WO2020209194A1 - Film de revêtement dur, procédé de production associé, article pourvu d'un film de revêtement dur et appareil d'affichage d'image - Google Patents

Film de revêtement dur, procédé de production associé, article pourvu d'un film de revêtement dur et appareil d'affichage d'image Download PDF

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Publication number
WO2020209194A1
WO2020209194A1 PCT/JP2020/015297 JP2020015297W WO2020209194A1 WO 2020209194 A1 WO2020209194 A1 WO 2020209194A1 JP 2020015297 W JP2020015297 W JP 2020015297W WO 2020209194 A1 WO2020209194 A1 WO 2020209194A1
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Prior art keywords
hard coat
layer
film
group
coat layer
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PCT/JP2020/015297
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English (en)
Japanese (ja)
Inventor
悠太 福島
彩子 松本
暢之 芥川
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富士フイルム株式会社
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Priority to JP2021513614A priority Critical patent/JP7291209B2/ja
Priority to KR1020217031869A priority patent/KR20210136065A/ko
Priority to CN202080028146.0A priority patent/CN113678029B/zh
Publication of WO2020209194A1 publication Critical patent/WO2020209194A1/fr

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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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors

Definitions

  • the present invention relates to a hard coat film and a method for manufacturing the same, an article provided with the hard coat film, and an image display device.
  • Image display devices such as plasma displays (PDPs), electroluminescence displays (ELDs), vacuum fluorescent displays (VFDs), field emission displays (FEDs), and liquid crystal displays (LCDs) prevent scratches on the display surface. Therefore, it is preferable to provide an optical film (hard coat film) having a hard coat layer on the base material.
  • PDPs plasma displays
  • ELDs electroluminescence displays
  • VFDs vacuum fluorescent displays
  • FEDs field emission displays
  • LCDs liquid crystal displays
  • Patent Document 1 describes a laminate for a touch panel having a resin cured layer on a polyimide film or an aramid film base material and having repeated bending resistance.
  • Patent Document 2 describes a transparent flexible hard coat film having a hard coat layer obtained by polymerizing a composition composed of a polyorganosiloxane having an alicyclic epoxy group and a reaction diluent.
  • the base material of the flexible hard coat film As the base material of the flexible hard coat film, the polyimide film, the polyamide-imide film, the aramid film and the like described in Patent Document 1 are attracting attention because they are excellent in hardness and repeated bending resistance.
  • the present inventors examined the problems of the above-mentioned base material, it was found that there is a problem of light resistance caused by the decomposition of the aromatic ring in the molecule when irradiated with ultraviolet rays.
  • Specific examples thereof include coloring of the base material by irradiation with ultraviolet rays (light-resistant coloring) and poor adhesion between the base material and the hard coat layer (light-resistant adhesion).
  • the light-resistant adhesion can be improved by forming a mixed layer in which the hard coat layer and the components of the base material are mixed between the hard coat layer and the base material. ..
  • a mixed layer in which the hard coat layer and the components of the base material are mixed between the hard coat layer and the base material. ..
  • it is necessary to swell or dissolve the surface of the base material in the step of applying and drying the composition for forming the hard coat layer, and the base material It was found that the surface hardness of the hard coat layer may be significantly reduced, or the base material component may be eluted in the entire hard coat layer to reduce the hardness of the hard coat layer.
  • an object of the present invention is to provide a hard coat film having high hardness, excellent light adhesion, and excellent resistance to repeated bending, a method for producing the same, an article and an image display device provided with the hard coat film. It is in.
  • ⁇ 4> The hard coat film according to any one of ⁇ 1> to ⁇ 3>, wherein the hard coat layer contains a cured product of a curable resin having a number average molecular weight of 1500 or more.
  • the curable resin contains polyorganosylsesquioxane (X) having a polymerizable group.
  • X polyorganosylsesquioxane
  • ⁇ 6> The hard coat film according to any one of ⁇ 1> to ⁇ 5>, wherein the adhesive layer contains an ultraviolet absorber.
  • ⁇ 7> An article comprising the hard coat film according to any one of ⁇ 1> to ⁇ 6>.
  • ⁇ 8> An image display device provided with the hard coat film according to any one of ⁇ 1> to ⁇ 6>.
  • the step (3) of impregnating a part of the adhesive into the film substrate The step (4) of adhering the hard coat layer and the film base material by irradiating with heating or active energy rays, The step (5) of peeling the temporary support from the hard coat layer and A method for producing a hard coat film having.
  • a method for producing a hard coat film which comprises a step (4') of adhering the hard coat layer and the film base material by irradiating with heating or active energy rays.
  • the method for producing a hard coat film according to ⁇ 10> which comprises a step (5') of peeling the protective film from the hard coat layer.
  • the hard coat film of the present invention is a hard coat film having a base material, an adhesive layer, and a hard coat layer in this order, and the base material is at least one selected from the group consisting of a polyimide resin, a polyamideimide resin, and an aramid resin. It is a film containing a resin, and is a hard coat film having a mixed layer in which a base material component and an adhesive layer component are mixed between the adhesive layer and the base material.
  • 1 and 2 show a schematic view (cross-sectional view) of an example of the hard coat film of the present invention.
  • the hard coat film 10 of FIG. 1 has a base material 1, a mixed layer 2, an adhesive layer 3, and a hard coat layer 4 in this order.
  • the hard coat film 11 of FIG. 2 has a base material 1, a mixed layer 2, an adhesive layer 3, a hard coat layer 4, and a scratch resistant layer 5 in this order.
  • the mechanism by which the hard coat film of the present invention is excellent in light adhesion, high hardness, and excellent resistance to repeated bending is not clear, but the present inventors speculate as follows.
  • the hard coat film of the present invention is characterized by having a mixed layer in which a base material component and an adhesive component are mixed between the adhesive layer and the base material. Since the content of the base material component that is easily deteriorated by ultraviolet rays can be reduced in the mixed layer as compared with the base material alone, deterioration by ultraviolet rays is unlikely to occur. Deterioration due to ultraviolet rays gradually progresses from the surface of the base material to the inside of the base material.
  • the mixed layer can be controlled by the components of the adhesive and the bonding process, and the components / composition ratio of the composition for forming the hard coat layer and the coating / drying process are not restricted. Therefore, it is possible to prevent a decrease in hardness that occurs when the above-mentioned mixed layer is formed, and it is considered that both light-resistant adhesion and hardness can be achieved at the same time.
  • the base material of the hard coat film of the present invention is a film containing at least one selected from the group consisting of a polyimide resin, a polyamide-imide resin and an aramid resin.
  • the substrate has a transmittance of 70% or more, more preferably 80% or more, and even more preferably 90% or more in the visible light region.
  • the film containing the above resin is preferably used as a base material because it has a large number of breaks and bends measured by a MIT tester according to JIS (Japanese Industrial Standards) P8115 (2001) and has a relatively high hardness.
  • a MIT tester according to JIS (Japanese Industrial Standards) P8115 (2001) and has a relatively high hardness.
  • the aramid described in Example 1 of Japanese Patent No. 56994454, the polyimides described in JP-A-2015-508345, JP-A-2016-521216, and WO2017 / 0142787 are preferably used as the base material. Can be done.
  • the thickness of the base material is more preferably 100 ⁇ m or less, further preferably 80 ⁇ m or less, and most preferably 50 ⁇ m or less.
  • the thickness of the base material is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and most preferably 15 ⁇ m or more.
  • the substrate may be formed by thermally melting a thermoplastic polymer to form a film, or may be formed from a solution in which the polymer is uniformly dissolved by a solution film forming (solvent casting method).
  • a solution film forming solvent casting method
  • the above-mentioned softening material and various additives can be added at the time of heat melting.
  • the base material is prepared by the solution film forming method
  • the above-mentioned softening material and various additives can be added to the polymer solution (hereinafter, also referred to as doping) in each preparation step.
  • the timing of addition may be any in the doping preparation step, but the step of adding and preparing the additive may be added to the final preparation step of the doping preparation step.
  • the coating film may be heated for drying and / or baking of the coating film.
  • the heating temperature of the coating film is usually 50 to 350 ° C.
  • the coating film may be heated under an inert atmosphere or under reduced pressure.
  • the solvent can be evaporated and removed by heating the coating film.
  • the resin film may be formed by a method including a step of drying the coating film at 50 to 150 ° C. and a step of baking the dried coating film at 180 to 350 ° C.
