WO2018037489A1 - Hard coat film - Google Patents
Hard coat film Download PDFInfo
- Publication number
- WO2018037489A1 WO2018037489A1 PCT/JP2016/074567 JP2016074567W WO2018037489A1 WO 2018037489 A1 WO2018037489 A1 WO 2018037489A1 JP 2016074567 W JP2016074567 W JP 2016074567W WO 2018037489 A1 WO2018037489 A1 WO 2018037489A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hard coat
- coat layer
- film
- less
- layer
- Prior art date
Links
Images
Classifications
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- 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
- C08J2379/00—Characterised by the use of 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to a hard coat film provided with a base film and a hard coat layer, and particularly to a hard coat film suitable for use in a flexible display.
- various displays such as a liquid crystal display (LCD), an organic EL display (OELD), and a touch panel are widely used.
- the surface of these various displays is often provided with a hard coat film in which a hard coat layer is provided on a base film in order to prevent scratches.
- a bendable display As a display as described above, a bendable display, a so-called flexible display has been developed.
- the flexible display is expected to have a wide range of uses, for example, for a stationary display that is bent and installed on a cylindrical column, or for a mobile display that can be folded and rolled.
- hard coat films for flexible displays hard coat films disclosed in Patent Documents 1 and 2 have been proposed.
- the flexible display may be repeatedly bent (bent) as described in Patent Document 3 instead of forming the curved surface only once.
- interference fringes may occur in the hard coat film due to various factors.
- interference fringes are generated in the hard coat film, there are problems that the appearance is also lowered and the visibility as a display is lowered.
- the present invention has been made in view of such a situation, and provides a hard coat film that has bending resistance capable of withstanding repeated bending, is less likely to curl, and is less likely to cause interference fringes. With the goal.
- the present invention provides a base film, a first hard coat layer laminated on at least one main surface side of the base film, and the first hard coat layer.
- a hard coat film comprising a second hard coat layer laminated on the main surface opposite to the base film side, wherein the base film is a polyimide film, and the first hard coat
- the layer and the second hard coat layer are made of different materials, and the difference between the refractive index of the first hard coat layer and the refractive index of the second hard coat layer is 0.04 or less in absolute value.
- a hard coat film characterized in that the total thickness of the first hard coat layer and the second hard coat layer is 7 ⁇ m or more and 35 ⁇ m or less (Invention 1).
- the base film is a polyimide film, and the total thickness of the first hard coat layer and the second hard coat layer is in the above range. Therefore, it has excellent bending resistance. Further, the difference between the refractive index of the first hard coat layer and the refractive index of the second hard coat layer is in the above range, and the thickness of the first hard coat layer and the thickness of the second hard coat layer. When the total is within the above range, the hard coat film is less prone to interference fringes. Further, the first hard coat layer and the second hard coat layer are made of different materials, and the total thickness of the first hard coat layer and the second hard coat layer is in the above range. Thus, the hard coat film is less likely to curl and has excellent scratch resistance.
- the first hard coat layer and the second hard coat layer are made of a material obtained by curing a composition containing an active energy ray-curable component, and the first hard coat layer It is preferable that the coat layer is made of a material softer than the second hard coat layer (Invention 2).
- the first hard coat layer is made of a material obtained by curing a composition containing an active energy ray-curable component modified with an alkylene oxide
- the second hard coat layer The coating layer is preferably made of a material obtained by curing a composition containing an active energy ray-curable component that has not been modified with an alkylene oxide (Invention 3).
- the active energy ray-curable component is preferably a polyfunctional (meth) acrylate monomer (Invention 4).
- the refractive index of the first hard coat layer is preferably 1.40 or more and 1.80 or less (Invention 5).
- the refractive index of the second hard coat layer is preferably 1.40 or more and 1.80 or less (Invention 6).
- the thickness of the first hard coat layer is preferably 3 ⁇ m or more and 30 ⁇ m or less (Invention 7).
- the thickness of the second hard coat layer is preferably 0.75 ⁇ m or more and 10 ⁇ m or less (Invention 8).
- the thickness of the polyimide film is preferably 5 ⁇ m or more and 300 ⁇ m or less (Invention 9).
- the hard coat film according to the above inventions (Inventions 1 to 9) is preferably used as a flexible member constituting a flexible display (Invention 10).
- an adhesive layer is laminated on at least one main surface side of the base film (Invention 11).
- the hard coat film according to the present invention is excellent in scratch resistance, has bending resistance capable of withstanding repeated bending, hardly causes curling, and does not easily cause interference fringes.
- FIG. 1 is a cross-sectional view of a hard coat film according to an embodiment of the present invention.
- a hard coat film 1 according to the present embodiment includes a base film 2, a first hard coat layer 3 laminated on one main surface side (the upper side in FIG. 1) of the base film, and a first hard coat. It comprises a second hard coat layer 4 laminated on the main surface side (upper side in FIG. 1) opposite to the base film 2 side in the layer 3.
- the first hard coat layer 3 and the second hard coat layer 4 are made of different materials.
- the base film 2 is a polyimide film.
- the base film 2 is a polyimide film
- the base film 2 can be prevented from being bent or whitened. Excellent flexibility. Therefore, when the flexible display using the hard coat film 1 according to the present embodiment is repeatedly bent at a predetermined portion, the appearance of the bent portion and the visibility are suppressed from being lowered at the bent portion. Is done.
- the difference between the refractive index of the first hard coat layer 3 and the refractive index of the second hard coat layer 4 is 0.04 or less in absolute value
- the thickness of the first hard coat layer 3 and the second hard coat layer 3 The total thickness of the two hard coat layers 4 is 7 ⁇ m or more and 35 ⁇ m or less.
- the total thickness of the first hard coat layer 3 and the second hard coat layer 4 is 7 ⁇ m or more, the thickness becomes considerably larger than the wavelength of light, and the first hard coat layer 4 Interference between the light reflected at the interface between the coat layer 3 and the base film 2 and the reflected light on the surface of the second hard coat layer 4 is less likely to occur. Furthermore, when the intensity (reflection intensity) of the light reflected at the interface between the first hard coat layer 3 and the base film 2 passes through the first hard coat layer 3 and the second hard coat layer 4. Since it becomes weak, interference with the reflected light on the surface of the second hard coat layer 4 also hardly occurs from such a side surface. By these actions, generation of interference fringes is suppressed in the hard coat film 1.
- the measurement wavelength of the refractive index in this specification shall be 589 nm, and measurement temperature shall be 25 degreeC. Details of the method of measuring the refractive index are as shown in the test examples described later.
- the difference between the refractive index of the first hard coat layer 3 and the refractive index of the second hard coat layer 4 is preferably 0.02 or less in absolute value, particularly 0. .01 or less is preferable.
- the hard coat film 1 has excellent scratch resistance.
- the total thickness of the first hard coat layer 3 and the second hard coat layer 4 is preferably 9 ⁇ m or more, particularly 10 ⁇ m or more. Preferably there is.
- the total thickness of the first hard coat layer 3 and the second hard coat layer 4 is 35 ⁇ m or less, the hard coat film 1 is easy to bend and has excellent bending resistance. It becomes. From such a viewpoint, the total thickness of the first hard coat layer 3 and the second hard coat layer 4 is preferably 30 ⁇ m or less, and particularly preferably 25 ⁇ m or less.
- the total thickness of the first hard coat layer 3 and the second hard coat layer 4 is in the above range, and the first hard coat layer 3 and the second hard coat layer 4 are Since the first hard coat layer 3 is made of a material softer than the second hard coat layer 4, curling hardly occurs when the hard coat film 1 is manufactured.
- the base film 2 of the hard coat film 1 according to the present embodiment is a polyimide film and is transparent and yellowish when used for a display. It is preferable that it is a polyimide film with few. Thereby, it is possible to obtain a display (in particular, a flexible display) that displays a clear and highly reproducible image.
- the polyimide film used in the present embodiment preferably has a transmittance of 75% or more at a wavelength of 550 nm, more preferably 80% or more, and 85% or more from the viewpoint of transparency. Some are particularly preferred.
- the transmittance measuring method in this specification is as shown in the examples described later.
- a polyimide film used by this embodiment that whose absolute value of b * of the L * a * b * color system by a transmission measurement method is 10 or less is preferable from a viewpoint of reducing yellowishness, 5 What is below is more preferable, and what is 3 or less is especially preferable.
- the measurement method of b * in this specification is as shown in the examples described later.
- the polyimide film refers to a film containing polyimide, that is, a polymer having an imide bond in the main chain, preferably 50% by mass or more, particularly preferably 80% by mass or more, and more preferably 90% by mass or more.
- Poly (meth) acrylimide does not have an imide bond in the main chain, and is not polyimide, but when such a poly (meth) acrylimide film is repeatedly bent, whitening occurs.
- a polyimide film is usually formed by polymerizing a tetracarboxylic anhydride (preferably an aromatic tetracarboxylic dianhydride) and a diamine (preferably an aromatic diamine) in a solution to form a polyamic acid, and then the polyamide film.
- the acid can be obtained by forming the film into a film and then dehydrating and ring-closing the polyamic acid moiety, but is not limited thereto.
- the polyimide in the polyimide film may be modified.
- the aromatic ring usually contained in polyimide may be modified with an aliphatic hydrocarbon, whereby the base film 2 is excellent in adhesiveness with the second hard coat layer 4.
- the lower limit of the refractive index of the polyimide film is usually 1.50 or more, preferably 1.55 or more, and more preferably 1.60 or more.
- the refractive index of a polyimide film is 1.85 or less normally as an upper limit, Preferably it is 1.80 or less, More preferably, it is 1.75 or less.
