WO2022191328A1 - Film et son procédé de production, film stratifié et affichage - Google Patents

Film et son procédé de production, film stratifié et affichage Download PDF

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Publication number
WO2022191328A1
WO2022191328A1 PCT/JP2022/011069 JP2022011069W WO2022191328A1 WO 2022191328 A1 WO2022191328 A1 WO 2022191328A1 JP 2022011069 W JP2022011069 W JP 2022011069W WO 2022191328 A1 WO2022191328 A1 WO 2022191328A1
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Prior art keywords
film
group
carbon atoms
film according
layer
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PCT/JP2022/011069
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English (en)
Japanese (ja)
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祐介 田口
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株式会社カネカ
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Priority to JP2023505659A priority Critical patent/JPWO2022191328A1/ja
Publication of WO2022191328A1 publication Critical patent/WO2022191328A1/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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/20—Layered products comprising a layer of natural or synthetic rubber comprising silicone rubber
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings

Definitions

  • the present invention relates to a single-layer film made of a cured composition and its application.
  • Patent Literature 1 and Patent Literature 2 propose the use of a hard coat film in which a hard coat layer made of a cured product of a curable resin composition is provided on a film substrate as a cover window material for a display. .
  • foldable displays Curved displays and foldable displays (foldable displays) are being developed, and the cover windows of these displays are required to be flexible in addition to surface hardness. Furthermore, foldable displays are required to have excellent resilience so that bending marks are less likely to remain on the bent portion when the screen is flattened from a bent state.
  • a hard-coated film in which a hard-coated layer is provided in contact with the film substrate, tends to leave bending marks and has problems with resilience.
  • An object of the present invention is to provide a film having excellent folding restorability.
  • One embodiment of the present invention is a single-layer film consisting of a cured product layer of a composition containing a polyorganosiloxane compound having an epoxy group.
  • the thickness of the film may be 40-120 ⁇ m.
  • a polyorganosiloxane compound having an epoxy group is a condensate of a silane compound represented by the following general formula (1). YR 1 -(Si(OR 2 ) x R 3 3-x ) (1)
  • R 1 is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms
  • R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 3 is a hydrogen atom; or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms and an aralkyl group having 7 to 12 carbon atoms
  • x is an integer of 2 or 3
  • Y is a glycidyloxy group or an alicyclic epoxy group.
  • R 1 may be a substituted or unsubstituted alkylene group having 1 to 3 carbon atoms, and Y may be an alicyclic epoxy group.
  • R 1 may be a substituted or unsubstituted alkylene group having 4 to 16 carbon atoms and Y may be a glycidyloxy group.
  • the above single-layer film is formed by applying a composition containing a polyorganosiloxane compound on a substrate and then irradiating an active energy ray to cure the composition on the substrate to form a cured product layer, from the substrate It is obtained by peeling off the cured product layer.
  • the substrate preferably has a water contact angle of 74 to 107° on the surface to which the composition is applied.
  • a laminated film may be formed by bonding a film composed of the above-mentioned cured product layer to another transparent resin film via an adhesive layer.
  • a double-sided pressure-sensitive adhesive sheet is preferable as the adhesive layer for bonding the film composed of the cured product layer and the transparent resin film.
  • the thickness of the transparent resin film may be 50 ⁇ m or less.
  • the above film and laminated film can be used as a cover window arranged on the viewing side surface of the image display panel.
  • the display may be a foldable display that can be folded.
  • the above films are less likely to leave bending marks and have excellent bending restoration properties.
  • FIG. 2 is a cross-sectional view of a laminate in which a cured product layer is adhered and laminated on a base material; It is a figure which shows the state which peeled the base material and hardened material layer of the laminated body of FIG. It is a sectional view of a layered product of one embodiment.
  • One embodiment of the present invention is a single-layer film composed of a cured product layer obtained by curing a curable composition.
  • a curable composition By coating the curable composition on the substrate 1 and curing the composition, as shown in FIG. can get.
  • a film 3 composed of a single cured material layer not laminated with other films or the like is obtained as shown in FIG.
  • the curable composition contains a polyorganosiloxane compound containing epoxy groups as a curable resin component.
  • a polyorganosiloxane compound containing epoxy groups as a curable resin component.
  • Such curable compositions are disclosed in WO2014/204010, WO2016/098596, WO2018/096729, WO2020/040209, JP-A-2016-193956, JP-A-2017-8142, and the like. , these descriptions can be referred to and incorporated.
  • the curable composition preferably contains a photocationic polymerization initiator in addition to the polyorganosiloxane compound as a curable resin component.
  • a polyorganosiloxane compound having an epoxy group is obtained by condensation of a silane compound having an epoxy group.