  • Surface treatment may be applied to at least one main surface of the base material.
  • the adhesive layer is a layer provided for adhering the hard coat layer on the base material in order to form the hard coat layer on the surface of the base material.
  • any appropriate form of adhesive can be adopted.
  • Specific examples include water-based adhesives, solvent-based adhesives, emulsion-based adhesives, solvent-free adhesives, active energy ray-curable adhesives, and thermosetting adhesives.
  • the active energy ray-curable adhesive include an electron beam-curable adhesive, an ultraviolet curable adhesive, and a visible light-curable adhesive.
  • Aqueous adhesives, active energy ray-curable adhesives and thermosetting adhesives can be preferably used.
  • water-based adhesive examples include isocyanate-based adhesives, polyvinyl alcohol-based adhesives (PVA-based adhesives), gelatin-based adhesives, vinyl-based latex-based adhesives, water-based polyurethanes, and water-based polyesters.
  • active energy ray-curable adhesive examples include (meth) acrylate-based adhesives.
  • the curable component in the (meth) acrylate-based adhesive include a compound having a (meth) acryloyl group and a compound having a vinyl group. Further, a compound having an epoxy group or an oxetanyl group can also be used as the cationic polymerization curable adhesive.
  • the compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in the molecule, and various generally known curable epoxy compounds can be used.
  • Preferred epoxy compounds include compounds having at least two epoxy groups and at least one aromatic ring in the molecule (aromatic epoxy compounds) and at least one of them having at least two epoxy groups in the molecule. Examples thereof include a compound (alicyclic epoxy compound) formed between two adjacent carbon atoms constituting an alicyclic ring.
  • Specific examples of the thermosetting adhesive include phenol resin, epoxy resin, polyurethane curable resin, urea resin, melamine resin, acrylic reaction resin and the like. Specific examples thereof include bisphenol F type epoxides.
  • the adhesive preferably has a different composition from the hard coat layer.
  • a PVA-based adhesive is used as the adhesive constituting the adhesive layer.
  • a PVA-based adhesive it is possible to bond the materials together even when a material that does not transmit active energy rays is used.
  • an active energy ray-curable adhesive is used as the adhesive constituting the adhesive layer. If an active energy ray-curable adhesive is used, sufficient delamination force can be obtained even for a material whose surface is hydrophobic and which cannot be adhered with a PVA adhesive.
  • the adhesive include an adhesive containing an epoxy compound containing no aromatic ring in the molecule and cured by heating or irradiation with active energy rays, as shown in JP-A-2004-245925.
  • an adhesive containing an epoxy compound containing no aromatic ring in the molecule and cured by heating or irradiation with active energy rays as shown in JP-A-2004-245925.
  • (a) the (meth) acrylic compound having two or more (meth) acryloyl groups in the molecule and (b) the molecule.
  • An active energy ray-curable adhesive containing a (meth) acrylic compound having a hydroxyl group and having only one polymerizable double bond, and (c) a phenolethylene oxide-modified acrylate or a nonylphenolethylene oxide-modified acrylate. Can be mentioned.
  • the storage elastic modulus of the adhesive layer is preferably 1.0 ⁇ 10 6 Pa or more, and more preferably 1.0 ⁇ 10 7 Pa or more in the region of 70 ° C. or lower.
  • the upper limit of the storage elastic modulus of the adhesive layer is, for example, 1.0 ⁇ 10 10 Pa.
  • the thickness of the adhesive layer is typically preferably 0.01 ⁇ m to 7 ⁇ m, and more preferably 0.01 ⁇ m to 5 ⁇ m.
  • the adhesive layer in the present invention is located between the hard coat layer and the base material, it has a large effect on hardness. Therefore, when an adhesive is used instead of the adhesive layer of the present invention, the hardness may be significantly reduced. From the viewpoint of hardness, it is preferable that the adhesive layer is thin and has a high storage elastic modulus.
  • the active energy ray-curable adhesive it is also important to select an initiator and a photosensitizer.
  • a (meth) acrylate-based adhesive is described in Examples of JP-A-2018-17996.
  • the cationic polymerization-curable adhesive can be produced by referring to the descriptions in JP-A-2018-355361 and JP-A-2018-41079.
  • the PVA-based adhesive preferably contains an additive that improves the adhesiveness to the base material and the hard coat layer.
  • the type of additive is not particularly limited, but it is preferable to use a compound or the like containing boronic acid or the like.
  • the difference in refractive index between the adhesive layer and the hard coat layer is preferably 0.05 or less, and more preferably 0.02 or less, from the viewpoint of suppressing interference fringes.
  • the method for adjusting the refractive index of the adhesive layer is not particularly limited, but it is preferable to add hollow particles when the refractive index is to be lowered, and particles such as zirconia when the refractive index is to be improved. ..
  • Japanese Patent Application Laid-Open No. 2018-17996 describes a specific example of an adhesive having a refractive index of 1.52 to 1.64.
  • the adhesive layer contains an ultraviolet absorber.
  • an ultraviolet absorber is added to the adhesive layer, it is preferably added to the thermosetting adhesive from the viewpoint of bleeding out and inhibition of curing.
  • UV absorber examples of the ultraviolet absorber include a benzotriazole compound, a triazine compound, and a benzoxazine compound.
  • the benzotriazole compound is a compound having a benzotriazole ring, and specific examples thereof include various benzotriazole-based ultraviolet absorbers described in paragraph 0033 of JP2013-1111835.
  • the triazine compound is a compound having a triazine ring, and specific examples thereof include various triazine-based ultraviolet absorbers described in paragraph 0033 of JP2013-1111835.
  • As the benzoxazine compound for example, those described in paragraph 0031 of JP-A-2014-209162 can be used.
  • the content of the ultraviolet absorber in the adhesive layer is, for example, about 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer contained in the adhesive, but is not particularly limited. Further, regarding the ultraviolet absorber, reference is also made to paragraph 0032 of JP2013-1111835.
  • an ultraviolet absorber having high heat resistance and low volatilization is preferable. Examples of such an ultraviolet absorber include UVSORB101 (manufactured by FUJIFILM Fine Chemicals Co., Ltd.), TINUVIN 360, TINUVIN 460, TINUVIN 1577 (manufactured by BASF), LA-F70, LA-31, LA-46 (manufactured by ADEKA) and the like. Can be mentioned.
  • the adhesive in the present invention preferably contains a compound having a molecular weight of 500 or less, and more preferably 300 or less, from the viewpoint of forming a mixed layer described later. Further, from the same viewpoint, it is preferable to contain components having SP values of 21 to 26.
  • the SP value (solubility parameter) in the present invention is a value calculated by the Hoy method, and the Hoy method is described in POLYMERHANDBOOKFOURTHETION.
  • the adhesive in the present invention preferably has a high affinity with the base material from the viewpoint of forming a mixed layer described later.
  • the affinity between the base material and the adhesive can be confirmed by observing the change in the base material when the base material is immersed in the adhesive layer. It is preferable to use an adhesive that makes the base material cloudy or dissolves when the base material is immersed in the adhesive because a mixed layer described later can be effectively formed.
  • a mixed layer in which the components of the adhesive layer and the components of the base material are mixed is formed between the adhesive layer and the base material layer.
  • the mixed layer refers to a region where the compound distribution (components of the adhesive layer and components of the base material) gradually changes from the adhesive layer side to the base material layer side between the adhesive layer and the base material.
  • the adhesive layer refers to a portion that contains the components of the adhesive layer and does not contain the components of the base material
  • the base material includes the components of the base material and is the adhesive layer. The part that does not contain the component will be shown.
  • the mixed layer contains all or part of the components of the base material and the adhesive layer. Both can be measured as detected portions, and the film thickness in this region can also be measured from the cross-sectional information of TOF-SIMS.
  • TOF-SIMS time-of-flight secondary ion mass spectrometer
  • the thickness of the mixed layer is preferably 0.1 to 10.0 ⁇ m, more preferably 1.0 ⁇ m to 6.0 ⁇ m. It is preferable that the thickness of the mixed layer is 0.1 ⁇ m or more to obtain the effect of improving the light-resistant adhesion, and the thickness of 1.0 ⁇ m or more is preferable because the light-resistant adhesion can be improved even when irradiated with ultraviolet rays for a long period of time. On the other hand, when the thickness of the mixed layer is 10 ⁇ m or less, the hardness becomes good, and when the thickness is 6.0 ⁇ m or less, the hardness can be further maintained, which is preferable.