- primer treatment or oxidation may be performed on one side or both sides as desired for the purpose of improving adhesion with a layer (second hard coat layer 4 or an adhesive layer described later) provided on the surface.
- Surface treatment can be performed by a method, an uneven method or the like.
- the oxidation method include corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment, and examples of the unevenness method include a sand blast method and a solvent treatment method.
- the thickness of the polyimide film is preferably 5 ⁇ m or more as a lower limit, particularly preferably 7.5 ⁇ m or more, and more preferably 10 ⁇ m or more.
- the upper limit of the thickness of the polyimide film is preferably 300 ⁇ m or less, particularly preferably 90 ⁇ m or less, more preferably 50 ⁇ m or less, and most preferably 30 ⁇ m or less.
- the polyimide film is easily colored, when the thickness of the polyimide film is not more than the above, transparency is ensured and the b * value is also kept low, and it can be suitably used for optical use. Moreover, when the thickness of the polyimide film is not more than the above, the hard coat film 1 exhibits predetermined flexibility and is easily bent.
- the first hard coat layer 3 of the hard coat film 1 according to this embodiment is laminated on one main surface side (the upper side in FIG. 1) of the base film 2; As described above, the second hard coat layer 4 exhibits the effect of suppressing the generation of interference fringes and scratch resistance.
- the material of the first hard coat layer 3 has a refractive index difference from the refractive index of the second hard coat layer 4 in the above-described range, and exhibits desired scratch resistance together with the second hard coat layer 4. If it is, it will not be specifically limited.
- the first hard coat layer 3 is preferably made of a material obtained by curing a composition containing an active energy ray-curable component, and particularly preferably made of a material softer than the second hard coat layer 4. . Specifically, it is preferably made of a material obtained by curing a composition containing an active energy ray-curable component modified with alkylene oxide.
- Active energy ray curable component examples include polyfunctional (meth) acrylate monomers, (meth) acrylate prepolymers, active energy ray curable polymers, and the like. However, among them, a polyfunctional (meth) acrylate monomer and / or a (meth) acrylate prepolymer is preferable, and a polyfunctional (meth) acrylate monomer is more preferable.
- the polyfunctional (meth) acrylate monomer and the (meth) acrylate prepolymer may be used alone or in combination.
- (meth) acrylate means both acrylate and methacrylate. The same applies to other similar terms.
- multifunctional (meth) acrylate monomers examples include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene glycol diene.
- polyfunctional (meth) acrylate monomers modified with alkylene oxide are preferable from the viewpoint of bending resistance and curling suppression of the obtained hard coat film.
- alkylene oxide-modified trimethylolpropane tri (meth) acrylate, alkylene oxide-modified dipentaerythritol hexa (meth) acrylate, and alkylene oxide-modified dipentaerythritol tetra (meth) acrylate are preferable, and ethylene oxide-modified tripentayl is particularly preferable.
- the polyfunctional (meth) acrylate modified with alkylene oxide has a long distance between cross-linking points, exhibits relatively soft physical properties after curing, and has a small amount of curing shrinkage.
- the amount of alkylene oxide introduced with respect to the polyfunctional (meth) acrylate is preferably 2 mol or more, particularly preferably 6 mol or more, and more preferably 20 mol with respect to 1 mol of the polyfunctional (meth) acrylate.
- the above is preferable.
- the introduction amount is preferably 50 mol or less, particularly preferably 45 mol or less, and further preferably 40 mol or less.
- the proportion of the alkylene oxide-modified polyfunctional (meth) acrylate in the active energy ray-curable component is preferably 30% by mass or more and 50% by mass or more from the viewpoint of bending resistance and curl suppression. More preferably, it is particularly preferably 80% by mass or more, and further preferably 90% by mass or more. In addition, the said ratio may be 100 mass%.
- examples of the (meth) acrylate-based prepolymer include polyester acrylate-based, epoxy acrylate-based, urethane acrylate-based, polyol acrylate-based prepolymers, and the like.
- polyester acrylate-based prepolymer examples include esterification of a hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding alkylene oxide to carboxylic acid with (meth) acrylic acid.
- the epoxy acrylate prepolymer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it.
- the urethane acrylate prepolymer can be obtained, for example, by esterifying a polyurethane oligomer obtained by a reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid.
- the polyol acrylate prepolymer can be obtained, for example, by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.
- the above prepolymers may be used alone or in combination of two or more.
- (1-2-2) Photopolymerization initiator When the first hard coat layer 3 is made of a material obtained by curing a composition containing an active energy ray-curable component, and ultraviolet rays are used as active energy rays.
- the composition preferably contains a photopolymerization initiator. By containing the photopolymerization initiator in this manner, the active energy ray-curable component can be efficiently polymerized, and the polymerization curing time and the amount of ultraviolet irradiation can be reduced.
- photopolymerization initiator examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2- Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′- Ethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-e
- the content of the photopolymerization initiator in the composition is preferably 0.01 parts by mass or more as a lower limit with respect to 100 parts by mass of the active energy ray-curable component, and particularly 0.1 parts by mass or more. It is preferable that the amount is 1 part by mass or more. Moreover, it is preferable that it is 20 mass parts or less as an upper limit, It is especially preferable that it is 10 mass parts or less, Furthermore, it is preferable that it is 5 mass parts or less.
- the composition constituting the first hard coat layer 3 may contain silica nanoparticles. Thereby, the amount of cure shrinkage of the first hard coat layer 3 can be further reduced.
- the average particle diameter of the silica nanoparticles is preferably 2 nm or more as a lower limit, particularly preferably 6 nm or more, and more preferably 8 nm or more. Moreover, it is preferable that it is 300 nm or less as an upper limit, It is especially preferable that it is 100 nm or less, Furthermore, it is preferable that it is 50 nm or less. When the average particle diameter of the silica nanoparticles is 2 nm or more, an effect of reducing the amount of cure shrinkage of the first hard coat layer 3 is more easily obtained.
- the average particle diameter of the silica nanoparticles is 300 nm or less, light scattering is unlikely to occur in the obtained first hard coat layer 3, and the transparency of the first hard coat layer 3 is increased.
- the average particle diameter of a silica nanoparticle shall be measured by the zeta potential measuring method.
- Silica nanoparticles usually have a silanol group on the surface, and the silanol group may reduce the dispersibility in organic solvents and resins with low polarity.
- the silica nanoparticles may be modified with an organic substance for the purpose of improving dispersibility.
- Silica nanoparticles are preferably used in the form of an organosol (colloid). By using it in the form of an organosol, the dispersibility of the silica nanoparticles is improved, and the homogeneity and light transmittance of the obtained first hard coat layer 3 are improved.
- Modification with an organic substance can be performed by a conventional method.
- a silane coupling agent having a structure such as CH 2 ⁇ C (CH 3 ) COO (CH 2 ) 3 Si (OCH 3 ) 3 is added to the organosol of silica nanoparticles, heated to about 50 ° C., and stirred for several hours. By doing so, the surface of the silica particles can be modified.
- the structure and amount of the silane coupling agent to be used are appropriately selected according to the required degree of dispersibility of the silica nanoparticles.
- methyl ethyl ketone, methyl isobutyl ketone, and the like which are excellent in compatibility with the active energy ray-curable component and excellent in volatility when the first hard coat layer 3 is formed, are preferable.
- the content thereof is preferably 5% by mass or more as the lower limit in the first hard coat layer 3, and particularly 10
- the content is preferably at least mass%, more preferably at least 30 mass%.
- the content of silica nanoparticles in the first hard coat layer 3 is preferably 80% by mass or less, particularly preferably 75% by mass or less, and more preferably 70% by mass or less as an upper limit. Preferably there is.
- the refractive index of the first hard coat layer 3 can be easily set to a value close to the refractive index of the second hard coat layer 4, and the hard coat layer The layer formation using the composition for use becomes easy.
- content of a silica nanoparticle can be calculated
- composition constituting the first hard coat layer 3 of the present embodiment may contain various additives in addition to the components described above.
- various additives include ultraviolet absorbers, antioxidants, light stabilizers, antistatic agents, silane coupling agents, anti-aging agents, thermal polymerization inhibitors, colorants, surfactants, storage stabilizers, plasticizers.
- the refractive index of the first hard coat layer 3 is preferably 1.40 or more as a lower limit, particularly preferably 1.43 or more, and more preferably 1.45 or more. It is preferable that Further, the refractive index of the first hard coat layer 3 is preferably 1.80 or less as an upper limit, particularly preferably 1.70 or less, and further preferably 1.60 or less. When the refractive index of the first hard coat layer 3 is in the above range, the refractive index difference from the refractive index of the second hard coat layer 4 can be easily set in the above-described range.
- the thickness of the first hard coat layer 3 is preferably 3 ⁇ m or more, particularly preferably 4 ⁇ m or more, and further preferably 5 ⁇ m or more.
- the thickness of the first hard coat layer 3 is preferably 30 ⁇ m or less, particularly preferably 20 ⁇ m or less, and further preferably 15 ⁇ m or less.
- the thickness of the first hard coat layer 3 is 3 ⁇ m or more, curling generated during the production of the hard coat film 1 can be easily suppressed, and the scratch resistance of the first hard coat layer 3 is obtained. Will be better.
- the thickness of the first hard coat layer 3 is 30 ⁇ m or less, the hard coat film 1 is easily bent and is excellent in bending resistance.
- the second hard coat layer 4 of the hard coat film 1 imparts high surface hardness to the hard coat film 1 and has excellent scratch resistance. To do.
- the second hard coat layer 4 is not particularly limited as long as it satisfies the above-described relationship with the refractive index of the first hard coat layer 3 and has a predetermined hardness.