  • silane compound A silane compound having an epoxy group is represented by the following general formula (1). YR 1 -(Si(OR 2 ) x R 3 3-x ) (1)
  • R 1 is a substituted or unsubstituted alkylene group having 1 to 16 carbon atoms.
  • R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • R 3 is a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms and an aralkyl group having 7 to 12 carbon atoms.
  • x is an integer of 2 or 3;
  • Y is a monovalent organic group containing an epoxy group.
  • the silane compound represented by general formula (1) has two or three (--OR 2 ) in one molecule, and Si--OR 2 is hydrolyzable. After hydrolysis of Si--OR 2 , it is condensed to form a polyorganosiloxane compound which is a condensate of a silane compound.
  • R 1 examples include methylene, diethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, and hexadecamethylene.
  • Examples include unsubstituted linear alkylene such as methylene group.
  • R 1 may further have a substituent having 1 to 6 carbon atoms. Examples of substituents include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, phenyl group and the like. From the viewpoint of the flexibility of the cured product, R 1 is preferably unsubstituted linear alkylene.
  • the number of carbon atoms (alkylene chain length) of R 1 may affect the hardness and flexibility of the cured film. If the number of carbon atoms is 17 or more, the surface hardness of the cured film tends to decrease. From the viewpoint of increasing surface hardness such as pencil hardness, R 1 preferably has 1 to 3 carbon atoms. On the other hand, R 1 preferably has 4 to 16 carbon atoms from the viewpoint of enhancing the bending resistance and bending recovery of the cured film.
  • R 2 is preferably an alkyl group, specific examples of which include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl group, cyclohexyl group, ethylhexyl group, and the like.
  • R2 is preferably a methyl group, an ethyl group or a propyl group, most preferably a methyl group.
  • R 3 is a hydrocarbon group
  • specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, and isobutyl. group, cyclohexyl group, ethylhexyl group, benzyl group, phenyl group, tolyl group, xylyl group, naphthyl group, phenethyl group and the like.
  • x is 3 in the general formula (1), the silane compound does not have R3.
  • organic group Y containing an epoxy group examples include a glycidyloxy group represented by the following formula and an alicyclic epoxy group.
  • a 3,4-epoxycyclohexyl group is preferred as the alicyclic epoxy group.
  • Y is an alicyclic epoxy group
  • the cured film tends to have high surface hardness.
  • Y is a glycidyloxy group
  • the cured product tends to be excellent in flexibility.
  • R 1 in general formula (1) is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of increasing the surface hardness of the cured film.
  • silane compounds in which R 1 is an alkylene group having 1 to 3 carbon atoms and Y is a 3,4-epoxycyclohexyl group include (3,4-epoxycyclohexyl)methyldimethoxy Silane, (3,4-epoxycyclohexyl)dimethylmethoxysilane, (3,4-epoxycyclohexyl)triethoxysilane, (3,4-epoxycyclohexyl)methyldiethoxysilane, (3,4-epoxycyclohexyl)dimethylethoxysilane , ⁇ (3,4-epoxycyclohexyl)methyl ⁇ trimethoxysilane, ⁇ (3,4-epoxycyclohexyl)methyl ⁇ methyldimethoxysilane, ⁇ (3,4-epoxycyclohexyl)methyl ⁇ dimethylmethoxysilane, ⁇ (3, 4-epoxycyclo
  • R 1 in the general formula (1) is preferably an alkylene group having 4 to 16 carbon atoms from the viewpoint of enhancing the flex resistance and folding restorability of the cured film.
  • the number of carbon atoms in R 1 is 4 or more, the distance between the epoxy group and the silicon atom is long. The membrane exhibits excellent flex resistance and bending recovery.
  • the number of carbon atoms in R 1 may be 6 or more or 8 or more. As described above, when the number of carbon atoms in R1 is excessively large, the surface hardness of the cured film tends to decrease.
  • the number of carbon atoms in R 1 is preferably 14 or less, more preferably 12 or less.
  • silane compounds in which R 1 is an alkylene group having 4 to 16 carbon atoms and Y is a glycidyloxy group include 4-glycidyloxybutyltrimethoxysilane and 4-glycidyloxybutyl methyldimethoxysilane, 4-glycidyloxybutyltriethoxysilane, 4-glycidyloxybutylmethyldiethoxysilane, 5-glycidyloxypentyltrimethoxysilane, 5-glycidyloxypentylmethyldimethoxysilane, 5-glycidyloxypentyltriethoxysilane, 5-glycidyloxypentylmethyldiethoxysilane, 6-glycidyloxyhexyltrimethoxysilane, 6-glycidyloxyhexylmethyldimethoxysilane, 6-glycidyloxyhexyltriethoxysilane, 6-glycidyloxyhex
  • Si--O--Si bonds are formed by hydrolysis and condensation of the Si--OR 2 moieties of the above-mentioned silane compounds to produce condensates of the silane compounds (polyorganosiloxane compounds). From the viewpoint of suppressing ring-opening of epoxy groups, it is preferable to carry out the reaction under neutral or basic conditions.