  • the hard coat layer of the hard coat film of the present invention preferably contains a cured product of a cured component of the composition for forming a hard coat layer.
  • the curing component of the composition for forming a hard coat layer in the present invention is not particularly limited, but is preferably a curable resin having a number average molecular weight of 1500 or more, and contains polyorganosylsesquioxane (X) having a polymerizable group. It is more preferable to do so.
  • the hardness of the composition for forming a hard coat layer is significantly reduced when the composition for forming a hard coat layer is impregnated into the base material without using an adhesive layer, and the effect of the present invention is remarkable, which is preferable. .. Further, it is preferable to use polyorganosilsesquioxane (X) having a polymerizable group because a hard coat film having excellent hardness and repeated bending resistance can be provided.
  • the cured product of polyorganosylsesquioxane (X) having a polymerizable group is obtained by heating and / or irradiating a curable composition containing polyorganosylsesquioxane (X) having a polymerizable group with ionizing radiation. It is preferably cured.
  • the polymerizable group in the polyorganosylsesquioxane (X) having a polymerizable group is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferable.
  • a generally known radically polymerizable group can be used, and a preferred one is a (meth) acryloyl group.
  • a generally known cationically polymerizable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, and the like.
  • Vinyloxy groups and the like can be mentioned.
  • an alicyclic ether group and a vinyloxy group are preferable, an epoxy group, an oxetanyl group and a vinyloxy group are particularly preferable, and an epoxy group is most preferable.
  • Polyorganosylsesquioxane having a polymerizable group also referred to as “polyorganosylsesquioxane (X)” has at least a siloxane structural unit containing a polymerizable group, and has the following general formula (1). It is preferably polyorganosylsesquioxane represented by.
  • Rb may include a (meth) acryloyl group or an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, a vinyloxy group and the like.
  • an alicyclic ether group and a vinyloxy group are preferable, and represents a group containing an epoxy group, an oxetanyl group and a vinyloxy group
  • Rc represents a monovalent group.
  • the plurality of Rb and Rc may be the same or different.
  • the plurality of Rc may form a bond with each other.
  • [SiO 1.5 ] in the general formula (1) represents a structural portion composed of a siloxane bond (Si—O—Si) in the polyorganosylsesquioxane.
  • Polyorganosylsesquioxane is a network-type polymer or polyhedral cluster having a siloxane structural unit derived from a hydrolyzable trifunctional silane compound, and can form a random structure, a ladder structure, a cage structure, or the like by a siloxane bond. ..
  • the structural portion represented by [SiO 1.5 ] may have any of the above structures, but preferably contains a large amount of ladder structure. By forming the ladder structure, the deformation recovery of the hard coat film can be kept good.
  • the formation of the rudder structure is qualitatively determined by the presence or absence of absorption derived from Si-O-Si expansion and contraction, which is characteristic of the rudder structure appearing near 1020-1050 cm -1 when FT-IR (Fourier Transform Infrared Spectroscopy) is measured. You can check.
  • Rb may include a (meth) acryloyl group or an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, a vinyloxy group and the like.
  • Rb in the general formula (1) is a group (a group other than an alkoxy group and a halogen atom) bonded to a silicon atom in a hydrolyzable trifunctional silane compound used as a raw material of polyorganosylsesquioxane; for example, it will be described later. It is derived from Rb etc. in the hydrolyzable silane compound represented by the formula (B) of.
  • Rc represents a monovalent group.
  • the monovalent group represented by Rc includes a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted.
  • Substituted aralkyl groups can be mentioned.
  • Examples of the alkyl group represented by Rc include alkyl groups having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl group, isopropyl group, isobutyl group, s-butyl group and t-butyl. Examples thereof include linear or branched alkyl groups such as groups and isopentyl groups. Examples of the cycloalkyl group represented by Rc include a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • Examples of the alkenyl group represented by Rc include an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a linear or branched alkenyl group such as a vinyl group, an allyl group and an isopropenyl group.
  • Examples of the aryl group represented by Rc include an aryl group having 6 to 15 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.
  • Examples of the aralkyl group represented by Rc include an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.
  • Examples of the above-mentioned substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted aryl group and substituted aralkyl group include hydrogen atoms or main ribs in each of the above-mentioned alkyl group, cycloalkyl group, alkenyl group, aryl group and aralkyl group. At least one selected from the group consisting of an ether group, an ester group, a carbonyl group, a halogen atom (fluorine atom, etc.), an acrylic group, a methacryl group, a mercapto group, and a hydroxy group (hydroxyl group) in part or all of the case. Examples thereof include groups substituted with.
  • Rc is preferably a substituted or unsubstituted alkyl group, and more preferably an unsubstituted alkyl group having 1 to 10 carbon atoms.
  • the plurality of Rc may form a bond with each other. It is preferable that two or three Rcs form a bond with each other, and more preferably two Rcs form a bond with each other.
  • the group (Rc 2 ) formed by bonding two Rc to each other is preferably an alkylene group formed by bonding a substituted or unsubstituted alkyl group represented by the above-mentioned Rc.
  • Examples of the alkylene group represented by Rc 2 include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, an s-butylene group, a t-butylene group, an n-pentylene group and an isopentylene group.
  • the alkylene group represented by Rc 2 is preferably an unsubstituted alkylene group having 2 to 20 carbon atoms, more preferably an unsubstituted alkylene group having 2 to 20 carbon atoms, and further preferably having an unsubstituted carbon number of 2 to 8 carbon atoms. It is an alkylene group, and particularly preferably an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, and an n-octylene group.
  • the alkylene group represented by Rc 2 described above is a trivalent group in which an arbitrary hydrogen atom in the alkylene group is reduced by one. ..
  • Rc in the general formula (1) is a group (a group other than an alkoxy group and a halogen atom) bonded to a silicon atom in a hydrolyzable silane compound used as a raw material of polyorganosylsesquioxane; for example, the formula described later.
  • q is more than 0 and r is 0 or more.
  • q / (q + r) is preferably 0.5 to 1.0.
  • X polyorganosylsesquioxane
  • r / (q + r) is preferably 0.005 to 0.20.
  • r / (q + r) is more preferably 0.005 to 0.10, further preferably 0.005 to 0.05, and particularly preferably 0.005 to 0.025.
  • the number average molecular weight (Mn) of polyorganosilsesquioxane (X) in terms of standard polystyrene by gel permeation chromatography (GPC) is preferably 1500 to 80,000, more preferably 2000 to 50,000.
  • the molecular weight dispersion (Mw / Mn) of polyorganosilsesquioxane (X) in terms of standard polystyrene by GPC is, for example, 1.0 to 20.0, preferably 1.0 to 10.0.
  • Polyorganosylsesquioxane (X) can be produced by a known production method, and is not particularly limited, but can be produced by a method of hydrolyzing and condensing one or more hydrolyzable silane compounds.
  • a hydrolyzable trifunctional silane compound (a compound represented by the following formula (B)) for forming a siloxane structural unit containing an epoxy group is used as the hydrolyzable silane compound.
  • r in the general formula (1) is more than 0, it is preferable to use a compound represented by the following formula (C1), (C2) or (C3) in combination as the hydrolyzable silane compound.
  • Rb in the formula (B) has the same meaning as Rb in the general formula (1), and the same applies to preferred examples.
  • X 2 in the formula (B) represents an alkoxy group or a halogen atom.
  • the alkoxy group in X 2 include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group and an isobutyloxy group.
  • the halogen atom in X 2 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
  • an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. Note that three X 2 can be the same, respectively, may be different.
  • the compound represented by the above formula (B) is a compound that forms a siloxane structural unit having Rb.
  • Rc 1 in the formula (C1) has the same meaning as Rc in the general formula (1), and the same applies to preferred examples.
  • Rc 2 in the formula (C2) is synonymous with a group (Rc 2 ) formed by binding two Rc in the general formula (1) to each other, and the same applies to preferred examples.
  • Rc 3 in the formula (C3) is synonymous with a group (Rc 3 ) formed by binding three Rc in the general formula (1) to each other, and a preferred example is also the same.
  • X 3 in the above formulas (C1) to (C3) has the same meaning as X 2 in the above formula (B), and the same applies to preferred examples.
  • a plurality of X 3 may be the same, respectively, it may be different.
  • hydrolyzable silane compound a hydrolyzable silane compound other than the compounds represented by the above formulas (B) and (C1) to (C3) may be used in combination.