- the second hard coat layer 4 is preferably made of a material obtained by curing a composition containing an active energy ray-curable component, and is particularly modified with alkylene oxide from the viewpoint of obtaining superior scratch resistance. It is preferably made of a material obtained by curing a composition containing a non-active energy ray-curable component.
- the active energy ray-curable component the same active energy ray-curable component as that used for the first hard coat layer 3 can be used. However, it is preferable to use an active energy ray-curable component that is not modified with alkylene oxide. Specifically, a polyfunctional (meth) acrylate not modified with alkylene oxide, a urethane acrylate prepolymer, a mixture thereof, and the like are preferable, and in particular, from the viewpoint of obtaining bending resistance without impairing scratch resistance.
- the second hard coat layer 4 is formed from an active energy ray-curable component containing a polyfunctional (meth) acrylate modified with alkylene oxide
- the second hard coat layer is used from the viewpoint of scratch resistance.
- the content of the polyfunctional (meth) acrylate modified with alkylene oxide in the entire active energy ray-curable component used in No. 4 is preferably 60% by mass or less, and preferably 30% by mass or less. More preferred is 10% by mass or less. In addition, as a lower limit, it is 0 mass%.
- the composition preferably contains a photopolymerization initiator.
- a photoinitiator the thing similar to the above-mentioned photoinitiator used for the 1st hard-coat layer 3 can be used.
- the second hard coat layer 4 in the present embodiment may contain a filler. Thereby, a high surface hardness can be imparted to the second hard coat layer 4 and the scratch resistance can be further improved.
- the filler may be either an organic filler or an inorganic filler, but from the viewpoint of imparting a high surface hardness to the second hard coat layer 4, it is preferable to use an inorganic filler, It is preferable to use an inorganic filler chemically modified with an organic compound having a polymerizable functional group that is polymerized by irradiation with active energy rays.
- a filler can be used individually by 1 type or in combination of 2 or more types.
- the inorganic filler examples include metal oxides such as silica, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide;
- metal oxides such as silica, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide
- metal oxides such as silica, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide
- fillers made of metal fluorides such as magnesium fluoride and sodium fluoride.
- silica and aluminum oxide are preferable from the viewpoint of little influence on optical characteristics, and silica is particularly preferable.
- the surface of the filler may be chemically modified, and is particularly preferably chemically modified with an organic compound having a polymerizable functional group that is polymerized by irradiation with active energy rays.
- the specific configuration of the chemical modification is not limited, and an example is a configuration in which a polymerizable functional group is added via a silane coupling agent or the like.
- the active energy ray irradiation causes the filler and the active energy ray-curable component to be chemically bonded to each other, so that peeling between them is less likely to occur, and the hardness of the second hard coat layer 4 is high. Easy to be.
- a filler chemically modified with an organic compound having a polymerizable functional group is referred to as a reactive filler.
- the type of filler is silica, it is referred to as a reactive silica filler.
- the shape of the filler may be spherical or non-spherical. When it is non-spherical, it may be indefinite, or may have a shape with a high aspect ratio such as a needle shape or a scale shape. From the viewpoint of ensuring the transparency of the second hard coat layer 4, the filler is preferably spherical.
- the average particle diameter of the filler is preferably 1 nm or more, particularly preferably 3 nm or more, more preferably 5 nm or more, as a lower limit. When the average particle diameter of the filler is 1 nm or more, dispersibility is improved.
- the average particle size of the filler is preferably 500 nm or less, particularly preferably 200 nm or less, and more preferably 50 nm or less, as an upper limit. When the average particle diameter of the filler is 500 nm or less, light scattering hardly occurs in the obtained second hard coat layer 4, and the transparency of the second hard coat layer 4 is increased.
- the average particle diameter of a filler shall measure a primary particle diameter with the zeta potential measurement method.
- the 2nd hard-coat layer 4 of this embodiment contains a filler
- the content is 5 mass% or more as a lower limit, It is especially preferable that it is 20 mass% or more, Furthermore, It is preferable that it is 50 mass% or more.
- the filler content in the second hard coat layer 4 is preferably 90% by mass or less, particularly preferably 80% by mass or less, and more preferably 70% by mass or less as an upper limit. It is preferable. When the filler content is 90% by mass or less, layer formation is facilitated.
- the second hard coat layer 4 of the present embodiment may contain various additives similar to the various additives used in the first hard coat layer 3 in addition to the components described above.
- the refractive index of the second hard coat layer 4 is preferably 1.40 or more as a lower limit, particularly preferably 1.43 or more, and more preferably 1.45 or more. Further, the refractive index of the second hard coat layer 4 is preferably 1.80 or less as an upper limit, particularly preferably 1.70 or less, and further preferably 1.60 or less. When the refractive index of the second hard coat layer 4 is in the above range, the difference in refractive index from the refractive index of the first hard coat layer 3 can be easily set in the above-described range.
- the thickness of the second hard coat layer 4 is preferably 0.75 ⁇ m or more, particularly preferably 1 ⁇ m or more, and further preferably 1.5 ⁇ m or more.
- the thickness of the second hard coat layer 4 is preferably 10 ⁇ m or less, particularly preferably 8 ⁇ m or less, and further preferably 6 ⁇ m or less.
- the scratch resistance of the second hard coat layer 4 becomes more excellent.
- the thickness of the second hard coat layer 4 is 10 ⁇ m or less, the hard coat film 1 is more suppressed from curling.
- the ratio of the thickness of the first hard coat layer 3 to the thickness of the second hard coat layer 4 is preferably 10:90 to 90:10, particularly preferably 40:60 to 80:20. Further, it is preferably 50:50 to 80:20. When the ratio is within the above range, the hard coat film 1 to be obtained has excellent scratch resistance and flex resistance, and curling is further suppressed.
- the hard coat film 1 which concerns on this embodiment can be preferably manufactured with the following method.
- a composition containing an active energy ray-curable component is used to form the first hard coat layer 3 and the second hard coat layer 4.
- composition for 1st hard coat layer 3 which contains the composition (1st composition for 1st hard coat layer 3) which comprises the 1st hard coat layer 3, and the solvent as needed.
- the composition of the second hard coat layer 4 (the composition for the second hard coat layer 4) and, if desired, the second hard coat layer 4 composition further containing a solvent are applied.
- the solvent examples include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether, and the like. Alcohols, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as 2-pentanone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate, and cellosolv solvents such as ethyl cellosolve. Only one type of solvent may be used, or two or more types may be mixed and used.
- the concentration / viscosity of the coating solution is not particularly limited as long as it can be coated, and can be appropriately selected according to the situation.
- the coating liquid of the composition for the first hard coat layer 3 is applied to one main surface of the base film 2 and dried, and then irradiated with active energy rays under the conditions described below. Thereby, the coating film of the 1st composition for hard-coat layers 3 hardens
- an active energy ray is irradiated on the below-mentioned conditions. Thereby, the coating film of the 2nd composition for hard-coat layers 4 hardens
- the formation method of the 1st hard-coat layer 3 and the 2nd hard-coat layer 4 is not restricted to the above-mentioned method, Two-layer coating liquid is apply
- the coating liquid may be applied by a conventional method, for example, a bar coating method, a knife coating method, a Mayer bar method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method.
- the coating film can be dried, for example, by heating at 40 to 180 ° C. for about 30 seconds to 5 minutes.
- ultraviolet rays As the active energy ray, ultraviolet rays, electron beams and the like can be used. Ultraviolet irradiation can be performed with a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, or the like. The irradiation amount of ultraviolet rays is preferably about 50 to 1000 mW / cm 2 in illuminance and about 50 to 1000 mJ / cm 2 in light quantity.
- the electron beam irradiation can be performed by an electron beam accelerator or the like, and the irradiation amount of the electron beam is preferably about 10 to 1000 krad.
- the coating film of the first hard coat layer 3 composition and the second hard coat layer 4 composition coating film are shielded from oxygen. It is preferable to irradiate with ultraviolet rays. Thereby, a hard coat film having excellent flex resistance and high surface hardness is effectively formed without being inhibited by oxygen.
- a cover sheet is laminated on the coating film or an oxygen concentration of It is preferable to set it in a low atmosphere, for example, a nitrogen atmosphere.
- the reflected light is detected corresponding to each measurement wavelength as a relative value (hereinafter referred to as “reflectance”) where the reflected light from the barium sulfate crystal is 100. That is, a chart in which the horizontal axis is the measurement wavelength and the vertical axis is the reflectance can be obtained. The chart is usually wavy with a plurality of minimum and maximum values.
- the maximum reflectance difference is preferably 1.5 or less, particularly preferably 1.1 or less, and more preferably 0.6 or less. It can be said that the occurrence of interference fringes is suppressed when the reflectance is 1.5 or less.
- the hard coat film 1 according to the present embodiment uses a first hard coat having a predetermined refractive index difference and thickness for preventing interference fringes without adding micro-order fine particles. This is solved by providing the layer 3 and the second hard coat layer 4. For this reason, the hard coat film 1 which concerns on this embodiment can be made into the film excellent in the image clarity rather than the case where an interference fringe is prevented by adding micro order fine particle.
- the image definition is preferably 400% or more, more preferably 430% or more, and particularly preferably 450% or more.
- the image definition is the total value of each image definition measured with five types of slits (slit widths: 0.125 mm, 0.25 mm, 0.5 mm, 1 mm and 2 mm) in accordance with JIS K7374. Can be obtained as
- the haze value of the hard coat film 1 measured in accordance with JIS K7136 is preferably 1% or less. More preferably, it is made into 8% or less, and it is especially preferable to set it as 0.5% or less.
