVE, LTC-755, LTC-310 (all of which are Toray Dow) Corning Inc.), KR-3700, KR-3701, X-40-3237-1, X-40-3240, X-40-3291-1, X-40-3229, X-40-3323, X-40 -3306, X-40-3270-1 (all from Shin-Etsu Chemical Co., Ltd.), AS-PSA001, AS-PSA002, AS-PSA003, AS-PSA004, AS-PSA 05, AS-PSA012, AS-PSA014, PSA-7465 (all manufactured by Arakawa Chemical Industries, Ltd.), TSR1512, TSR1516, TSR1521 (all planned by
  • etching with Ar gas (voltage: 5 kV, current: 2 nA, etching rate: 20 nm / min (PET film conversion)) is performed for 0 min, 1 min, 2 min, 3 min, Fluorine atom content ratio per unit volume (“F ⁇ ” / “CH 3 ”) obtained by averaging the ratio of the counts of anions (“F ⁇ ” and “CH 3 SiO 2 ⁇ ”) detected during the etching time of SiO 2 - ”) and the.
  • the value of [the fluorine atom content ratio of the layer B] / [the fluorine atom content ratio of the layer A] was taken as the ratio of the fluorine atom content ratio.
  • This value has the same meaning as the result of calculating the ratio of the values of each layer by measuring the fluorine atom content ratio (atomic number fraction) of each of layer A and layer B using XPS.
  • ⁇ Coating solution 1 composition Addition type organosilicone (Shin-Etsu Chemical Co., Ltd., KS-847): 67 parts by mass Platinum catalyst (Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 0.7 parts by mass Addition type fluorinated silicone (Toray Dow Corning Co., Ltd.) Syl-off 3062): 100 parts by mass Crosslinking agent (Toray Dow Corning, Syl-off 3062A): 0.5 parts by mass Platinum catalyst (Toray Dow Corning, FSX K-3077): 0.5 parts Department
  • ⁇ Coating solution 2 composition Addition type fluorinated silicone (Shin-Etsu Chemical Co., Ltd., X-70-201S): 100 parts by mass Platinum catalyst (Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 0.5 parts by mass
  • a PET film ("T100-38" manufactured by Mitsubishi Chemical Corporation, 38 ⁇ m thick) is used as a polymer film, and the coating solution 1 is coated on the polymer film by a bar coater (No. 4 bar), in an oven at 150 ° C. For 30 seconds to cure the resin of layer A, and a polymer film having layer A (undercoat layer) was formed.
  • the coating solution 2 is further applied by a bar coater (No. 4 bar) on the layer A of the polymer film having the layer A (undercoat layer), and dried in an oven at 150 ° C. for 30 seconds to obtain a resin of the layer B Was cured to produce a laminated film in which the B layer (release layer) was provided on the A layer (undercoat layer).
  • Example 2 A laminated film was produced in the same manner as in Example 1 except that the solid content concentration of the coating solution 2 was 4% by mass. In addition, since the coating liquid 2 is apply
  • Comparative Example 1 A polymer film was prepared in substantially the same manner as in Example 1, except that only the coating solution 2 was applied by a bar coater (No. 4 bar) without forming the layer A (undercoat layer) on the polymer film. A laminated film consisting only of B and B layers (releasing layers) was produced.
  • Comparative Example 2 A laminated film was produced in the same manner as in Comparative Example 1 except that the solid content concentration of the coating solution 2 was 4% by mass. In addition, since the coating liquid 2 is apply
  • Comparative Example 3 In the same manner as in Example 1 except that the layer B (releasing layer) was not formed without applying the coating solution 2 on the layer A (undercoat layer), substantially a polymer film and A laminated film consisting only of layer A (undercoat layer) was produced.
  • Coating solution 3 was prepared with the following composition.
  • ⁇ Coating solution 3 composition> Addition type organosilicone (Shin-Etsu Chemical Co., Ltd., KS-847H): 67 parts by mass Platinum catalyst (Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 0.7 parts by mass
  • the coating solution 3 was coated on a polymer film by a bar coater (No. 4 bar) and dried in an oven at 150 ° C. for 30 seconds to provide an A layer (undercoat layer). Next, it was tried to apply the coating solution 2 by a bar coater (No. 4 bar) on the layer A (undercoat layer). However, the coating solution 2 is not uniformly applied on the layer A (undercoat layer), and a phenomenon (repelling) occurs in the form of spots or lines (mesh), so that the layer B (release layer) could not form.
  • Comparative Example 5 With regard to the B layer (release layer), a laminated film was to be produced in the same manner as in Comparative Example 4 except that the solid content concentration of the coating liquid 2 was 4 mass%. However, the “coating solution 2” is not uniformly applied on the layer A (undercoat layer), and a phenomenon (repelling) occurs in the form of spots or lines (mesh), so that the layer B (release layer) ) could not form.
  • ⁇ Coating solution 4 composition> Addition type organosilicone (Shin-Etsu Chemical Co., Ltd., KS-847): 133 parts by mass Platinum catalyst (Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 1.3 parts by mass Addition type fluorinated silicone (Toray Dow Corning Co., Ltd.) Syl-off 3062): 100 parts by mass Crosslinking agent (Toray Dow Corning, Syl-off 3062A): 0.5 parts by mass Platinum catalyst (Toray Dow Corning, FSX K-3077): 0.5 parts Department
  • a laminated film was produced in the same manner as in Example 3 except that the coating solution 5 was applied instead of the coating solution 4 to form a layer A (undercoat layer) on the polymer film.
  • ⁇ Coating solution 6 composition Addition type organosilicone (Shin-Etsu Chemical Co., Ltd., KS-847): 267 parts by mass Platinum catalyst (Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 2.0 parts by mass Addition type fluorinated silicone (Toray Dow Corning Co., Ltd.) Syl-off 3062): 100 parts by mass Crosslinking agent (Toray Dow Corning, Syl-off 3062A): 0.5 parts by mass Platinum catalyst (Toray Dow Corning, FSX K-3077): 0.5 parts Department
  • a laminated film was produced in the same manner as in Example 3, except that the coating solution 6 was applied instead of the coating solution 4 to form a layer A (undercoat layer) on the polymer film.
  • the thickness of the layer B (releasing layer) is formed thin (the concentration of the coating solution 2 is “0.5 mass%”), compared to the example 1
  • the releasability of the same level as that of the release film of Example 2 (the concentration of the coating solution 2 is “4% by mass”) in which the layer B (release layer) is thick is obtained. From this, it has been found that it is possible to produce a release film having excellent releasability to a silicone adhesive with a smaller amount of fluorine-based material.
  • the release films of Examples 3 to 5 in which the fluorine atom content ratio of the layer A (undercoat layer) is smaller than that of Example 1 also provide the same level of releasability as the release film of Example 1. It has been found that it is possible to produce a release film having excellent releasability with respect to a silicone pressure sensitive adhesive, with a smaller amount of fluorine-based material.
  • the fluorine atom content ratio by TOF-SIMS is measured for the samples of Comparative Example 3 (only A layer) and Comparative Example 2 (only B layer), It is the value of the layer. As a result, it was confirmed that the content of fluorine atoms per unit volume was higher in layer B than in layer A. In addition, since the composition of the coating liquid is the same, this value was used as the value of the fluorine atom content ratio of each layer in Examples 1 and 2 and Comparative Example 1. Furthermore, the fluorine atom content ratio of the layer A in Examples 3 to 5 was calculated from the raw material composition ratio based on the value of the fluorine atom content ratio in Example 1.
  • the fluorine atom content of layer A is the largest on the surface (etching time 0 minutes in TOF-SIMS) and decreases as the etching time becomes longer (that is, the closer to the substrate PET film side), the fluorine on the surface side It is considered that a graded structure in which the atomic content ratio increases is formed.
  • the values shown in Table 1 are average values in the thickness direction.