  • the weight average molecular weight of the polyorganosiloxane compound is preferably 500 or more. Also from the viewpoint of suppressing volatilization, the weight average molecular weight of the polyorganosiloxane compound is preferably 500 or more. On the other hand, if the molecular weight is excessively high, cloudiness may occur due to, for example, a decrease in compatibility with other components in the composition. Therefore, the weight average molecular weight of the polyorganosiloxane compound is preferably 20,000 or less.
  • the molecular weight of the polyorganosiloxane compound can be controlled by appropriately selecting the amount of water used in the reaction and the type and amount of catalyst. For example, the molecular weight can be increased by increasing the amount of water initially charged.
  • a structure forming a Si—O—Si bond (referred to as “SiO 3/2 body” or “T3 body”) and two of the three alkoxy groups undergo a condensation reaction to Si—O— It may include structures forming Si bonds (referred to as “SiO 2/2 bodies” or “T2 bodies”).
  • the polyorganosiloxane compound has a molar ratio of SiO 3/2 bodies to SiO 2/2 bodies: [SiO 3/2 bodies]/[SiO 2/2 bodies] of less than 5.
  • [SiO 3/2 body]/[SiO 2/2 body] may be 4 or less, 3 or less, or 2 or less, or may be 0.
  • neutral salt catalysts include salts composed of acids and bases, and salts composed of cations of alkali metals or alkaline earth metals and anions of halogens are preferred.
  • neutral salt catalysts include lithium chloride, sodium chloride, potassium chloride, beryllium chloride, magnesium chloride, calcium chloride, lithium bromide, sodium bromide, potassium bromide, beryllium bromide, magnesium bromide, bromide.
  • a plurality of silane compounds may be condensed.
  • a silane compound in which Y in general formula (1) is an alicyclic epoxy group and a silane compound in which Y in general formula (1) is a glycidyloxy group may be condensed.
  • a silane compound containing no epoxy group may be used. From the viewpoint of improving the mechanical strength of the cured film, the number of epoxy groups contained in one molecule of the polyorganosiloxane compound is preferably as large as possible.
  • the molar ratio of the silane compound having no epoxy group to the silane compound having an epoxy group is preferably 2 or less, more preferably 1 or less, further preferably 0.4 or less, and 0.2.
  • the following are particularly preferable, and 0 is acceptable.
  • the curable composition contains the above polyorganosiloxane compound as a curable resin component.
  • the curable composition preferably contains a photopolymerization initiator in addition to the polyorganosiloxane compound as the curable resin, and further contains a reactive diluent, a photosensitizer, particles and other solids (non-volatile matter). of additives.
  • the content of the polyorganosiloxane compound in the curable composition is preferably 40 parts by weight or more, more preferably 50 parts by weight or more, relative to the total solid content of 100 parts by weight. Preferably, 60 parts by weight or more is more preferable.
  • the curable composition preferably contains a photocationic polymerization initiator.
  • a photocationic polymerization initiator is a compound (photoacid generator) that generates an acid upon irradiation with an active energy ray. The acid generated from the photoacid generator causes the epoxy groups of the above polyorganosiloxane compound to react and cure through intermolecular cross-linking.
  • Photoacid generators include strong acids such as toluenesulfonic acid or boron tetrafluoride; onium salts such as sulfonium salts, ammonium salts, phosphonium salts, iodonium salts, and selenium salts; iron-allene complexes; silanol-metal chelate complexes.
  • sulfonic acid derivatives such as disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidosulfonates, and benzoinsulfonates; and organic halogen compounds.
  • the content of the photocationic polymerization initiator in the curable composition is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, relative to 100 parts by weight of the polyorganosiloxane compound.
  • the curable composition may contain a reactive diluent.
  • reactive diluents include cationically polymerizable compounds other than the above polyorganosiloxane compounds.
  • Polymerizable functional groups of the reactive diluent include epoxy groups, vinyl ether groups, oxetane groups, alkoxysilyl groups, and the like.
  • the content of the reactive diluent in the curable composition is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, relative to 100 parts by weight of the polyorganosiloxane compound.
  • the curable composition may contain a photosensitizer for the purpose of improving the photosensitivity of the photocationic polymerization initiator (photoacid generator).
  • a photosensitizer that can absorb light in a wavelength range that the photoacid generator itself cannot absorb is more efficient.