- the other main surface side of the base film 2 in the hard coat film 1 (the surface side opposite to the surface on which the first hard coat layer 3 and the second hard coat layer 4 are laminated) ),
- the pressure-sensitive adhesive layer 5 may be laminated as shown in FIG. 2 (the hard coat film shown in FIG. 2 is denoted by “1A”). By laminating such a pressure-sensitive adhesive layer 5, the hard coat film 1A can be easily attached to a desired adherend.
- the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 5 is not particularly limited, and a known pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive, a rubber pressure-sensitive adhesive, or a silicone pressure-sensitive adhesive can be used.
- the thickness of the pressure-sensitive adhesive layer 5 is not particularly limited, but is usually 5 to 100 ⁇ m, preferably 10 to 60 ⁇ m.
- the hard coat film 1A according to the present embodiment can be manufactured basically in the same manner as the hard coat film 1 described above. What is necessary is just to form the adhesive layer 5 by a conventional method.
- the release sheet may be laminated
- the hard coat film 1, 1 ⁇ / b> A is, for example, a flexible display in various electronic devices, particularly mobile electronic devices, specifically, a liquid crystal display (LCD), an organic EL. It can be preferably used as a flexible member for the surface layer (protective film) of various flexible displays such as displays (OELD) and electronic paper modules (film-shaped electronic paper).
- LCD liquid crystal display
- organic EL organic EL
- OELD displays
- electronic paper modules film-shaped electronic paper
- the side of the hard coat film 1, 1A where the first hard coat layer 3 and the second hard coat layer 4 are present is the inner side. It is preferable to bend. This makes it difficult for defects such as cracks to occur in the first hard coat layer 3 and the second hard coat layer 4.
- Acetic anhydride and pyridine were added to the obtained polyamic acid solution, and after sufficiently stirring, it was coated on a glass plate and slowly heated from room temperature to 180 ° C. After reaching 180 ° C., the mixture was heated for a certain period of time, and then evacuated to completely remove volatile components. Finally, a polyimide film with a film thickness of 25 ⁇ m was obtained by cooling to room temperature under vacuum. When the polyimide film was measured, b * was 0.61, the refractive index was 1.62, and the transmittance at a wavelength of 550 nm was 90%.
- the film thickness of the polyimide film was measured using a constant pressure thickness measuring instrument (manufactured by Teclock Co., product name “PG-02”) in accordance with JIS K7130.
- a simultaneous measurement spectroscopic color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name “SQ-2000”) is used as a measuring device, and a C light source 2 ° field of view (C / 2) is used as a light source Used, b * of the L * a * b * color system was measured by transmission measurement.
- the transmittance at a wavelength of 550 nm was measured using an ultraviolet visible near infrared spectral transmittance meter (manufactured by Shimadzu Corporation, product name “UV3600”).
- Example 1 100 parts by mass of ethylene oxide-modified dipentaerythritol hexaacrylate (introduced 12 mol of ethylene oxide) as an active energy ray-curable component (in terms of solid content; hereinafter the same), 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator, was stirred and mixed in a mixed solvent in which methyl isobutyl ketone and cyclohexanone were mixed at a mass ratio of 1: 1 to obtain a first hard coat layer composition coating solution.
- the coating liquid of the said composition for 1st hard-coat layers was apply
- the coating film of the 1st composition for hard-coat layers was formed by making it heat-dry for minutes.
- the coating film of the first hard coat layer composition is cured by irradiating ultraviolet rays under the following conditions, and the 5 ⁇ m thick first coating film is cured. 1 hard coat layer was formed.
- a coating liquid of the second hard coat layer composition is applied onto the obtained first hard coat layer, and is dried by heating at 70 ° C. for 1 minute, for the second hard coat layer.
- a coating film of the composition was formed.
- the coating film of the second hard coat layer composition is cured by irradiating ultraviolet rays from the coating film side of the second hard coat layer composition under the following conditions, and the second hard coat layer composition has a thickness of 5 ⁇ m.
- a hard coat layer was formed. Thereby, the hard coat in which the first hard coat layer (thickness: 5 ⁇ m) and the second hard coat layer (thickness: 5 ⁇ m) were formed in order on the polyimide film (thickness: 25 ⁇ m) as the base film. A film was obtained.
- UV irradiation device UV irradiation device manufactured by GS Yuasa Corporation
- Light source High pressure mercury lamp
- Lamp power 1.4 kW
- Illuminance 100 mW / cm 2
- Light intensity 240 mJ / cm 2
- Conveyor speed 1.2m / min ⁇ UV irradiation under nitrogen atmosphere (oxygen concentration 1% or less)
- Examples 2 to 5 Comparative Examples 1 to 6
- Kinds and blending ratios of components constituting the first hard coat layer composition and the second hard coat layer composition, the thicknesses of the first hard coat layer and the second hard coat layer, and the substrate A hard coat film was produced in the same manner as in Example 1 except that the type and thickness of the film were changed as shown in Table 1.
- the total thickness of the first hard coat layer and the second hard coat layer was calculated and shown in Table 1.
- the refractive indices of the first hard coat layer and the second hard coat layer were measured under the conditions of a measurement wavelength of 589 nm and a measurement temperature of 25 ° C. (product name “M- 2000 "”) and measured according to JIS K7142 (2008). The results are shown in Table 2.
- Test Example 3 Evaluation of scratch resistance
- the surface of the hard coat layer of the hard coat film produced in Examples and Comparative Examples was rubbed 10 times with a load of 125 g weight / cm 2 using # 0000 steel wool, and the range of 100 mm in length and 20 mm in width was tested. It was. The number of scratches in the test range was visually confirmed under a three-wavelength fluorescent lamp, and scratch resistance was evaluated according to the following criteria. The results are shown in Table 2. ⁇ : The number of scratches was less than 20. X: The number of scratches was 20 or more.
- the hard coat films obtained in the examples were excellent in scratch resistance and optical properties, were excellent in flex resistance, and were less likely to cause interference fringes and curls.
- the hard coat film of the present invention is suitable as a flexible member constituting a flexible display that is repeatedly bent, particularly as a protective film located on the surface layer.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Liquid Crystal (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
Description
図1は、本発明の一実施形態に係るハードコートフィルムの断面図である。本実施形態に係るハードコートフィルム1は、基材フィルム2と、基材フィルムの一方の主面側(図1における上側)に積層された第1のハードコート層3と、第1のハードコート層3における基材フィルム2側とは反対の主面側(図1における上側)に積層された第2のハードコート層4とを備えて構成される。なお、第1のハードコート層3および第2のハードコート層4は、互いに異なる材料からなる。 Hereinafter, embodiments of the present invention will be described.
FIG. 1 is a cross-sectional view of a hard coat film according to an embodiment of the present invention. A hard coat film 1 according to the present embodiment includes a
(1-1)基材フィルム
本実施形態に係るハードコートフィルム1の基材フィルム2は、ポリイミドフィルムであり、ディスプレイ用である場合には、透明かつ黄色味の少ないポリイミドフィルムであることが好ましい。これにより、クリアかつ色再現性の高い画像を表示するディスプレイ(特にフレキシブルディスプレイ)を得ることができる。 (1) Constituent Member of Hard Coat Film (1-1) Base Film The
本実施形態に係るハードコートフィルム1の第1のハードコート層3は、基材フィルム2の一方の主面側(図1における上側)に積層され、前述した通り、第2のハードコート層4とともに干渉縞の発生を抑制する作用および耐擦傷性を発揮する。 (1-2) First Hard Coat Layer The first
活性エネルギー線硬化性成分としては、多官能性(メタ)アクリレート系モノマー、(メタ)アクリレート系プレポリマー、活性エネルギー線硬化性ポリマー等が挙げられるが、中でも多官能性(メタ)アクリレート系モノマーおよび/または(メタ)アクリレート系プレポリマーであることが好ましく、多官能性(メタ)アクリレート系モノマーであることがより好ましい。多官能性(メタ)アクリレート系モノマーおよび(メタ)アクリレート系プレポリマーは、それぞれ単独で使用してもよいし、両者を併用してもよい。なお、本明細書において、(メタ)アクリレートとは、アクリレートおよびメタクリレートの両方を意味する。他の類似用語も同様である。 (1-2-1) Active energy ray curable component Examples of the active energy ray curable component include polyfunctional (meth) acrylate monomers, (meth) acrylate prepolymers, active energy ray curable polymers, and the like. However, among them, a polyfunctional (meth) acrylate monomer and / or a (meth) acrylate prepolymer is preferable, and a polyfunctional (meth) acrylate monomer is more preferable. The polyfunctional (meth) acrylate monomer and the (meth) acrylate prepolymer may be used alone or in combination. In the present specification, (meth) acrylate means both acrylate and methacrylate. The same applies to other similar terms.