  • hydrolyzable trifunctional silane compounds hydrolyzable monofunctional silane compounds
  • hydrolyzable bifunctional silane compounds other than the compounds represented by the above formulas (B) and (C1) to (C3).
  • Rc is derived from Rc 1 to Rc 3 in the hydrolyzable silane compounds represented by the above formulas (C1) to (C3)
  • q / (q + r) in order to adjust q / (q + r) in the general formula (1), the above The compounding ratio (molar ratio) of the compounds represented by the formulas (B) and (C1) to (C3) may be adjusted.
  • the value represented by the following (Z2) is set to 0.5 to 1.0, and these compounds are hydrolyzed. And it may be produced by a method of condensing.
  • (Z2) Compound (molar amount) represented by the formula (B) / ⁇ Compound (molar amount) represented by the formula (B) + Compound (molar amount) represented by the formula (C1) + Formula (C2) ) Compound (molar amount) x 2 + Compound represented by formula (C3) (molar amount) x 3 ⁇
  • the amount and composition of the hydrolyzable silane compound used can be appropriately adjusted according to the desired structure of polyorganosylsesquioxane (X).
  • hydrolysis and condensation reactions of the hydrolyzable silane compound can be carried out simultaneously or sequentially.
  • the order in which the reactions are carried out is not particularly limited.
  • the condensation rate of polyorganosylsesquioxane (X) is preferably 80% or more from the viewpoint of film hardness.
  • the condensation rate is more preferably 90% or more, and even more preferably 95% or more.
  • the condensation ratio is calculated by performing 29 Si NMR (nuclear magnetic resonance) spectrum measurement on a hard coat film sample having a hard coat layer containing a cured product of polyorganosylsesquioxane (X) and using the measurement results. It is possible.
  • the cured product of polyorganosylsesquioxane (X) preferably has the above-mentioned polymerizable group polymerized.
  • the reaction rate of the above polymerization reaction is determined by FT-IR (Fourier Transform Infrared Spectroscopy) single reflection ATR (For samples before and after complete curing and heat treatment of the composition for forming a hard coat layer containing polyorganosylsesquioxane (X). Attenuated Total Reflection) measurement can be performed, and it can be calculated from the change in peak height derived from the polymerizable group.
  • Polyorganosilsesquioxane (X) may be used alone or in combination of two or more having different structures.
  • the content of the cured product of polyorganosylsesquioxane (X) is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, based on the total mass of the hard coat layer. It is preferable, and more preferably 80% by mass or more and 100% by mass or less.
  • the hard coat layer may contain components other than the above, and may contain, for example, a dispersant, a leveling agent, an antifouling agent, an antistatic agent, an ultraviolet absorber, and the like.
  • the film thickness of the hard coat layer is not particularly limited, but is preferably 1 to 100 ⁇ m, more preferably 1 to 50 ⁇ m, and even more preferably 3 to 20 ⁇ m.
  • the thickness of the hard coat layer is calculated by observing the cross section of the hard coat film with an optical microscope.
  • the cross-section sample can be prepared by a microtome method using a cross-section cutting device Ultra Microtome, a cross-section processing method using a focused ion beam (FIB) device, or the like.
  • the hard coat film of the present invention may have other layers in addition to the hard coat layer.
  • a mode in which a low refractive index layer for imparting antireflection property and a scratch resistant layer for imparting scratch resistance are preferably mentioned on the hard coat layer, and a plurality of these may be provided.
  • the hard coat film of the present invention preferably has a scratch resistant layer on the surface of the hard coat layer opposite to the base material, whereby scratch resistance can be further improved.
  • the scratch-resistant layer preferably contains a cured product of a compound having two or more (meth) acryloyl groups in one molecule (also referred to as “polyfunctional (meth) acrylate compound)”.
  • the polyfunctional (meth) acrylate compound is preferably a compound having three or more (meth) acryloyl groups in one molecule.
  • the polyfunctional (meth) acrylate compound may be a crosslinkable monomer, a crosslinkable oligomer, or a crosslinkable polymer.
  • polyfunctional (meth) acrylate compound examples include an ester of a polyhydric alcohol and (meth) acrylic acid. Specifically, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipenta.
  • Elythritol tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol hexa (meth) acrylate, etc. can be mentioned, but in terms of high cross-linking, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol Pentaacrylate, dipentaerythritol hexaacrylate, or a mixture thereof is preferable.
  • Only one type of polyfunctional (meth) acrylate compound may be used, or two or more types having different structures may be used in combination.
  • the content of the cured product of the polyfunctional (meth) acrylate compound is preferably 80% by mass or more, more preferably 85% by mass or more, and further preferably 90% by mass or more, based on the total mass of the scratch-resistant layer.
  • the scratch-resistant layer may contain components other than the above, and may contain, for example, inorganic particles, a leveling agent, an antifouling agent, an antistatic agent, an interlayer adhesion agent, a slip agent, and the like.
  • the interlayer adhesion agent refers to a component that adheres the hard coat and the scratch resistant layer when the scratch resistant layer and the hard coat layer are laminated.
  • the interlayer adhesion agent preferably contains both the cross-linking group of the curing component of the hard coat layer and the scratch resistant layer. Further, it is preferable that the slip agent contains the following fluorine-containing compound.
  • the fluorine-containing compound may be a monomer, an oligomer, or a polymer.
  • the fluorine-containing compound preferably has a substituent that contributes to bond formation or compatibility with the polyfunctional (meth) acrylate compound in the scratch-resistant layer.
  • the substituents may be the same or different, and it is preferable that there are a plurality of the substituents.
  • the substituent is preferably a polymerizable group, and may be a polymerizable reactive group exhibiting any one of radical polymerizable, cationically polymerizable, anionic polymerizable, contractile polymerizable and addition polymerizable, as an example of a preferable substituent.
  • Examples include acryloyl group, methacryloyl group, vinyl group, allyl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group and amino group. Among them, a radically polymerizable group is preferable, and an acryloyl group and a methacryloyl group are particularly preferable.
  • the fluorine-containing compound may be a polymer or an oligomer with a compound containing no fluorine atom.
  • preferable fluorine-containing compounds include R-2020, M-2020, R-3833, M-3833 and Optool DAC (trade name) manufactured by Daikin Chemical Industries, Ltd., and Megafuck F-171 manufactured by DIC Corporation. , F-172, F-179A, RS-78, RS-90, Defenser MCF-300 and MCF-323 (hereinafter referred to as trade names), but are not limited thereto.
  • the amount of the fluorine-containing compound added is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, still more preferably 0.5 to 5% by mass, based on the total mass of the scratch-resistant layer. 0.5 to 2% by mass is particularly preferable.
  • the thickness of the scratch-resistant layer is preferably 0.1 ⁇ m to 4 ⁇ m, more preferably 0.1 ⁇ m to 2 ⁇ m, and particularly preferably 0.1 ⁇ m to 1 ⁇ m.
  • the present invention also relates to an article provided with the above-mentioned hard coat film of the present invention and an image display device provided with the above-mentioned hard coat film of the present invention.
  • the hard coat film of the present invention is particularly preferably applied to a flexible display such as a smartphone.
  • the method for producing a hard coat film of the present invention is not particularly limited, but as one of preferred embodiments, after forming at least one hard coat layer on the temporary support, the hard coat film is formed through an adhesive layer.
  • a method (aspect A) of transferring the hard coat layer from the temporary support onto the substrate can be mentioned.
  • the hard coat layer is transferred from the temporary support to the protective film, and then the hard coat layer is further passed through the adhesive layer.
  • Aspect B can be mentioned as a method of transferring from a protective film onto a substrate.
  • a composition for forming a hard coat layer is applied onto a temporary support, dried, and then cured to form at least one hard coat layer.
  • FIG. 3 and 4 show schematic views for explaining the method for producing the hard coat film of the aspect A.
  • FIG. 3 shows a state in which the hard coat layer 4 is formed on the temporary support 6 by performing the above step (1).
  • (B) represents a state in which the base material 1 is laminated on the side of the hard coat layer 4 opposite to the temporary support 6 via the adhesive layer 3 by performing the above step (2).
  • (C) represents a state in which the step (3) is performed and a part of the adhesive is impregnated into the base material 1 to form the mixed layer 2.
  • (D) represents a state in which ultraviolet rays (UV) are irradiated from the temporary support 6 side as an example of the step (4).