  • Photosensitizers include anthracene derivatives, benzophenone derivatives, thioxanthone derivatives, anthraquinone derivatives, benzoin derivatives and the like.
  • the content of the photosensitizer in the curable composition is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and even more preferably 10 parts by weight or less with respect to 100 parts by weight of the photoacid generator.
  • the curable composition may contain particles for the purpose of adjusting film properties such as surface hardness and flex resistance, and suppressing curing shrinkage.
  • the particles organic particles, inorganic particles, organic-inorganic composite particles, etc. may be appropriately selected and used.
  • the particles may be surface-modified, and polymerizable functional groups may be introduced by surface modification.
  • the average particle diameter of the particles is, for example, about 5 nm to 10 ⁇ m.
  • the content of the particles in the curable composition is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, relative to 100 parts by weight of the polyorganosiloxane compound.
  • the curable composition may be solventless or may contain a solvent. When a solvent is included, it is preferable that the solvent does not dissolve the polyimide film.
  • the content of the solvent in the curable composition is preferably 500 parts by weight or less, more preferably 300 parts by weight or less, and even more preferably 100 parts by weight or less based on 100 parts by weight of the polyorganosiloxane compound.
  • the curable composition may contain additives such as inorganic pigments, organic pigments, surface conditioners, surface modifiers, plasticizers, dispersants, wetting agents, thickeners and antifoaming agents.
  • the curable composition may also contain a thermoplastic, thermosetting or photocurable resin material other than the above polyorganosiloxane compound.
  • the curable composition may contain a radical polymerization initiator in addition to the photocationic polymerization initiator.
  • the curable composition is applied on one main surface 1A of the substrate 1, and the solvent is removed by drying if necessary, and then the curable composition is irradiated with an active energy ray to cure the composition.
  • a laminate 10 is obtained in which a cured film (cured product layer) 3 of a curable composition is adhered and laminated on a substrate 1 .
  • the cured layer 3 that is not laminated with other films or the like is obtained as a single layer film.
  • the substrate organic substances such as resins, ceramics represented by glass, and inorganic substances such as metals can be used, among which resin films are preferable.
  • the material of the resin film is not particularly limited, and polyester-based resin, polyolefin-based resin, polyamide-based resin, polyimide-based resin, urethane-based resin, (meth)acrylic-based resin, polycarbonate-based resin, cellulose-based resin, silicone-based resin, etc. mentioned.
  • polyester-based resins are preferred, and polyethylene terephthalate (PET) is particularly preferred.
  • the thickness of the substrate 1 is not particularly limited, and is, for example, 1 to 1000 ⁇ m, preferably 5 to 500 ⁇ m, more preferably 10 to 200 ⁇ m, even more preferably 15 to 150 ⁇ m.
  • the substrate 1 preferably has a water contact angle of 74 to 107° on the surface 1A to which the curable composition is applied.
  • the water contact angle of the surface 1A is more preferably 80-100°, more preferably 80-90°. If the water contact angle of the substrate 1 is too low, it tends to be difficult to separate the cured product layer 3 from the substrate 1 . If the water contact angle of the substrate 1 is excessively high, repelling is large when the curable composition is applied to the substrate, making it difficult to form a coating film, or during heating or curing, the coating film or curing may be difficult. The film tends to be difficult to handle due to spontaneous separation of the film from the substrate.
  • the surface 1A of the base material 1 to which the curable composition is applied may be coated in order to keep the contact angle within the above range.
  • the coating treatment include release treatment using a silicone-based release agent, a non-silicone release agent, an inorganic thin film, or the like. Surface treatments such as corona treatment and plasma treatment may be performed to control the water contact angle.
  • Surface 1B of substrate 1 may also be surface-treated.
  • the curable composition By applying the curable composition on the substrate 1 and irradiating it with active energy rays, an acid is generated from the photocationic polymerization initiator, and the epoxy group of the polyorganosiloxane compound is ring-opened and cationic polymerized, and cured. progresses.
  • additives such as reactive diluents and particles contained in the curable composition contain epoxy groups, in addition to polymerization reactions between polyorganosiloxane compounds, polymerization reactions between siloxane compounds and additives also occur. .
  • Ultraviolet rays are preferable as active energy rays.
  • the cumulative irradiation dose of active energy rays is, for example, about 50 to 10000 mJ/cm 2 , and may be set according to the type and amount of the cationic photopolymerization initiator, the thickness of the film, and the like.
  • the emission dose of the active energy rays is not particularly limited, it is preferably 40 W/cm or more, preferably 80 W/cm or more, and may be 120 W/cm or more from the viewpoint of the mechanical strength of the resulting film.