第1のハードコート層3が、活性エネルギー線硬化性成分を含有する組成物を硬化させた材料からなる場合において、活性エネルギー線として紫外線を用いる場合には、当該組成物は、光重合開始剤を含有することが好ましい。このように光重合開始剤を含有することにより、活性エネルギー線硬化性成分を効率良く重合させることができ、また重合硬化時間および紫外線の照射量を少なくすることができる。 (1-2-2) Photopolymerization initiator When the first
第1のハードコート層3を構成する組成物は、シリカナノ粒子を含有してもよい。これにより、第1のハードコート層3の硬化収縮量をより小さくすることができる。 (1-2-3) Silica nanoparticles The composition constituting the first
本実施形態の第1のハードコート層3を構成する組成物は、前述した成分以外に、各種添加剤を含有してもよい。各種添加剤としては、例えば、紫外線吸収剤、酸化防止剤、光安定剤、帯電防止剤、シランカップリング剤、老化防止剤、熱重合禁止剤、着色剤、界面活性剤、保存安定剤、可塑剤、滑剤、消泡剤、有機系充填材、濡れ性改良剤、塗面改良剤等が挙げられる。 (1-2-4) Other components The composition constituting the first
第1のハードコート層3の屈折率は、下限値として1.40以上であることが好ましく、特に1.43以上であることが好ましく、さらには1.45以上であることが好ましい。また、第1のハードコート層3の屈折率は、上限値として1.80以下であることが好ましく、特に1.70以下であることが好ましく、さらには1.60以下であることが好ましい。第1のハードコート層3の屈折率が上記の範囲にあることにより、第2のハードコート層4の屈折率との屈折率差を前述した範囲に設定し易くなる。 (1-2-5) Physical Properties The refractive index of the first
本実施形態に係るハードコートフィルム1の第2のハードコート層4は、ハードコートフィルム1に高い表面硬度を付与し、耐擦傷性を優れたものにする。この第2のハードコート層4は、第1のハードコート層3の屈折率と前述した関係を満たし、所定の硬度を有するものであれば特に限定されない。かかる第2のハードコート層4は、活性エネルギー線硬化性成分を含有する組成物を硬化させた材料からなることが好ましく、特に、より優れた耐擦傷性を得る観点から、アルキレンオキシドによって変性されていない活性エネルギー線硬化性成分を含有する組成物を硬化させた材料からなることが好ましい。 (1-3) Second Hard Coat Layer The second
本実施形態に係るハードコートフィルム1は、次の方法によって好ましく製造することができる。なお、本方法では、一例として、第1のハードコート層3および第2のハードコート層4の形成に、活性エネルギー線硬化性成分を含有する組成物を使用するものとする。 (2) Manufacturing method of hard coat film The hard coat film 1 which concerns on this embodiment can be preferably manufactured with the following method. In this method, as an example, a composition containing an active energy ray-curable component is used to form the first
(3-1)最大反射率差
前述した通り、本実施形態に係るハードコートフィルム1においては、干渉縞の発生が抑制される。このことは、目視による評価以外に、最大反射率差の測定値により判断することができる。最大反射率差を測定するには、まず、フィルム法線方向を0°として、入射角8°方向から光を照射し、その反射した光を積分球により集光することにより反射光として検出する。なお、光の照射は、波長を変化させて行い、それぞれの波長に対応する反射光を検出する。 (3) Physical Properties of Hard Coat Film (3-1) Maximum Reflectance Difference As described above, the occurrence of interference fringes is suppressed in the hard coat film 1 according to this embodiment. This can be judged by the measured value of the maximum reflectance difference in addition to the visual evaluation. In order to measure the maximum reflectance difference, first, the film normal direction is set to 0 °, light is irradiated from the direction of an incident angle of 8 °, and the reflected light is collected by an integrating sphere to be detected as reflected light. . In addition, light irradiation is performed by changing the wavelength, and reflected light corresponding to each wavelength is detected.
本実施形態に係るハードコートフィルム1は、干渉縞防止を、マイクロオーダーの微粒子を添加するのではなく、所定の屈折率差および厚さを有する第1のハードコート層3および第2のハードコート層4を設けることにより解決する。このため、本実施形態に係るハードコートフィルム1は、マイクロオーダーの微粒子を添加することにより干渉縞を防止する場合よりも、像鮮明度に優れたフィルムとすることができる。 (3-2) Image Visibility The hard coat film 1 according to the present embodiment uses a first hard coat having a predetermined refractive index difference and thickness for preventing interference fringes without adding micro-order fine particles. This is solved by providing the
ディスプレイに適用した際、より鮮明な画像を表示させる観点から、JIS K7136に準拠して測定されるハードコートフィルム1のヘーズ値を1%以下とすることが好ましく、0.8%以下とすることがより好ましく、0.5%以下とすることが特に好ましい。 (3-3) Haze value From the viewpoint of displaying a clearer image when applied to a display, the haze value of the hard coat film 1 measured in accordance with JIS K7136 is preferably 1% or less. More preferably, it is made into 8% or less, and it is especially preferable to set it as 0.5% or less.
ディスプレイに適用した際、より鮮明な画像を表示させる観点から、ハードコートフィルム1におけるハードコート層3のJIS Z8741-1997に準拠した60°光沢度(グロス値)を、100%以上の値とすることが好ましく、120%以上の値とすることがより好ましく、140%以上の値とすることが特に好ましい。 (3-4) 60 ° Glossiness 60 ° glossiness (gloss value) based on JIS Z8741-1997 of the
ハードコートフィルム1における基材フィルム2の他方の主面側(第1のハードコート層3および第2のハードコート層4が積層された面とは反対側の面側)には、図2に示すように、粘着剤層5が積層されてもよい(図2に示すハードコートフィルムの符号を「1A」と記す)。このような粘着剤層5が積層されることで、ハードコートフィルム1Aを所望の被着体に簡易に貼付することができる。 (4) Other Embodiments The other main surface side of the
本実施形態に係るハードコートフィルム1,1Aには、他の層、例えば、粘接着剤層、バリア層、導電層、低反射層、易印刷層、防汚層などが積層されてもよい。 (5) Other embodiment-2
Other layers such as an adhesive layer, a barrier layer, a conductive layer, a low reflection layer, an easy printing layer, an antifouling layer, and the like may be laminated on the
以上の実施形態に係るハードコートフィルム1,1Aは、例えば、各種電子機器、特にモバイル電子機器における、フレキシブルディスプレイ、具体的には、液晶ディスプレイ(LCD)、有機ELディスプレイ(OELD)、電子ペーパーモジュール(フィルム状電子ペーパー)等の各種フレキシブルディスプレイの表層(保護フィルム)のフレキシブル部材として好ましく使用することができる。 (6) Use of Hard Coat Film The hard coat film 1, 1 </ b> A according to the above embodiment is, for example, a flexible display in various electronic devices, particularly mobile electronic devices, specifically, a liquid crystal display (LCD), an organic EL. It can be preferably used as a flexible member for the surface layer (protective film) of various flexible displays such as displays (OELD) and electronic paper modules (film-shaped electronic paper).
N,N-ジメチルアセトアミド溶媒中にて、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル、ビフェニルテトラカルボン酸二無水物、および2,2-ビス(3,4-ジカルボキシフェニル)ヘキサフルオロプロパン酸二無水物を、冷却下で混合溶解し、その後、常温で10時間撹拌することにより、ポリアミド酸溶液を得た。 [Production Example 1] (Preparation of base film)
In a N, N-dimethylacetamide solvent, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, biphenyltetracarboxylic dianhydride, and 2,2-bis (3,4- Dicarboxyphenyl) hexafluoropropanoic acid dianhydride was mixed and dissolved under cooling, and then stirred at room temperature for 10 hours to obtain a polyamic acid solution.
上記b*については、JIS Z8722に従い、測定装置として同時測定方式分光式色差計(日本電色工業社製,製品名「SQ-2000」)、光源としてC光源2°視野(C/2)を用い、透過測定法によりL*a*b*表色系のb*を測定した。
上記波長550nmにおける透過率は、紫外線可視近赤外分光透過率計(島津製作所製,製品名「UV3600」)を用いて測定した。 The film thickness of the polyimide film was measured using a constant pressure thickness measuring instrument (manufactured by Teclock Co., product name “PG-02”) in accordance with JIS K7130.
For the above b *, in accordance with JIS Z8722, a simultaneous measurement spectroscopic color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name “SQ-2000”) is used as a measuring device, and a C
The transmittance at a wavelength of 550 nm was measured using an ultraviolet visible near infrared spectral transmittance meter (manufactured by Shimadzu Corporation, product name “UV3600”).
活性エネルギー線硬化性成分としてのエチレンオキシド変性ジペンタエリスリトールヘキサアクリレート(エチレンオキシド12モル導入)100質量部(固形分換算;以下同じ)と、光重合開始剤としての1-ヒドロキシシクロヘキシルフェニルケトン5質量部とを、メチルイソブチルケトンおよびシクロヘキサノンを1:1の質量比で混合した混合溶媒中にて撹拌混合して、第1のハードコート層用組成物の塗工液を得た。 [Example 1]
100 parts by mass of ethylene oxide-modified dipentaerythritol hexaacrylate (introduced 12 mol of ethylene oxide) as an active energy ray-curable component (in terms of solid content; hereinafter the same), 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator, Was stirred and mixed in a mixed solvent in which methyl isobutyl ketone and cyclohexanone were mixed at a mass ratio of 1: 1 to obtain a first hard coat layer composition coating solution.
<紫外線照射条件>
・紫外線照射装置:ジーエスユアサコーポレーション社製紫外線照射装置
・光源:高圧水銀灯
・ランプ電力:1.4kW
・照度:100mW/cm2
・光量:240mJ/cm2
・コンベアスピード:1.2m/min
・窒素雰囲気下にて紫外線照射(酸素濃度1%以下) Next, a coating liquid of the second hard coat layer composition is applied onto the obtained first hard coat layer, and is dried by heating at 70 ° C. for 1 minute, for the second hard coat layer. A coating film of the composition was formed. And the coating film of the second hard coat layer composition is cured by irradiating ultraviolet rays from the coating film side of the second hard coat layer composition under the following conditions, and the second hard coat layer composition has a thickness of 5 μm. A hard coat layer was formed. Thereby, the hard coat in which the first hard coat layer (thickness: 5 μm) and the second hard coat layer (thickness: 5 μm) were formed in order on the polyimide film (thickness: 25 μm) as the base film. A film was obtained.