  • UV ultraviolet rays
  • FIG. 4 schematically shows the manufacturing method of the aspect A of the hard coat film 11 having the scratch resistant layer, and is the same as that of FIG. 3 except that the scratch resistant layer 5 is added.
  • the step (1) is a step of applying the composition for forming a hard coat layer on the temporary support, drying the composition, and then curing the composition to form at least one hard coat layer.
  • the temporary support is not particularly limited as long as it has a smooth surface.
  • the temporary support preferably has a surface roughness of about 30 nm or less and does not interfere with the application of the composition for forming a hard coat layer, and a temporary support made of various materials is used.
  • a polyethylene terephthalate (PET) film, a cycloolefin resin film, a triacetyl cellulose (TAC) film and the like are preferably used.
  • the surface roughness is measured using SPA-400 (manufactured by Hitachi High-TechnoScience) under the measurement conditions of a measurement range of 5 ⁇ m ⁇ 5 ⁇ m, a measurement mode: DFM, and a measurement frequency: 2 Hz.
  • composition for forming a hard coat layer is a composition for forming the above-mentioned hard coat layer.
  • the composition for forming a hard coat layer usually takes the form of a liquid.
  • the composition for forming a hard coat layer is preferably prepared by dissolving or dispersing a curable resin and, if necessary, various additives and a polymerization initiator in an appropriate solvent.
  • the concentration of the solid content is generally about 10 to 90% by mass, preferably about 20 to 80% by mass, and particularly preferably about 40 to 70% by mass.
  • the curable resin preferably contains a cationic photopolymerization initiator or a radical photopolymerization initiator, depending on the type of polymerizable group contained therein. Only one kind of initiator may be used, or two or more kinds having different structures may be used in combination.
  • the cationic photopolymerization initiator may be any as long as it can generate a cation as an active species by light irradiation, and a known cationic photopolymerization initiator can be used without any limitation. Specific examples thereof include known sulfonium salts, ammonium salts, iodonium salts (for example, diaryliodonium salts), triarylsulfonium salts, diazonium salts, iminium salts and the like.
  • a cationic photopolymerization initiator represented by the formulas (25) to (28) shown in paragraphs 0050 to 0053 of JP-A-8-143806, paragraph of JP-A-8-283320.
  • Examples thereof include those exemplified as the cationic polymerization catalyst in 0020.
  • the cationic photopolymerization initiator can be synthesized by a known method and is also available as a commercially available product.
  • Commercially available products include, for example, CI-1370, CI-2064, CI-2397, CI-2624, CI-2739, CI-2734, CI-2758, CI-2823, CI-2855 and CI-5102 manufactured by Nippon Sotatsu. Etc., PHOTOINITIATOR 2047 manufactured by Rhodia, UVI-6974, UVI-6990 manufactured by Union Carbite, CPI-10P manufactured by Sun Appro, and the like.
  • a diazonium salt, an iodonium salt, a sulfonium salt, and an iminium salt are preferable from the viewpoint of the sensitivity of the photopolymerization initiator to light, the stability of the compound, and the like. Further, from the viewpoint of light resistance, the iodonium salt is most preferable.
  • Specific commercial products of the iodonium salt-based cationic photopolymerization initiator include, for example, B2380 manufactured by Tokyo Kasei Co., Ltd., BBI-102 manufactured by Midori Kagaku Co., Ltd., WPI-113 manufactured by Wako Pure Chemical Industries, Ltd., and Wako Pure Chemical Industries, Ltd. WPI-124, WPI-169 manufactured by Wako Pure Chemical Industries, Ltd., WPI-170 manufactured by Wako Pure Chemical Industries, Ltd., and DTBPI-PFBS manufactured by Toyo Synthetic Chemical Industries, Ltd. can be mentioned.
  • the content of the polymerization initiator in the composition for forming a hard coat layer may be appropriately adjusted within a range in which the polymerization reaction (cationic polymerization) of the curable resin proceeds satisfactorily, and is not particularly limited. For example, it is in the range of 0.1 to 200 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the curable resin.
  • the radical photopolymerization initiator may be any one capable of generating radicals as an active species by light irradiation, and known radical photopolymerization initiators can be used without any limitation.
  • radical photopolymerization initiator triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethyl benzoic acid, 4- Ethyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4- Diisopropylthioxanson or the like may be used in combination.
  • the above radical photopolymerization initiators and auxiliaries can be synthesized by known methods and are also available as commercial products.
  • the content of the radical photopolymerization initiator in the composition for forming a mixed layer may be appropriately adjusted within a range in which the polymerization reaction (radical polymerization) of the radically polymerizable compound proceeds satisfactorily, and is not particularly limited. ..
  • it is in the range of 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the curable resin.
  • composition for forming a hard coat layer may further contain one or more optional components in addition to the above-mentioned curable resin and polymerization initiator.
  • optional component include a solvent and various additives.
  • solvent As the solvent that can be contained as an optional component, an organic solvent is preferable, and one kind or two or more kinds of organic solvents can be mixed and used at an arbitrary ratio.
  • organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol, and i-butanol; ketones such as acetone, methylisobutylketone, methylethylketone, and cyclohexanone; cellosolves such as ethylcellosolve; toluene.
  • Aromatic substances such as xylene; glycol ethers such as propylene glycol monomethyl ether; acetate esters such as methyl acetate, ethyl acetate and butyl acetate; diacetone alcohol and the like.
  • the amount of the solvent in the composition can be appropriately adjusted within a range in which the coating suitability of the composition can be ensured.
  • the total amount of the polyorganosylsesquioxane (a1) and the polymerization initiator can be 50 to 500 parts by mass, preferably 80 to 200 parts by mass with respect to 100 parts by mass.
  • the composition may further optionally contain one or more of the known additives, if necessary.
  • additives include dispersants, leveling agents, antifouling agents, antistatic agents, ultraviolet absorbers and the like.
  • dispersants for details thereof, for example, paragraphs 0032 to 0034 of JP2012-229412 can be referred to.
  • the present invention is not limited to these, and various additives generally used in the polymerizable composition can be used. Further, the amount of the additive added to the composition may be appropriately adjusted, and is not particularly limited.
  • composition for forming a hard coat layer used in the present invention can be prepared by mixing the various components described above simultaneously or sequentially in any order.
  • the preparation method is not particularly limited, and a known stirrer or the like can be used for the preparation.
  • the method for applying the composition for forming a hard coat layer is not particularly limited, and a known method can be used. For example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method and the like can be mentioned.
  • the type of ionizing radiation in curing the hard coat layer is not particularly limited, and examples thereof include X-rays, electron beams, ultraviolet rays, visible light, and infrared rays, but ultraviolet rays are preferably used.
  • the irradiation dose of ionizing radiation for example when the coating film is ultraviolet-curable, preferably to cure the curable compound by irradiation with irradiation dose of ultraviolet rays of 10mJ / cm 2 ⁇ 6000mJ / cm 2 by an ultraviolet lamp. More preferably 50mJ / cm 2 ⁇ 6000mJ / cm 2, further preferably 100mJ / cm 2 ⁇ 6000mJ / cm 2. It is also preferable to combine heating during ionizing radiation irradiation in order to promote curing of the coating film.
  • the heating temperature is preferably 40 ° C. or higher and 140 ° C. or lower, and preferably 60 ° C. or higher and 140 ° C. or lower. It is also preferable to irradiate the ionizing radiation a plurality of times.
  • the oxygen concentration at the time of curing is preferably 0 to 1.0% by volume, more preferably 0 to 0.1% by volume, and most preferably 0 to 0.05% by volume. By making the oxygen concentration at the time of curing smaller than 1.0% by volume, it becomes less susceptible to the inhibition of curing by oxygen, and a strong film is formed.
  • the specific configuration when the hard coat film includes two or more hard coat layers, or when the hard coat film contains other layers described above in addition to the hard coat layer is not particularly limited, but a layer applied directly on the temporary support.
  • a structure in which (that is, the layer that becomes the outermost surface of the hard coat film) is a scratch resistant layer is preferable because the scratch resistance is good.
  • each layer can be designed so that the adhesion between the layers is good. preferable.
  • Specific examples thereof include a method in which the reactive groups of the curable resins in adjacent layers are used as reactive groups capable of binding to each other, and a method in which the above-mentioned interlayer adhesion agent is used. Further, from the same viewpoint, it is preferable that the layer formed first is cured by semi-curing and then the layer formed later is laminated.