  • the curing temperature is not particularly limited, it is usually 90° C. or lower.
  • the curing temperature is preferably 30° C. or higher, and may be 70° C. or higher or 80° C. or higher. By raising the curing temperature, the curing reaction is accelerated, and the mechanical strength of the film 3 may be improved.
  • the thickness of the film 3 is preferably 10 ⁇ m or more, more preferably 40 ⁇ m or more, even more preferably 45 ⁇ m or more, and may be 50 ⁇ m or more or 90 ⁇ m or more. If the thickness of the film 3 is 40 ⁇ m or more, mechanical properties such as surface hardness tend to be enhanced. In addition, the film 3 is excellent in folding stability even when the thickness is 40 ⁇ m or more.
  • the thickness of the film 3 is preferably 500 ⁇ m or less, more preferably 150 ⁇ m or less, even more preferably 120 ⁇ m or less. If the thickness of the film 3 is more than 500 ⁇ m, the transparency and bending restorability may be poor.
  • the single-layer film 3 made of a cured material layer is not laminated with other films or the like, so interfacial peeling does not occur and it is excellent in handleability. In addition, the single-layer film 3 is less likely to leave bending marks, and is excellent in bending restorability.
  • the bending restorability is evaluated by the following method.
  • a 30 mm ⁇ 70 mm rectangular sample is bent 180° with a radius of 3 mm with the center of the long side as the bending axis, and held for 24 hours in an environment with a temperature of 60° C. and a relative humidity of 90%. After that, with the bending load removed, the sample was placed on a horizontal table in an environment with a temperature of 23°C and a relative humidity of 55%. do.
  • the bending angle (bending recovery angle) is 180°.
  • the larger the folding recovery angle the higher the folding recovery property, and the foldable display has the advantage that the bending marks are less likely to remain in the bent portion.
  • the folding recovery angle of the film 3 is preferably 90° or more, more preferably 120° or more, still more preferably 150° or more, and ideally 180°.
  • the single-layer film 3 composed of a cured polyorganosiloxane compound layer also has excellent bending resistance.
  • the mandrel radius at which cracks occur is preferably 6 mm or less, more preferably 3 mm or less, and may be 2 mm or less or 1 mm or less.
  • the number of times of bending until cracks or breakage occurs is preferably 100,000 or more when a repeated bending test with a radius of 3 mm is performed using a U-shaped bending tester.
  • the film 3 preferably has a pencil hardness test of 6B or more in accordance with JIS-K5600.
  • the pencil hardness may be 4B or higher, or 2B or higher, and may be 3H or higher, or 4H or higher.
  • the total light transmittance of the film 3 is preferably 85% or higher, more preferably 88% or higher, even more preferably 90% or higher, and may be 91% or higher, or 92% or higher.
  • the haze of the film 3 is preferably 1.5% or less, more preferably 0.9% or less, still more preferably 0.6% or less, and may be 0.2% or less.
  • the yellowness index (YI) of film 3 is preferably 3.0 or less, preferably 2.0 or less, preferably 1.0 or less, and particularly preferably 0.7 or less.
  • FIG. 3 is a cross-sectional view of a laminated film in which a film 3 and a transparent resin film 5 are bonded together with an adhesive layer 7 interposed therebetween.
  • Resin materials for the transparent resin film include polyester resins such as polyethylene terephthalate and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene, polypropylene, and cyclic polyolefin; polyamide resins; polyimide resins; ) acrylic resins, polycarbonate resins, cellulose resins such as triacetyl cellulose, silicone resins, and the like. Among them, polyester-based resins are preferred, and polyethylene terephthalate is particularly preferred.
  • the transparent resin film 5 may contain two or more resin materials.
  • the thickness of the transparent resin film 5 is not particularly limited, it is preferably 5 to 100 ⁇ m, and may be 10 to 75 ⁇ m or 20 to 50 ⁇ m. If the thickness is too small, the mechanical properties may be insufficient, and if the thickness is too large, the flexibility and transparency of the laminated film may be insufficient.
  • the thickness of the transparent resin film 5 is preferably 50 ⁇ m or less, and may be 40 ⁇ m or less, 30 ⁇ m or less, or 25 ⁇ m or less. Even if the thickness of the transparent resin film 5 is small, the laminated film 20 having excellent surface hardness can be obtained because the film 3 composed of the cured material layer laminated on the surface thereof has high mechanical strength.
  • a pressure-sensitive adhesive (pressure-sensitive adhesive) is preferable. Since the adhesive does not require curing after bonding, it is difficult for stress to occur at the bonding interface due to curing shrinkage or the like. Therefore, even when the thickness of the transparent resin film 5 is small, the laminate film 20 is less likely to curl.