<Ultraviolet irradiation conditions>
・ Ultraviolet irradiation device: UV irradiation device manufactured by GS Yuasa Corporation ・ Light source: High pressure mercury lamp ・ Lamp power: 1.4 kW
Illuminance: 100 mW / cm 2
・ Light intensity: 240 mJ / cm 2
・ Conveyor speed: 1.2m / min
・ UV irradiation under nitrogen atmosphere (oxygen concentration 1% or less)
第1のハードコート層用組成物および第2のハードコート層用組成物を構成する各成分の種類および配合比、第1のハードコート層および第2のハードコート層の厚さ、ならびに基材フィルムの種類および厚さを表1に示すように変更する以外、実施例1と同様にしてハードコートフィルムを製造した。 [Examples 2 to 5, Comparative Examples 1 to 6]
Kinds and blending ratios of components constituting the first hard coat layer composition and the second hard coat layer composition, the thicknesses of the first hard coat layer and the second hard coat layer, and the substrate A hard coat film was produced in the same manner as in Example 1 except that the type and thickness of the film were changed as shown in Table 1.
A:エチレンオキシド変性ジペンタエリスリトールヘキサアクリレート(エチレンオキシド12モル導入)
B:エチレンオキシド変性ジペンタエリスリトールヘキサアクリレート(エチレンオキシド6モル導入)
C:エチレンオキシド変性ペンタエリスリトールテトラアクリレート(エチレンオキシド35モル導入)
D:ビニルエステル樹脂(日立化成社製,製品名「ヒタロイド7663」)
E:ジペンタエリスリトールヘキサアクリレート
F:シリカナノ粒子(シリカゾル)(日産化学工業社製,製品名「MIBK-ST」,平均粒径:10nm)
G:1-ヒドロキシシクロヘキシルフェニルケトン
H:ジペンタエリスリトールヘキサアクリレート40質量部、反応性シリカフィラー(平均粒径:15nm)60質量部および1-ヒドロキシシクロヘキシルフェニルケトン10質量部の混合物
I:6官能のウレタンアクリレート系プレポリマー50質量部、ペンタエリスリトールテトラアクリレート50質量部および1-ヒドロキシシクロヘキシルフェニルケトン10質量部の混合物 Details of the abbreviations and the like described in Table 1 are as follows.
A: Ethylene oxide modified dipentaerythritol hexaacrylate (12 mol of ethylene oxide introduced)
B: Ethylene oxide modified dipentaerythritol hexaacrylate (6 mol of ethylene oxide introduced)
C: Ethylene oxide modified pentaerythritol tetraacrylate (35 mol of ethylene oxide introduced)
D: Vinyl ester resin (manufactured by Hitachi Chemical Co., Ltd., product name “Hitaroid 7663”)
E: Dipentaerythritol hexaacrylate F: Silica nanoparticles (silica sol) (manufactured by Nissan Chemical Industries, product name “MIBK-ST”, average particle size: 10 nm)
G: 1-hydroxycyclohexyl phenyl ketone H: Mixture of 40 parts by mass of dipentaerythritol hexaacrylate, 60 parts by mass of reactive silica filler (average particle size: 15 nm) and 10 parts by mass of 1-hydroxycyclohexyl phenyl ketone I: 6 functional Mixture of 50 parts by weight of urethane acrylate prepolymer, 50 parts by weight of pentaerythritol tetraacrylate and 10 parts by weight of 1-hydroxycyclohexyl phenyl ketone
PI:ポリイミドフィルム
PET:ポリエチレンテレフタレートフィルム(三菱樹脂社製,製品名「ダイヤホイルT-60」,厚さ:50μm) The details of the abbreviations described in Table 2 are as follows.
PI: Polyimide film PET: Polyethylene terephthalate film (manufactured by Mitsubishi Plastics, product name “Diafoil T-60”, thickness: 50 μm)
(1)基材フィルムの屈折率
実施例および比較例で使用した基材フィルムの屈折率を、測定波長589nm、測定温度25℃の条件で、アッベ屈折率計(アタゴ社製,製品名「多波長アッベ屈折率計DR-M2」)を使用して、JIS K7142(2008)に準じて測定した。結果を表2に示す。 [Test Example 1] (Measurement of refractive index)
(1) Refractive index of base film The refractive index of the base film used in the examples and comparative examples was measured under the conditions of a measurement wavelength of 589 nm and a measurement temperature of 25 ° C. Measured according to JIS K7142 (2008) using a wavelength Abbe refractometer DR-M2 "). The results are shown in Table 2.
片面が易接着処理されたポリエチレンテレフタレートフィルム(東洋紡社製,製品名「コスモシャインA4100」,厚さ:50μm)の未処理面に、実施例および比較例と同様にして、厚さ200nmの第1のハードコート層または第2のハードコート層を形成した。次いで、ポリエチレンテレフタレートフィルムの易接着処理面を紙やすりで擦り、油性ペン(ゼブラ社製,製品名「マッキー黒」)で黒色に塗り潰した。 (2) Refractive Index of Hard Coat Layer Same as in Examples and Comparative Examples on the untreated surface of polyethylene terephthalate film (product name “COSMO SHINE A4100”, thickness: 50 μm) manufactured by Toyobo Co., Ltd. Thus, a first hard coat layer or a second hard coat layer having a thickness of 200 nm was formed. Next, the easy-adhesion treated surface of the polyethylene terephthalate film was rubbed with sandpaper and painted black with an oil-based pen (product name “Mackey Black” manufactured by Zebra).
上記で測定した第1のハードコート層の屈折率から第2のハードコート層の屈折率を差し引き、屈折率差を算出した。結果を表2に示す。 (3) Calculation of refractive index difference The refractive index difference was calculated by subtracting the refractive index of the second hard coat layer from the refractive index of the first hard coat layer measured above. The results are shown in Table 2.
(1)目視評価
実施例および比較例で製造したハードコートフィルムを、両面粘着シート(リンテック社製,製品名「OPTERIA MO-3006C」,厚さ:25μm)を介して黒色のアクリル板(三菱レイヨン社製,製品名「アクリライトL502」)に貼付した。このとき、ハードコートフィルムの基材フィルムがアクリル板に接触するように貼付した。 [Test Example 2] (Evaluation of interference fringes)
(1) Visual evaluation The hard coat films produced in the examples and comparative examples were transferred to a black acrylic plate (Mitsubishi Rayon) via a double-sided PSA sheet (product name “OPTERIA MO-3006C”, thickness: 25 μm, manufactured by Lintec Corporation). The product name “Acrylite L502”). At this time, it stuck so that the base film of a hard coat film might contact an acrylic board.
良好(◎):干渉縞がほとんど見えない
概ね良好(○):干渉縞が見え難い
やや不良(△):干渉縞が見える
不良(×):干渉縞がはっきりと見える About the obtained laminated body, the interference fringe was confirmed visually from the hard-coat layer side under 3 wavelength fluorescent lamps, and the following references | standards evaluated. The results are shown in Table 2.
Good (◎): Interference fringes are almost invisible Almost good (○): Interference fringes are difficult to see Somewhat bad (△): Interference fringes are visible Bad (×): Interference fringes are clearly visible
(1)で得られた積層体について、以下の条件にて、分光光度計で反射率スペクトルの波長500~600nm間での最大反射率差を測定した。結果を表2に示す。
<測定条件>
・分光光度計:島津製作所社製,製品名「紫外可視近赤外分光光度計UV-3600」
・試料フォルダー:島津製作所社製,製品名「大型試料室MPC-3100」
・積分球:島津製作所社製,製品名「積分球付属装置ISR-3100」
・入射角:8° (2) Measurement of maximum reflectance difference With respect to the laminate obtained in (1), the maximum reflectance difference between wavelengths of 500 to 600 nm of the reflectance spectrum was measured with a spectrophotometer under the following conditions. The results are shown in Table 2.
<Measurement conditions>
・ Spectrophotometer: manufactured by Shimadzu Corporation, product name "UV-Vis Near-Infrared Spectrophotometer UV-3600"
・ Sample folder: manufactured by Shimadzu Corporation, product name “Large Sample Chamber MPC-3100”
・ Integral sphere: manufactured by Shimadzu Corporation, product name “Integral sphere attachment device ISR-3100”
-Incident angle: 8 °
実施例および比較例で製造したハードコートフィルムのハードコート層表面について、#0000のスチールウールを用いて、125g重/cm2の荷重で10往復擦り、長さ100mm、幅20mmの範囲を試験範囲とした。その試験範囲における傷本数を、3波長蛍光灯下で目視により確認し、以下の基準で耐擦傷性を評価した。結果を表2に示す。
○:傷本数が20本未満であった。
×:傷本数が20本以上であった。 [Test Example 3] (Evaluation of scratch resistance)
The surface of the hard coat layer of the hard coat film produced in Examples and Comparative Examples was rubbed 10 times with a load of 125 g weight / cm 2 using # 0000 steel wool, and the range of 100 mm in length and 20 mm in width was tested. It was. The number of scratches in the test range was visually confirmed under a three-wavelength fluorescent lamp, and scratch resistance was evaluated according to the following criteria. The results are shown in Table 2.
○: The number of scratches was less than 20.
X: The number of scratches was 20 or more.
実施例および比較例で製造したハードコートフィルムを、各辺がMD方向(ポリイミドフィルム製造時のライン方向)またはTD方向(MD方向に直交する方向)に平行になるように、100×100mmに裁断した後、基材フィルムがガラス板側となるように、ハードコートフィルムを平坦なガラス板の上に載置した。次いで、ガラス板の上面からハードコートフィルムの各角部頂点までの浮き高さを測定し、以下の判断基準でカールを評価した。結果を表2に示す。
非常に良好(◎):10サンプル中10サンプル全てが各角部の浮き高さの総和が20mm未満
良好(○):10サンプル中9~6サンプルが各角部の浮き高さの総和が20mm未満
不良(×):10サンプル中5~0サンプルが各角部の浮き高さの総和が20mm未満 [Test Example 4] (Curl evaluation)
The hard coat films produced in the examples and comparative examples are cut into 100 × 100 mm so that each side is parallel to the MD direction (line direction during polyimide film production) or TD direction (direction perpendicular to the MD direction). Then, the hard coat film was placed on a flat glass plate so that the base film was on the glass plate side. Subsequently, the floating height from the upper surface of the glass plate to each corner vertex of the hard coat film was measured, and the curl was evaluated according to the following criteria. The results are shown in Table 2.