  • the conditions for semi-curing for example if the coating is UV curable, preferably to cure the curable compound by irradiation with irradiation dose of ultraviolet rays 2mJ / cm 2 ⁇ 1000mJ / cm 2 by an ultraviolet lamp. More preferably 2mJ / cm 2 ⁇ 100mJ / cm 2, and further preferably from 5mJ / cm 2 ⁇ 50mJ / cm 2.
  • an ultraviolet lamp More preferably 2mJ / cm 2 ⁇ 100mJ / cm 2, and further preferably from 5mJ / cm 2 ⁇ 50mJ / cm 2.
  • a metal halide lamp, a high-pressure mercury lamp, or the like is preferably used.
  • the oxygen concentration at the time of curing is not particularly limited, but when a component (compound having a (meth) acryloyl group) that is susceptible to curing inhibition is contained, the oxygen concentration should be adjusted to 0.1 to 2.0% by volume. It is preferable because it is possible to form a semi-cured state in which the surface functionality remains.
  • the hard coat layer in direct contact with the adhesive layer is cured or cured. It is also preferable to include a step of accelerating the curing of all layers later. Hardness can be improved by accelerating the curing of all layers.
  • the method for accelerating the curing is the same method as the above-mentioned curing of the hard coat layer.
  • the step (2) is a step of laminating a film base material containing at least one of a polyimide resin, a polyamide-imide resin, or an aramid resin on the side opposite to the temporary support of the hard coat layer via an adhesive. ..
  • the adhesive layer used is as described above.
  • the method of providing the adhesive layer is not particularly limited, but for example, the adhesive is injected between the side opposite to the temporary support of the hard coat layer and the base film and passed through the nip roller to be uniform. It is possible to use a method of providing an adhesive layer having a large thickness, a method of uniformly applying the adhesive on the side opposite to the temporary support of the hard coat layer or on the base material, and a method of adhering to the other film. it can.
  • surface treatment Before performing the step (2), it is preferable to perform surface treatment on the side opposite to the temporary support of the hard coat layer or the surface of the base material, if necessary.
  • the surface treatment in this case include a method of modifying the film surface by corona discharge treatment, glow discharge treatment, ultraviolet irradiation treatment, flame treatment, ozone treatment, acid treatment, alkali treatment and the like.
  • the glow discharge treatment referred to here may be low-temperature plasma generated under a low-pressure gas of 10-3 to 20 Torr, and plasma treatment under atmospheric pressure is also preferable.
  • the plasma-excited gas is a gas that is plasma-excited under the above conditions, and includes fluorocarbons such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, and tetrafluoromethane, and mixtures thereof. Be done. Details of these are described in detail on pages 30 to 32 of Publication No. 2001-1745 of the Institute of Invention and Innovation (issued on March 15, 2001, Institute of Invention and Innovation), and are preferably used in the present invention. be able to. Of these treatments, plasma treatment and corona discharge treatment are preferable.
  • Examples of the plasma treatment include vacuum glow discharge, atmospheric pressure glow discharge, and the like, and other methods include frame plasma treatment and the like.
  • the methods described in JP-A-6-123062, JP-A-11-293011, JP-A-11-5857 and the like can be used.
  • corona discharge processing The corona discharge treatment can be performed by any conventionally known method, for example, Japanese Patent Application Laid-Open No. 48-5043, 47-51905, 47-28067, 49-83767, 51-41770. , 51-131576, Japanese Patent Application Laid-Open No. 2001-272503, and the like.
  • the step (3) is a step of impregnating a part of the adhesive into the base material.
  • the step (3) By impregnating a part of the adhesive layer into the base material, the light-resistant adhesion of the hard coat film can be improved. Since the ease of penetration of the adhesive in the step (3) differs depending on the type of the base material used, it can be appropriately adjusted depending on the components of the adhesive and the process. Examples of the method for adjusting the mixed layer by the process include the temperature and time of the step (3). The longer the time of the step (3) and the higher the temperature, the more the adhesive can be permeated into the base material.
  • the temperature and time of the step (3) are not particularly limited, and examples thereof include 30 ° C. to 200 ° C. (preferably 40 ° C. to 150 ° C.). The time may be 30 seconds to 5 minutes (preferably 1 minute to 4 minutes).
  • the step (4) is a step of adhering the hard coat layer and the base material by irradiating with heating or active energy rays.
  • the method of adhering the hard coat layer and the base material is not particularly limited, and can be appropriately changed depending on the components of the adhesive layer used.
  • the solvent water, alcohol, etc.
  • thermosetting adhesives thermosetting by heating.
  • the type of active energy ray is not particularly limited, and examples thereof include X-ray, electron beam, ultraviolet ray, visible light, and infrared ray, but ultraviolet ray is preferably used.
  • the surface to be irradiated with the active energy rays in the step (4) is not particularly specified, and can be determined according to the transmittance of the active energy rays used in each member.
  • the curing conditions in the case of ultraviolet curing are the same as the curing conditions of the hard coat layer described above. In step (4), both heating and irradiation with active energy rays may be performed.
  • the step (5) is a step of peeling the temporary support from the hard coat layer.
  • the peeling force when peeling the temporary support from the hard coat layer in the step (5) is that the laminate obtained in the step (4) is cut to a width of 25 mm, and the base material side of the laminate is made of glass with an adhesive. It can be quantified by measuring the peeling force when the film is immobilized on a substrate and peeled off at a speed of 300 mm / min in the 90 ° direction.
  • the peeling force measured by the above method is preferably 0.1 N / 25 mm to 10.0 N / 25 mm, and more preferably 0.2 N / 25 mm to 8.0 N / 25 mm.
  • the peeling force is 0.1 N / 25 mm or more, the hard coat layer is difficult to peel off from the temporary support in steps other than step (5), which is preferable.
  • the peeling force is 10.0 N / 25 mm or less, the hard coat layer is unlikely to remain partially on the temporary support or the adhesive layer is unlikely to be peeled off in the step (5), which is preferable.
  • the peeling force between the temporary support and the hard coat layer varies depending on the type of the temporary support and the hard coat layer used, and can be appropriately adjusted.
  • Examples of the adjusting means include a method of using a temporary support that has been subjected to a mold release treatment, a method of adding a compound that promotes peeling to the composition for forming a hard coat layer, and the like.
  • Specific examples of the compound that promotes exfoliation include a compound having a long-chain alkyl group, a compound containing fluorine, a compound containing silicone, and the like.
  • the surface of the hard coat layer opposite to the base material may be surface-treated.
  • the type of surface treatment is not particularly limited, and examples thereof include treatments for imparting antifouling property, fingerprint resistance, and slipperiness.
  • the fluorine-containing compound and the leveling agent may not be sufficiently unevenly distributed on the outermost surface. In such a case, it is preferable to carry out the above treatment because it is possible to impart the water repellency and scratch resistance required for the hard coat surface.
  • Aspect B is specifically a production method including the following steps (1'), (A) to (B), (2') to (5').
  • FIG. 5 and 6 show schematic views for explaining the method for producing the hard coat film of the aspect B.
  • FIG. 5 shows a state in which the hard coat layer 4 is formed on the temporary support 6 by performing the above step (1').
  • (B) shows a state in which the protective film 9 is attached to the side of the hard coat layer 4 opposite to the temporary support 6 after the above step (A) is performed.
  • the protective film 9 includes an adhesive layer 7 and a support 8 for the protective film.
  • C represents a state in which the temporary support 6 is peeled from the hard coat layer 4 by performing the step (B).
  • step (d) step (2') is performed, and at least selected from the group consisting of a polyimide resin, a polyamide-imide resin, and an aramid resin via an adhesive layer 3 on the side of the hard coat layer 4 opposite to the protective film 9.
  • It represents a state in which the film base materials 1 containing one are laminated.
  • (E) represents a state in which the step (3') is performed and a part of the adhesive layer 3 is impregnated into the base material 1 to form the mixed layer 2.
  • (F) represents a state in which ultraviolet rays (UV) are irradiated from the protective film 9 side as an example of the step (4').
  • UV ultraviolet rays
  • FIG. 6 schematically shows the manufacturing method of the aspect B of the hard coat film 11 having the scratch resistant layer, and is the same as that of FIG. 5 except that the scratch resistant layer 5 is added.