  • the adhesive layer 7 is preferably a double-sided adhesive sheet.
  • the double-sided pressure-sensitive adhesive sheet include a double-sided transparent adhesive film with a substrate in which pressure-sensitive adhesive layers are provided on both sides of a transparent resin film, and a substrate-less double-sided pressure-sensitive adhesive sheet consisting of only a pressure-sensitive adhesive layer. From the viewpoint of transparency and thickness reduction, a substrate-less double-sided pressure-sensitive adhesive sheet is preferable.
  • an optical transparent pressure-sensitive adhesive tape called OCA (Optical Clear Adhesive) is preferable.
  • Polymer materials for the adhesive include (meth)acrylic resins, urethane resins, silicone resins, epoxy resins, crosslinked rubbers, thermoplastic elastomers, and the like. Among them, (meth)acrylic resins are preferred.
  • the thickness of the double-sided adhesive sheet 7 is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and may be 20 ⁇ m or more. Since the thickness of the double-sided pressure-sensitive adhesive sheet is large, the adhesiveness between the film 3 and the transparent resin film 5 is enhanced, and the stress generated at the bonding interface can be relieved by the double-sided pressure-sensitive adhesive sheet. Therefore, curling of the laminated film 20 is suppressed, and peeling of the laminated film 20 at the folded portion tends to be suppressed when the laminated film 20 is folded. From the viewpoint of transparency and reduction in thickness, the thickness of the double-sided pressure-sensitive adhesive sheet 7 is preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less, and may be 50 ⁇ m or less.
  • the film 3 and the transparent resin film 5 are attached to each other through the double-sided adhesive sheet 7.
  • a laminated film 20 is obtained.
  • the order of bonding is not particularly limited, and the transparent resin film 5 may be bonded after the film 3 and the double-sided adhesive sheet 7 are bonded together, or the film may be bonded after the transparent resin film 5 and the double-sided adhesive sheet 7 are bonded together. 3 may be pasted together.
  • the transparent resin film 5 is attached to the surface of the cured product layer 3 side of the laminate 10 in which the cured product layer 3 is closely laminated on the base material 1 via the double-sided adhesive sheet 7, the cured product layer 3 is removed from the base material. Material 1 may be peeled off.
  • the surface hardness can be improved by providing the cured material layer on the surface of any transparent resin film. Therefore, the use of the laminated film 20 may make it possible to apply the transparent resin film alone to applications in which application was difficult due to insufficient properties such as scratch resistance.
  • the surface hardness can be improved by bonding the film 3 composed of the cured material layer. Since the thickness of the transparent resin film 5 can be made small, it is difficult to leave a bending trace at the bent portion, and the restoring property is excellent.
  • the adhesive has a stress relieving effect, so the hard coat layer is directly placed on the transparent resin film. Compared with the formed hard coat film, peeling at the interface is less likely to occur, and there is a tendency that the flex resistance and folding restorability are improved.
  • the laminated film 20 in which the film 3 made of the cured polyorganosiloxane compound layer and the transparent resin film 5 are laminated together has excellent bending resistance.
  • the mandrel radius at which cracks occur in the film 3 is preferably 6 mm or less, more preferably 3 mm or less, and 2 mm or less. Alternatively, it may be 1 mm or less.
  • the mandrel radius at which cracks occur in the film 3 is preferably 3 mm or less, more preferably 2 mm or less, and 1 mm or less.
  • the pencil hardness of the surface of the laminated film 20 on the film 3 side is preferably 6B or higher, and may be 3B or higher or B or higher.
  • the total light transmittance of the laminated film 20 is preferably 85% or higher, more preferably 88% or higher, and even more preferably 90% or higher.
  • the haze of the laminated film 20 is preferably 1.5% or less, more preferably 1.0% or less.
  • Various functional layers may be provided on both sides or one side of the film 3 and laminated film 20 described above.
  • Examples of functional layers include antireflection layers, antiglare layers, antistatic layers, transparent electrodes, and the like.
  • a transparent pressure-sensitive adhesive layer may be added for bonding with other members.
  • Single-layer films and transparent resin film laminates can be used, for example, as cover window materials placed on the viewer-side surface of image display panels, and are excellent in flex resistance and folding recovery properties, and are therefore used in foldable displays ( It can also be suitably used as a cover window for a foldable display.
  • the polystyrene-equivalent weight average molecular weight Mw measured with a GPC apparatus "HLC-8220GPC" manufactured by Tosoh (columns: TSKgel GMH XL x 2, TSKgel G3000H XL , TSKgel G2000H XL ) was 3,000.
  • the ratio of [SiO 3/2 body]/[SiO 2/2 body] calculated from 29 Si-NMR measurement using a 600 MHz-NMR manufactured by Agilent was 2.3.