Very good (◎): all 10 samples out of 10 samples have a total floating height of less than 20 mm Good (◯): 9 to 10 samples out of 10 samples have a total floating height of 20 mm Less than defective (×): 5 to 0 out of 10 samples, the sum of the floating height of each corner is less than 20 mm
実施例および比較例で製造したハードコートフィルムについて、耐久試験機(ユアサシステム機器社製,製品名「面状体無負荷U字伸縮試験機 DLDMLH-FS」)を用い、ハードコート層を内側にして、試験速度60mm/sで、試験回数(往復数)および屈曲径を種々変更して、繰り返し屈曲させた。そして、ハードコート層のクラック・剥がれや、ハードコートフィルムの白化・屈曲跡の発生等の不良の発生の有無を確認し、以下の基準で耐屈曲性を評価した。結果を表2に示す。
◎:屈曲径5mm以下、かつ試験回数2万回以上でも不良の発生がなかった。
○:屈曲径10mm以下、かつ試験回数2万回以上でも不良の発生がなかった。
×:○の基準に未達であった。 [Test Example 5] (Bend resistance test)
For the hard coat films produced in the examples and comparative examples, the endurance tester (manufactured by Yuasa System Equipment Co., Ltd., product name “Planar body unloaded U-shaped stretch tester DLDMMLH-FS”) was used, with the hard coat layer on the inside. Then, at the test speed of 60 mm / s, the number of tests (the number of reciprocations) and the bending diameter were variously changed and bent repeatedly. And the presence or absence of generation | occurrence | production of defects, such as a crack and peeling of a hard-coat layer, whitening of a hard-coat film, and generation | occurrence | production of a bending trace, was confirmed, and the bending resistance was evaluated on the following references | standards. The results are shown in Table 2.
A: No defect occurred even when the bending diameter was 5 mm or less and the test number was 20,000 times or more.
○: No defect occurred even when the bending diameter was 10 mm or less and the test number was 20,000 times or more.
X: The standard of ○ was not achieved.
実施例および比較例で製造したハードコートフィルムについて、写像性測定器(スガ試験機社製,製品名「ICM-10P」)を使用し、JIS K7374に準拠して、5種類のスリット(スリット幅:0.125mm、0.25mm、0.5mm、1mm及び2mm)の合計値を像鮮明度(%)として測定した。その結果に基づき、像鮮明度400%未満を×、400%以上450%未満を○、450%以上を◎と評価した。結果を表2に示す。 [Test Example 6] (Evaluation of image definition)
For the hard coat films produced in the examples and comparative examples, using an image clarity measuring device (product name “ICM-10P” manufactured by Suga Test Instruments Co., Ltd.), 5 types of slits (slit width) : 0.125 mm, 0.25 mm, 0.5 mm, 1 mm, and 2 mm) were measured as image sharpness (%). Based on the results, an image definition of less than 400% was evaluated as x, 400% or more and less than 450% was evaluated as ◯, and 450% or more was evaluated as ◎. The results are shown in Table 2.
実施例および比較例で製造したハードコートフィルムについて、ヘーズメーター(日本電色工業社製,製品名「NDH5000」)を用い、JIS K7136に準拠してヘーズ値(%)を測定した。その結果に基づき、ヘーズ値1%超を×、1%以下0.5%超を○、0.5%以下を◎と評価した。結果を表2に示す。 [Test Example 7] (Evaluation of haze value)
About the hard coat film manufactured by the Example and the comparative example, the haze value (%) was measured based on JISK7136 using the haze meter (Nippon Denshoku Industries Co., Ltd. product name "NDH5000"). Based on the results, the haze value of 1% or more was evaluated as x, 1% or less of 0.5% or more as ◯, and 0.5% or less as ◎. The results are shown in Table 2.
実施例および比較例で製造したハードコートフィルムについて、グロスメーター(日本電色工業社製)を使用し、JIS Z8741-1997に準拠して60°光沢度(グロス値)を測定した。その結果に基づき、60°光沢度100%未満を×、100%以上140%未満を○、140%以上を◎と評価した。結果を表2に示す。 [Test Example 8] (Evaluation of 60 ° glossiness)
About the hard coat film manufactured by the Example and the comparative example, the glossiness (made by Nippon Denshoku Industries Co., Ltd.) was used, and 60 degree glossiness (gloss value) was measured based on JISZ8741-1997. Based on the results, 60 ° glossiness of less than 100% was evaluated as x, 100% to less than 140% was evaluated as ◯, and 140% or more was evaluated as ◎. The results are shown in Table 2.
2…基材フィルム
3…第1のハードコート層
4…第2のハードコート層
5…粘着剤層 DESCRIPTION OF
Claims (11)
- 基材フィルムと、前記基材フィルムの少なくとも一方の主面側に積層された第1のハードコート層と、前記第1のハードコート層における前記基材フィルム側とは反対の主面側に積層された第2のハードコート層とを備えたハードコートフィルムであって、
前記基材フィルムがポリイミドフィルムであり、
前記第1のハードコート層および前記第2のハードコート層が、互いに異なる材料からなり、
前記第1のハードコート層の屈折率と前記第2のハードコート層の屈折率との差が、絶対値で0.04以下であり、
前記第1のハードコート層の厚さおよび前記第2のハードコート層の厚さの合計が、7μm以上、35μm以下である
ことを特徴とするハードコートフィルム。 A base film, a first hard coat layer laminated on at least one main surface side of the base film, and a main surface side opposite to the base film side in the first hard coat layer A hard coat film comprising a second hard coat layer,
The base film is a polyimide film;
The first hard coat layer and the second hard coat layer are made of different materials,
The difference between the refractive index of the first hard coat layer and the refractive index of the second hard coat layer is 0.04 or less in absolute value,
The hard coat film, wherein a total thickness of the first hard coat layer and the second hard coat layer is 7 μm or more and 35 μm or less. - 前記第1のハードコート層および前記第2のハードコート層が、活性エネルギー線硬化性成分を含有する組成物を硬化させた材料からなり、
前記第1のハードコート層が、前記第2のハードコート層よりも柔らかい材料からなる
ことを特徴とする請求項1に記載のハードコートフィルム。 The first hard coat layer and the second hard coat layer are made of a material obtained by curing a composition containing an active energy ray-curable component,
The hard coat film according to claim 1, wherein the first hard coat layer is made of a material softer than the second hard coat layer. - 前記第1のハードコート層が、アルキレンオキシドによって変性された活性エネルギー線硬化性成分を含有する組成物を硬化させた材料からなり、
前記第2のハードコート層が、アルキレンオキシドによって変性されていない活性エネルギー線硬化性成分を含有する組成物を硬化させた材料からなる
ことを特徴とする請求項1または2に記載のハードコートフィルム。 The first hard coat layer is made of a material obtained by curing a composition containing an active energy ray-curable component modified with alkylene oxide,
The hard coat film according to claim 1 or 2, wherein the second hard coat layer is made of a material obtained by curing a composition containing an active energy ray-curable component that is not modified with an alkylene oxide. . - 前記活性エネルギー線硬化性成分が、多官能性(メタ)アクリレート系モノマーであることを特徴とする請求項2または3に記載のハードコートフィルム。 The hard coat film according to claim 2 or 3, wherein the active energy ray-curable component is a polyfunctional (meth) acrylate monomer.
- 前記第1のハードコート層の屈折率が、1.40以上、1.80以下であることを特徴とする請求項1~4のいずれか一項に記載のハードコートフィルム。 The hard coat film according to any one of claims 1 to 4, wherein a refractive index of the first hard coat layer is 1.40 or more and 1.80 or less.
- 前記第2のハードコート層の屈折率が、1.40以上、1.80以下であることを特徴とする請求項1~5のいずれか一項に記載のハードコートフィルム。 6. The hard coat film according to claim 1, wherein a refractive index of the second hard coat layer is 1.40 or more and 1.80 or less.
- 前記第1のハードコート層の厚さが、3μm以上、30μm以下であることを特徴とする請求項1~6のいずれか一項に記載のハードコートフィルム。 The hard coat film according to any one of claims 1 to 6, wherein the thickness of the first hard coat layer is 3 µm or more and 30 µm or less.
- 前記第2のハードコート層の厚さが、0.75μm以上、10μm以下であることを特徴とする請求項1~7のいずれか一項に記載のハードコートフィルム。 The hard coat film according to any one of claims 1 to 7, wherein a thickness of the second hard coat layer is 0.75 µm or more and 10 µm or less.
- 前記ポリイミドフィルムの厚さが、5μm以上、300μm以下であることを特徴とする請求項1~8のいずれか一項に記載のハードコートフィルム。 The hard coat film according to any one of claims 1 to 8, wherein the polyimide film has a thickness of 5 µm or more and 300 µm or less.
- フレキシブルディスプレイを構成するフレキシブル部材として使用されることを特徴とする請求項1~9のいずれか一項に記載のハードコートフィルム。 The hard coat film according to any one of claims 1 to 9, wherein the hard coat film is used as a flexible member constituting a flexible display.