  • the step (1') is the same as the step (1) of the aspect A. Also in the step (1'), as in the step (1), a specific configuration when the hard coat film contains two or more hard coat layers, or when the hard coat layer includes the other layers described above in addition to the hard coat layer. Is not particularly limited, but in the step (1'), a structure in which the layer to be laminated last is a scratch-resistant layer is preferable from the viewpoint of the scratch-resistant layer.
  • the step (A) is a step of laminating a protective film on the side opposite to the temporary support of the hard coat layer.
  • the protective film represents a laminated body composed of a support / adhesive layer, and it is preferable to bond the adhesive layer side of the protective film to the hard coat layer.
  • the protective film can be obtained by peeling the release film from the protective film with a release film composed of a support / adhesive layer / release film.
  • a commercially available protective film with a release film can be preferably used as the protective film with a release film.
  • AS3-304, AS3-305, AS3-306, AS3-307, AS3-310, AS3-0421, AS3-0520, AS3-0620, LBO-307, NBO-manufactured by Fujimori Kogyo Co., Ltd. 0424, ZBO-0421, S-362, TFB-4T3-367AS and the like can be mentioned.
  • the step (B) is a step of peeling the temporary support from the hard coat layer.
  • the adhesive force between the protective film and the hard coat layer needs to be higher than the peeling force between the temporary support and the hard coat layer.
  • the method for adjusting the peeling force between the temporary support and the hard coat layer is not particularly limited, but for example, a method of reducing the peeling force between the temporary support and the hard coat layer by using a temporary support that has been subjected to a mold release treatment. Can be mentioned.
  • the method for adjusting the adhesion between the protective film and the hard coat layer is not particularly limited. For example, in step (A), after the protective film is attached to the semi-cured hard coat layer, the hard coat layer is cured. There is a way to do it.
  • the step (2') is the same as the step (2) of the aspect A except that the temporary support is a protective film.
  • the step (3') is the same as the step (3) of the aspect A.
  • the step (4') is the same as the step (4) of the aspect A except that the temporary support is a protective film.
  • the step (5') is the same as the step (5) of the aspect A except that the temporary support is a protective film.
  • the number of steps is larger than that in the aspect A, but when the hard coat layer is formed, the temporary support is not present on the outermost surface of the hard coat, so that the fluorine-containing compound and the leveling agent are placed on the outermost surface. It is desirable when it is easy to unevenly distribute and it is desired to impart water repellency and scratch resistance to the hard coat surface.
  • the step (5) when it is desired to further improve the water repellency and scratch resistance, after the step (5), the surface of the hard coat layer opposite to the base material is subjected to the same surface treatment as in aspect A. You may.
  • ⁇ Preparation of base material> (Manufacturing of polyamide-imide powder) After adding 832 g of N, N-dimethylacetamide (DMAc) under a nitrogen stream to a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler, the temperature of the reactor was changed to 25. It was set to °C. To this, 64.046 g (0.2 mol) of bistrifluoromethylbenzidine (TFDB) was added and dissolved.
  • DMAc N, N-dimethylacetamide
  • TFDB bistrifluoromethylbenzidine
  • This reaction solution was heated to 80 ° C., and the polycondensation reaction was carried out under a nitrogen stream for 10 hours. Then, the reaction solution was cooled, 300 g of 5 mass% saline was added, and the organic layer was extracted. The organic layer was washed twice with 300 g of 5 mass% saline and 300 g of pure water, and then concentrated under the conditions of 1 mmHg and 50 ° C. to form a colorless and transparent liquid as a MIBK solution having a solid content concentration of 59.8 mass%.
  • Object ⁇ Compound (X) which is a polyorganosyl sesquioxane having an alicyclic epoxy group (Rb: 2- (3,4-epoxycyclohexyl) ethyl group, Rc: methyl group, q in the general formula (1))
  • Rb 2- (3,4-epoxycyclohexyl) ethyl group
  • Rc methyl group
  • MIBK methyl isobutyl ketone
  • the interlayer adhesion polymer is a compound that is unevenly distributed at the air interface of the hard coat layer and contributes to imparting adhesion to the scratch resistant layer.
  • composition for forming a hard coat layer HC-1 CPI-100P, leveling agent-1, and MIBK (methyl isobutyl ketone) are added to the MIBK solution containing the above compound (X), and the concentration of each component is adjusted to the following concentration, and the mixture is placed in a mixing tank. It was charged and stirred. The obtained composition was filtered through a polypropylene filter having a pore size of 0.4 ⁇ m to obtain a hard coat layer forming composition HC-1.
  • Compound (X) 98.7 parts by mass CPI-100P 1.3 parts by mass Leveling agent-1 0.01 parts by mass Methyl isobutyl ketone 100.0 parts by mass
  • composition for forming a hard coat layer HC-2 HC-2 was prepared by changing from HC-1 to the following composition ratio.
  • composition SR-1 for forming a scratch resistant layer
  • composition SR-1 for forming a scratch resistant layer
  • Each component was charged into a mixing tank with the composition described below, stirred, and filtered through a polypropylene filter having a pore size of 0.4 ⁇ m to obtain a scratch-resistant layer forming composition SR-1.
  • composition SR-2 for forming a scratch resistant layer was prepared by changing the composition ratio from SR-1 to the following.
  • the compounds used in the scratch-resistant layer forming composition are as follows.
  • DPHA Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.
  • RS-90 Sliding agent, manufactured by DIC Corporation
  • Compound P Photoacid generator represented by the following structural formula ( Wako Pure Chemical Industries, Ltd.)
  • UV curable adhesive composition UV-1 CEL2021P 70.0 parts by mass 1,4-butanediol diglycidyl ether 18.0 parts by mass 2-ethylhexyl glycidyl ether 10.0 parts by mass Irgacure 290 2.0 parts by mass
  • the compounds used in the ultraviolet curable adhesive composition are as follows.
  • CEL2021P The following compounds.
  • UV curable adhesive composition UV-2 CEL2021P 70.0 parts by mass 1,4-butanediol diglycidyl ether 18.0 parts by mass 2-ethylhexyl glycidyl ether 10.0 parts by mass Irgacure 290 3.0 parts by mass Ultraviolet absorber 10.5 parts by mass
  • the ultraviolet absorber 1 used in the curable adhesive composition is as follows. UV absorber 1:
  • Step (1) Formation of hard coat layer on temporary support
  • the scratch-resistant layer forming composition SR-1 was applied to a 100 ⁇ m polyethylene terephthalate film (FD100M, manufactured by FUJIFILM Corporation) as a temporary support using a die coater. After drying at 120 ° C. for 1 minute, it is resistant to ultraviolet rays under the conditions of an illuminance of 18 mW / cm 2 , an irradiation amount of 10 mJ / cm 2 , and an oxygen concentration of 1.0% using an air-cooled mercury lamp at 25 ° C. The scratch layer was semi-cured.
  • FD100M polyethylene terephthalate film
  • the composition for forming a hard coat layer HC-1 was applied to the side of the scratch-resistant layer opposite to the temporary support using a die coater. After drying for 1 minute at 120 ° C., using an air-cooled mercury lamp at a 25 ° C. conditions, illuminance 60 mW / cm 2, irradiation amount 600 mJ / cm 2, it was irradiated with ultraviolet rays under conditions of oxygen concentration 100 ppm. Furthermore by using an air-cooled mercury lamp at 100 ° C. conditions, fully cured the scratch layer and the hard coat layer by irradiation illuminance 60 mW / cm 2, irradiation amount 600 mJ / cm 2, the ultraviolet under the conditions of oxygen concentration 100ppm I let you.
  • Step (2) Formation of adhesive layer
  • a corona discharge treatment was performed on the surface of the hard coat layer prepared in the step (1) opposite to the scratch resistant layer.
  • a solid state corona discharge processor 6KVA model manufactured by Pillar
  • the corona discharge treatment was performed at 20 m / min.
  • the processing conditions were 0.375 kV ⁇ A ⁇ min / m 2
  • the processing discharge frequency was 9.6 kHz
  • the gap clearance between the electrode and the dielectric roll was 1.6 mm.
  • the corona discharge treatment surface side of the hard coat layer and the base material S-1 are overlapped while injecting the ultraviolet curable adhesive UV-1 between them, and by passing through a nip roller, the temporary support, the scratch resistant layer, A laminate having a hard coat layer, an adhesive layer, and a base material S-1 was formed.
  • Step (3) Formation of mixed layer
  • Step (4): Adhesion Step prepared in (3), from the opposite side of the base material of the laminate having a mixed layer, by using an air-cooled mercury lamp at a 25 ° C. conditions, illuminance 60 mW / cm 2, irradiation amount 600 mJ / cm 2 UV The adhesive layer was cured by irradiating with, and the hard coat layer and the base material S-1 were adhered to each other.