  • the residual rate of epoxy groups calculated from the 1 H-NMR spectrum measured with heavy acetone as a solvent using a 400 MHz-NMR manufactured by Bruker was 95% or more.
  • Polyorganosiloxane compound 2 had a weight average molecular weight Mw of 4500, a ratio of [SiO 3/2 bodies]/[SiO 2/2 bodies] of 2.1, and a residual epoxy group rate of 95% or more.
  • curable composition A photocationic polymerization initiator and a leveling agent were added to the curable resin component to prepare curable compositions A and B having the formulations shown in Table 1.
  • the numerical values in Table 1 are parts by weight, and the amount of the photopolymerization initiator and the leveling agent is the weight of the solid content of each component with respect to a total of 100 parts by weight of the resin components.
  • Example 1 50 ⁇ m thick PET film with release treatment on one side (Fujimori Kogyo “38E-0010NSP-5”, contact angle meter (Kyowa Interface Chemical “PCA-11”) Water contact angle on the release treated surface: 83°) was coated with the curable composition A using a bar coater and heated at 120°C for 10 minutes. Thereafter, while adjusting the surface temperature of the coating film to 30° C., the composition was cured by irradiating ultraviolet rays from a position of 200 mm using a high-pressure mercury lamp with an emission dose of 80 W/cm. After that, the cured product layer was peeled off from the release film to obtain a single-layer film having a thickness of 48 ⁇ m.
  • Example 2 Using a release film (“75E-0010NSK” manufactured by Fujimori Kogyo Co., Ltd.) having a thickness of 75 ⁇ m and a water contact angle of 84° on the release-treated surface, the surface temperature of the coating film during ultraviolet irradiation, the emission dose of a high-pressure mercury lamp, and The thickness of the cured product layer was changed as shown in Table 2. A single layer film was obtained in the same manner as in Example 1 except for the above.
  • a release film (“75E-0010NSK” manufactured by Fujimori Kogyo Co., Ltd.) having a thickness of 75 ⁇ m and a water contact angle of 84° on the release-treated surface
  • the thickness of the cured product layer was changed as shown in Table 2.
  • a single layer film was obtained in the same manner as in Example 1 except for the above.
  • Example 3 A release film (“50E-0010NSD” manufactured by Fujimori Industry Co., Ltd.) having a thickness of 50 ⁇ m and a water contact angle of 107° on the release-treated surface was used. A single layer film was obtained in the same manner as in Example 2 except for the above.
  • Example 4 As shown in Table 2, the surface temperature of the coating film during ultraviolet irradiation, the emission dose of the high-pressure mercury lamp, and the thickness of the cured product layer were changed. A single layer film was obtained in the same manner as in Example 1 except for the above.
  • Comparative Examples 1 and 2 ⁇ Comparative Examples 1 and 2>
  • a PET film having a thickness of 50 ⁇ m manufactured by Toray Industries, Ltd., “Lumirror U48”, water contact angle: 73°
  • the curable composition A was applied.
  • the curable composition layer B was used instead of the curable composition A to produce a single-layer film composed of a cured product layer. could not be peeled off.
  • Comparative Examples 3 and 4 ⁇ Comparative Examples 3 and 4>
  • a 75 ⁇ m thick PET film with a release treatment on one side (a release film attached to a transparent double-sided adhesive tape “8146-1” manufactured by 3M, a water contact angle on the release treatment surface: 108 °) as a base material, the curable composition A was applied to the release-treated surface, but significant repelling occurred, and a film could not be formed.
  • Comparative Example 4 in which the curable composition layer B was used instead of the curable composition A, similarly to Comparative Example 3, a film could not be formed.
  • ⁇ Mandrel radius> According to JIS K5600-5-1:1999, a cylindrical mandrel test was performed using a type 1 testing machine to determine the bending radius at which cracks occurred in the film.
  • ⁇ Bending restoration angle> A sample was prepared by cutting the film into a rectangle with a short side of 30 mm and a long side of 70 mm. The sample was bent 180° with a radius of 3 mm around the center of the long side as the bending axis, and held in an environment of 60° C. and 90% relative humidity for 24 hours. After that, with the bending load removed, the sample was placed on a horizontal table in an environment with a temperature of 23°C and a relative humidity of 55%. did.
  • Total light transmittance and haze> Measured by the method described in JIS K7361-1:1999 and JIS K7136:2000 using a haze meter "HZ-V3" manufactured by Suga Test Instruments. A D65 light source was used for the measurement, and the total light transmittance was calculated as the ratio of the total transmitted light flux (parallel light component and diffused light component) to the parallel incident light flux to the hard coat film.