- 前記基材フィルムの少なくとも一方の主面側には、粘着剤層が積層されていることを特徴とする請求項1~10のいずれか一項に記載のハードコートフィルム。 11. The hard coat film according to claim 1, wherein an adhesive layer is laminated on at least one main surface side of the base film.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020187024967A KR102619222B1 (en) | 2016-08-23 | 2016-08-23 | hard coat film |
JP2017507032A JP6216907B1 (en) | 2016-08-23 | 2016-08-23 | Hard coat film |
PCT/JP2016/074567 WO2018037489A1 (en) | 2016-08-23 | 2016-08-23 | Hard coat film |
CN202110239725.6A CN113009602B (en) | 2016-08-23 | 2016-08-23 | Hard coating film |
CN201680085288.4A CN109073789B (en) | 2016-08-23 | 2016-08-23 | Hard coating film |
TW106114771A TWI759298B (en) | 2016-08-23 | 2017-05-04 | Hard coat film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2016/074567 WO2018037489A1 (en) | 2016-08-23 | 2016-08-23 | Hard coat film |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018037489A1 true WO2018037489A1 (en) | 2018-03-01 |
Family
ID=60107319
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/074567 WO2018037489A1 (en) | 2016-08-23 | 2016-08-23 | Hard coat film |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6216907B1 (en) |
KR (1) | KR102619222B1 (en) |
CN (2) | CN109073789B (en) |
TW (1) | TWI759298B (en) |
WO (1) | WO2018037489A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020097165A (en) * | 2018-12-18 | 2020-06-25 | 三菱ケミカル株式会社 | Laminated film |
JP2021059040A (en) * | 2019-10-04 | 2021-04-15 | アイカ工業株式会社 | Hard coat film |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7119424B2 (en) * | 2017-03-02 | 2022-08-17 | 大日本印刷株式会社 | Optical film and image display device |
WO2018180304A1 (en) * | 2017-03-29 | 2018-10-04 | 大日本印刷株式会社 | Optical film and image display device |
JP7097959B2 (en) | 2017-10-27 | 2022-07-08 | アプライド マテリアルズ インコーポレイテッド | Flexible cover lens film |
KR102638825B1 (en) * | 2018-01-24 | 2024-02-21 | 주식회사 동진쎄미켐 | Polyimide film and method for producing the same |
KR102691346B1 (en) | 2018-05-10 | 2024-08-05 | 어플라이드 머티어리얼스, 인코포레이티드 | Replaceable cover lens for flexible display |
KR20240107376A (en) | 2018-08-14 | 2024-07-09 | 어플라이드 머티어리얼스, 인코포레이티드 | Multi-layer wet-dry hardcoats for flexible cover lens |
US11934056B2 (en) | 2019-06-26 | 2024-03-19 | Applied Materials, Inc. | Flexible multi-layered cover lens stacks for foldable displays |
CN114292541A (en) * | 2021-12-23 | 2022-04-08 | 南通纳尔材料科技有限公司 | Optically transparent anti-fouling scratch-resistant protective film composition |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09176485A (en) * | 1995-12-27 | 1997-07-08 | Tomoegawa Paper Co Ltd | Resin composition for coating film and molded article of coating film using the same |
JP2005096298A (en) * | 2003-09-25 | 2005-04-14 | Dainippon Printing Co Ltd | Optical film and optical display device equipped with it |
JP2007046031A (en) * | 2004-12-17 | 2007-02-22 | Nitto Denko Corp | Hard coating film and method for producing the same |
JP2008116596A (en) * | 2006-11-02 | 2008-05-22 | Riken Technos Corp | Hard coat film and antireflection film |
JP2010085501A (en) * | 2008-09-29 | 2010-04-15 | Fujifilm Corp | Liquid crystal display device |
JP2011152681A (en) * | 2010-01-26 | 2011-08-11 | Panasonic Electric Works Co Ltd | Hard coat film |
JP2013101330A (en) * | 2011-10-17 | 2013-05-23 | Dainippon Printing Co Ltd | Optical film, polarizing plate and image display device |
WO2016060213A1 (en) * | 2014-10-17 | 2016-04-21 | 三菱瓦斯化学株式会社 | Polyimide resin composition, polyimide film and laminate |
WO2016076243A1 (en) * | 2014-11-10 | 2016-05-19 | 住友化学株式会社 | Resin film, laminated film, optical member, display member, front plate, and method for producing laminated film |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4543441B2 (en) * | 1998-09-01 | 2010-09-15 | 凸版印刷株式会社 | Hard coat film or sheet |
JP2006058574A (en) * | 2004-08-19 | 2006-03-02 | Nitto Denko Corp | Hard coat film |
JP5713528B2 (en) * | 2008-11-18 | 2015-05-07 | 三菱化学株式会社 | Active energy ray-curable resin composition, hard coat cured film and laminate |
JP2013117584A (en) * | 2011-12-01 | 2013-06-13 | Keiwa Inc | Hard coat film, transparent conductive laminate, and touch panel |
JP5468167B1 (en) | 2013-05-20 | 2014-04-09 | 尾池工業株式会社 | Laminated body |
JP6227321B2 (en) * | 2013-08-05 | 2017-11-08 | リンテック株式会社 | Transparent conductive film with protective film |
JP2015069197A (en) | 2013-10-01 | 2015-04-13 | Dic株式会社 | Hard coat film and image display device |
WO2015076566A1 (en) * | 2013-11-19 | 2015-05-28 | 주식회사 엘지화학 | Plastic film |
JP2016002764A (en) * | 2014-06-19 | 2016-01-12 | 日本合成化学工業株式会社 | Laminate, use thereof, and production method thereof |
-
2016
- 2016-08-23 CN CN201680085288.4A patent/CN109073789B/en active Active
- 2016-08-23 KR KR1020187024967A patent/KR102619222B1/en active IP Right Grant
- 2016-08-23 JP JP2017507032A patent/JP6216907B1/en active Active
- 2016-08-23 WO PCT/JP2016/074567 patent/WO2018037489A1/en active Application Filing
- 2016-08-23 CN CN202110239725.6A patent/CN113009602B/en active Active
-
2017
- 2017-05-04 TW TW106114771A patent/TWI759298B/en active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09176485A (en) * | 1995-12-27 | 1997-07-08 | Tomoegawa Paper Co Ltd | Resin composition for coating film and molded article of coating film using the same |
JP2005096298A (en) * | 2003-09-25 | 2005-04-14 | Dainippon Printing Co Ltd | Optical film and optical display device equipped with it |
JP2007046031A (en) * | 2004-12-17 | 2007-02-22 | Nitto Denko Corp | Hard coating film and method for producing the same |
JP2008116596A (en) * | 2006-11-02 | 2008-05-22 | Riken Technos Corp | Hard coat film and antireflection film |
JP2010085501A (en) * | 2008-09-29 | 2010-04-15 | Fujifilm Corp | Liquid crystal display device |
JP2011152681A (en) * | 2010-01-26 | 2011-08-11 | Panasonic Electric Works Co Ltd | Hard coat film |
JP2013101330A (en) * | 2011-10-17 | 2013-05-23 | Dainippon Printing Co Ltd | Optical film, polarizing plate and image display device |
WO2016060213A1 (en) * | 2014-10-17 | 2016-04-21 | 三菱瓦斯化学株式会社 | Polyimide resin composition, polyimide film and laminate |
WO2016076243A1 (en) * | 2014-11-10 | 2016-05-19 | 住友化学株式会社 | Resin film, laminated film, optical member, display member, front plate, and method for producing laminated film |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020097165A (en) * | 2018-12-18 | 2020-06-25 | 三菱ケミカル株式会社 | Laminated film |
JP7225767B2 (en) | 2018-12-18 | 2023-02-21 | 三菱ケミカル株式会社 | laminated film |
JP2021059040A (en) * | 2019-10-04 | 2021-04-15 | アイカ工業株式会社 | Hard coat film |
JP7295769B2 (en) | 2019-10-04 | 2023-06-21 | アイカ工業株式会社 | hard coat film |
Also Published As
Publication number | Publication date |
---|---|
CN113009602B (en) | 2023-05-23 |
KR20190039466A (en) | 2019-04-12 |
CN109073789B (en) | 2021-07-13 |
CN109073789A (en) | 2018-12-21 |
JPWO2018037489A1 (en) | 2018-08-23 |
TWI759298B (en) | 2022-04-01 |
CN113009602A (en) | 2021-06-22 |
KR102619222B1 (en) | 2023-12-28 |
TW201808607A (en) | 2018-03-16 |
JP6216907B1 (en) | 2017-10-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6216907B1 (en) | Hard coat film | |
JP6345894B1 (en) | Flexible display | |
JP6291128B1 (en) | Flexible display | |
JP6307205B1 (en) | Hard coat film | |
JP6532929B2 (en) | Hard coat film | |
JP6189642B2 (en) | Touch panel | |
JP5486840B2 (en) | Antireflection film and polarizing plate using the same | |
JP2006137835A (en) | Material for forming anti-glare hard coat layer and anti-glare hard coat film | |
JP2007127823A (en) | Optical film and its manufacturing method | |
JP7347922B2 (en) | Fingerprint resistance evaluation method, optical member production method, and optical member | |
US20230311456A1 (en) | Display device member, optical laminate, and display device | |
JP7067900B2 (en) | Coat film | |
JP7547892B2 (en) | Display device components, display devices and electronic devices | |
WO2023085240A1 (en) | Hard coat film for project screen and project screen | |
JP2022079918A (en) | Film for molding | |
JP2022079917A (en) | Anti-reflection film | |
JP2020049917A (en) | Writing feeling enhancement sheet | |
JP2018180981A (en) | Film for touch panel and touch panel |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 2017507032 Country of ref document: JP |
|
ENP | Entry into the national phase |
Ref document number: 20187024967 Country of ref document: KR Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16914163 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 16914163 Country of ref document: EP Kind code of ref document: A1 |