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PCT/JP2018/045230 2017-12-11 2018-12-10 積層フィルム、離型フィルムおよび積層体 WO2019117059A1 (ja)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020121687A1 (ja) * 2018-12-11 2020-06-18 三菱ケミカル株式会社 離型フィルム
WO2021019845A1 (ja) * 2019-07-29 2021-02-04 三菱ケミカル株式会社 離型フィルム、フィルム積層体、これらの製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102459382B1 (ko) * 2021-03-05 2022-10-26 도레이첨단소재 주식회사 이형필름

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0577364A (ja) * 1991-09-24 1993-03-30 Lintec Corp 剥離シート
JP2005022382A (ja) * 2003-07-03 2005-01-27 Mitsubishi Plastics Ind Ltd フッ素系積層フィルム
JP2005047132A (ja) * 2003-07-28 2005-02-24 Mitsubishi Plastics Ind Ltd 離型用積層フィルム及びその製造方法
WO2005115751A1 (ja) * 2004-05-27 2005-12-08 Mitsubishi Plastics, Inc. 離型用積層フィルム

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0850999A3 (en) * 1996-12-30 1998-12-02 Dow Corning Corporation Silicone release coating compositions
US20050038183A1 (en) 2003-08-14 2005-02-17 Dongchan Ahn Silicones having improved surface properties and curable silicone compositions for preparing the silicones
BR112012011534A2 (pt) 2009-11-16 2016-06-28 3M Innovative Properties Co materiais de liberação de blenda de fluorossilicone
JP5472997B2 (ja) 2010-03-24 2014-04-16 信越ポリマー株式会社 離型用フィルム
EP3083857B1 (en) 2013-12-16 2024-05-15 3M Innovative Properties Company Blended release materials
WO2016174713A1 (ja) * 2015-04-27 2016-11-03 株式会社寺岡製作所 離型用粘着テープ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0577364A (ja) * 1991-09-24 1993-03-30 Lintec Corp 剥離シート
JP2005022382A (ja) * 2003-07-03 2005-01-27 Mitsubishi Plastics Ind Ltd フッ素系積層フィルム
JP2005047132A (ja) * 2003-07-28 2005-02-24 Mitsubishi Plastics Ind Ltd 離型用積層フィルム及びその製造方法
WO2005115751A1 (ja) * 2004-05-27 2005-12-08 Mitsubishi Plastics, Inc. 離型用積層フィルム

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020121687A1 (ja) * 2018-12-11 2020-06-18 三菱ケミカル株式会社 離型フィルム
CN113015623A (zh) * 2018-12-11 2021-06-22 三菱化学株式会社 脱模膜
EP3895891A4 (en) * 2018-12-11 2022-04-27 Mitsubishi Chemical Corporation RELEASE FILM
CN113015623B (zh) * 2018-12-11 2023-09-15 三菱化学株式会社 脱模膜
WO2021019845A1 (ja) * 2019-07-29 2021-02-04 三菱ケミカル株式会社 離型フィルム、フィルム積層体、これらの製造方法
EP4005792A4 (en) * 2019-07-29 2022-08-31 Mitsubishi Chemical Corporation MOLD RELEASE FILM, FILM LAMINATE, METHOD OF MAKING A MOLD RELEASE FILM AND METHOD OF MANUFACTURING A FILM LAMINATE

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