  • Table 1 shows the production conditions of the films of Examples 1 to 7 (water contact angle of the substrate, type of composition, curing conditions), applicability evaluation results, film thickness, and film evaluation results.
  • Table 1 shows the production conditions of the films of Examples 1 to 7 (water contact angle of the substrate, type of composition, curing conditions), applicability evaluation results, film thickness, and film evaluation results.
  • PEN polyethylene naphthalate
  • Teonex Q65-HA manufactured by Toyobo
  • TAC triacetyl cellulose
  • the PET film and PEN film with a thickness of 50 ⁇ m had a folding recovery angle of 70° or less
  • the films of Examples 1, 2, 5, and 6, which consist of a cured product layer of a polyorganosiloxane compound had a folding recovery angle of 70° or less.
  • the angle is 120° or more, and it can be seen that the bending marks are less likely to remain.
  • the films of Examples 1 and 2, which are composed of the cured product layer of the composition A having a polyorganosiloxane compound having an alicyclic epoxy group as a curable resin component have excellent folding recovery properties, and the PET film , the PEN film and the TAC film, the pencil hardness was higher, and the surface hardness was also excellent.
  • the film of Example 4 with a thickness of 120 ⁇ m had even higher pencil hardness.
  • the films of Examples 1 to 3 and 5 to 7 did not crack even with a mandrel radius of 1 mm, and exhibited excellent bending resistance.
  • the film of Example 4 having a thickness of 120 ⁇ m has a mandrel radius of 6 mm, and it can be seen that the film has good bending resistance even when the thickness is large.
  • the films of Examples 2, 5, and 6 had bending resistance to withstand repeated bending of 100,000 times.
  • All of the films of Examples 1 to 7 had high total light transmittance, small haze and YI, transparency comparable to optical films such as PET film, PEN film and TAC film, and a thickness of The large films of Examples 4 and 7 also had excellent transparency.
  • a transparent double-sided adhesive tape with a thickness of 25 ⁇ m A PET film with a thickness of 20 ⁇ m was attached to one side of 3M "8146-1", and then the films of Examples 2, 4, 6 and 7 were attached to the other side. , a laminated film having a total thickness of about 100 ⁇ m was produced.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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  • Laminated Bodies (AREA)

Abstract

Un mode de réalisation de la présente invention est un film monocouche composé d'une couche d'un produit durci d'une composition comprenant un composé polyorganosiloxane ayant un groupe époxy. Le composé polyorganosiloxane est un condensat d'un composé de silane représenté par la formule générale (1). R1 représente un groupe alkylène substitué ou non substitué en C1-16 ; R2 représente un atome d'hydrogène ou un groupe alkyle en C1-10 ; R3 représente un atome d'hydrogène ou un groupe hydrocarboné monovalent choisi parmi les groupes alkyle en C1-10, les groupes aryle en C6-25 et les groupes aralkyle en C7-12 ; x est un nombre entier de 2 ou 3 ; et Y est un groupe glycidyloxy ou un groupe époxy alicyclique.　Y-R1-(Si(OR2)xR3 3-x) … (1)
PCT/JP2022/011069 2021-03-12 2022-03-11 Film et son procédé de production, film stratifié et affichage WO2022191328A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011194647A (ja) * 2010-03-18 2011-10-06 Nippon Steel Chem Co Ltd 積層体フィルム
WO2015087686A1 (fr) * 2013-12-13 2015-06-18 株式会社ダイセル Polyorganosilsesquioxane, film de revêtement dur, feuille adhésive et stratifié
JP2017132879A (ja) * 2016-01-27 2017-08-03 東レ・ファインケミカル株式会社 シリコーン重合体およびその製造方法
WO2019176074A1 (fr) * 2018-03-15 2019-09-19 日立化成株式会社 Résine époxy, composition de résine époxy, feuille de résine, feuille de stade b, feuille de stade c, objet durci, feuille métallique pourvue de la résine, substrat métallique et dispositif semi-conducteur de puissance

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011194647A (ja) * 2010-03-18 2011-10-06 Nippon Steel Chem Co Ltd 積層体フィルム
WO2015087686A1 (fr) * 2013-12-13 2015-06-18 株式会社ダイセル Polyorganosilsesquioxane, film de revêtement dur, feuille adhésive et stratifié
JP2017132879A (ja) * 2016-01-27 2017-08-03 東レ・ファインケミカル株式会社 シリコーン重合体およびその製造方法
WO2019176074A1 (fr) * 2018-03-15 2019-09-19 日立化成株式会社 Résine époxy, composition de résine époxy, feuille de résine, feuille de stade b, feuille de stade c, objet durci, feuille métallique pourvue de la résine, substrat métallique et dispositif semi-conducteur de puissance

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