  • the hard coat film 1 was obtained by peeling the temporary support from the laminate obtained in the step (4) to which the hard coat layer and the base material S-1 were adhered.
  • Hard coat films 2 to 5 were obtained in the same manner as in Example 1 except that the film thickness of the hard coat layer, the base material, and the conditions for forming the mixed layer were changed as shown in Table 1.
  • the hard coat layer forming composition HC-1 was applied to a 100 ⁇ m polyethylene terephthalate film (FD100M, manufactured by FUJIFILM Corporation) as a temporary support using a die coater. After drying for 1 minute at 120 ° C., using an air-cooled mercury lamp at a 25 ° C. conditions, illuminance 60 mW / cm 2, irradiation amount 600 mJ / cm 2, it was irradiated with ultraviolet rays under conditions of oxygen concentration 100 ppm. Furthermore by using an air-cooled mercury lamp at 100 ° C. conditions, illuminance 60 mW / cm 2, irradiation amount 600 mJ / cm 2, was sufficiently cured hard coat layer by irradiation with ultraviolet rays under conditions of oxygen concentration 100 ppm.
  • Step (2) Formation of adhesive layer
  • the surface of the hard coat layer produced in the step (1) opposite to the temporary support side was subjected to a corona discharge treatment under the same conditions as in Example 1.
  • the corona discharge treatment surface side of the hard coat layer and the base material S-1 are overlapped while injecting the ultraviolet curable adhesive UV-1 between them, and by passing through a nip roller, the temporary support, the scratch resistant layer, A laminate having a hard coat layer, an adhesive layer, and a base material S-1 was formed.
  • Step (3) Formation of mixed layer
  • Step (4): Adhesion Step prepared in (3), from the opposite side of the base material of the laminate having a mixed layer, by using an air-cooled mercury lamp at a 25 ° C. conditions, illuminance 60 mW / cm 2, irradiation amount 600 mJ / cm 2 UV The adhesive layer was cured by irradiating with, and the hard coat layer and the base material S-1 were adhered to each other.
  • Step (5): Peeling of temporary support The hard coat film 6 was obtained by peeling the temporary support from the laminate obtained in the step (4) to which the hard coat layer and the base material S-1 were adhered.
  • a hard coat layer forming composition HC-2 was applied to the release-treated side of the non-silicone release film HP-A5 (manufactured by FUJI CORPORATION) using a die coater. After drying at 120 ° C. for 1 minute, the hard coat layer is irradiated with ultraviolet rays under the conditions of an illuminance of 18 mW / cm 2 , an irradiation amount of 10 mJ / cm 2 , and an oxygen concentration of 100 ppm using an air-cooled mercury lamp at 25 ° C. It was semi-cured.
  • the scratch-resistant layer forming composition SR-2 was applied to the side of the hard coat layer opposite to the temporary support using a die coater. After drying at 120 ° C. for 1 minute, the hard coat layer was cured under the conditions of an illuminance of 18 mW / cm 2 , an irradiation amount of 10 mJ / cm 2 , and an oxygen concentration of 1.0% using an air-cooled mercury lamp at 25 ° C. It was.
  • Step (A): Adhesion of hard coat protective film It is obtained by peeling the release film from the protective film with a release film (Musstack TFB AS3-304) manufactured by Fujimori Kogyo Co., Ltd. on the side opposite to the hard coat layer of the scratch resistant layer obtained in the step (1').
  • the protective film was attached so that the adhesive layer of the protective film faced the scratch-resistant layer.
  • a commercial laminator Bio330 manufactured by DAE-EL Co.
  • the temporary support was peeled off from the laminate obtained in the step (A).
  • Step (2'): Formation of adhesive layer The surface of the hard coat layer produced in the step (B) opposite to the scratch resistant layer was subjected to a corona discharge treatment under the same conditions as in the step (2) of Example 1. Next, the corona discharge-treated surface side of the hard coat layer and the base material S-1 are overlapped while injecting the ultraviolet curable adhesive UV-1 between them, and the nip roller is passed through the protective film and the scratch resistant layer. , A laminate having a hard coat layer, an adhesive layer and a base material S-1 was formed.
  • Step (3'): Formation of mixed layer A mixed layer was formed in the same manner as in step (3) of Example 1.
  • the hard coat film 7 was obtained by peeling the protective film from the laminate obtained in the step (4').
  • Example 6 In Example 6, immediately after passing through the nip roll in step (2), the same method was performed except that step (3) was not performed and bonding was performed by ultraviolet irradiation in step (4), and the hard coating of Comparative Example 1 was performed. I got a film.
  • Example 8 A hard coat film 8 was obtained in the same manner as in Example 1 except that the ultraviolet curable adhesive composition was changed as shown in Table 1.
  • the thickness of the hard coat layer, scratch resistant layer, adhesive layer, and mixed layer of the produced hard coat film is determined by cutting the hard coat film with a microtome and cutting the cross section with a scanning electron microscope (S-5200 manufactured by Hitachi High-Tech) and flight time. It was calculated by analysis with a type secondary ion mass spectrometer (TOF-SIMS V manufactured by ION-TOF) and is shown in Table 1. For the mixed layer, the thickness at which both the components of the base material and the adhesive layer were detected was calculated.
  • Pencil hardness The hard coat layer or scratch resistant layer side of the hard coat film was measured according to JIS K 5600-5-4 (1999) and evaluated in the following four stages.
  • the pencil hardness is practically required to be A to C, preferably A to B, and more preferably A.
  • the light-resistant adhesion was evaluated by the following method.
  • a grid test was conducted in accordance with JIS K5600. Specifically, 11 notches were made vertically and horizontally at 1 mm intervals on the surface of the hard coat layer or the scratch resistant layer side of the hard coat film to make 100 1 mm square grids.
  • a transparent pressure-sensitive adhesive tape (Cerotape (registered trademark) CT-15S manufactured by Nichiban Co., Ltd.) was attached onto this, and the tape was quickly peeled off, and the peeled portion was visually observed to evaluate the adhesion.
  • the measurement sample was evaluated after adjusting the humidity for 2 hours or more in a room having a temperature of 25 ° C. and a relative humidity of 60% before the adhesion evaluation.
  • Adhesion A Peeling point 0 squares
  • Adhesion B Peeling point 1 to 10 squares
  • Adhesion C Peeling point 11 to 49 squares
  • Adhesion D Peeling point 50 to 99 squares
  • Adhesion E Peeling point 100 squares or more (All pasted parts)
  • a super xenon weather meter SX75 manufactured by Suga Test Instruments Co., Ltd. was used for Xe irradiation.
  • Light-resistant adhesion requires A to C in practice, preferably A to B, and more preferably A.
  • the hard coat film of the example was excellent in all of pencil hardness, light adhesion resistance, and repeated bending resistance.
  • the hard coat film of Comparative Example 1 did not form a mixed layer, the pencil hardness was good, but the light-resistant adhesion was poor.
  • Base material 1 Base material 2 Mixed layer 3 Adhesive layer 4 Hard coat layer 5 Scratch resistant layer 6 Temporary support 7 Adhesive layer 8 Protective film support 9 Protective film 10, 11 Hard coat film UV UV

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Abstract

La présente invention concerne un film de revêtement dur qui comprend séquentiellement un matériau de base, une couche adhésive et une couche de revêtement dur dans cet ordre, le matériau de base étant un film qui contient au moins une résine choisie dans le groupe constitué par une résine polyimide, une résine polyamide-imide et une résine aramide ; et une couche mixte, dans laquelle les composants de la couche adhésive et les composants du matériau de base sont mélangés, étant présente entre la couche adhésive et le matériau de base. La présente invention concerne également un article pourvu du film de revêtement dur et un dispositif d'affichage d'image.
PCT/JP2020/015297 2019-04-12 2020-04-03 Film de revêtement dur, procédé de production associé, article pourvu d'un film de revêtement dur et appareil d'affichage d'image WO2020209194A1 (fr)

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JP2021513614A JP7291209B2 (ja) 2019-04-12 2020-04-03 ハードコートフィルムの製造方法
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CN202080028146.0A CN113678029B (zh) 2019-04-12 2020-04-03 硬涂膜及其制造方法、具备硬涂膜的物品及图像显示装置

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