WO2018037488A1 - Hard coat film - Google Patents
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- WO2018037488A1 WO2018037488A1 PCT/JP2016/074566 JP2016074566W WO2018037488A1 WO 2018037488 A1 WO2018037488 A1 WO 2018037488A1 JP 2016074566 W JP2016074566 W JP 2016074566W WO 2018037488 A1 WO2018037488 A1 WO 2018037488A1
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- hard coat
- film
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
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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
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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
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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 an object of the present invention is to provide a hard coat film which has bending resistance capable of withstanding repeated bending and hardly generates interference fringes.
- the present invention is a hard coat film comprising a base film and a hard coat layer laminated on at least one main surface side of the base film,
- the base film is a polyimide film
- the difference between the refractive index of the polyimide film and the refractive index of the hard coat layer is 0.04 or less in absolute value
- the thickness of the hard coat layer is 0.5 ⁇ m.
- a hard coat film characterized by being 10 ⁇ m or less is provided (Invention 1).
- the hard coat film according to the above invention (Invention 1) is excellent in flex resistance and scratch resistance because the base film is a polyimide film and the thickness of the hard coat layer is in the above range. Moreover, the said hard coat film becomes a thing which an interference fringe does not produce easily because the said refractive index difference exists in said range.
- the refractive index of the hard coat layer is preferably 1.40 or more and 1.85 or less (Invention 2).
- the thickness of the polyimide film is preferably 5 ⁇ m or more and 300 ⁇ m or less (Invention 3).
- the hard coat layer is preferably made of a material obtained by curing a composition containing an active energy ray-curable component and transition metal oxide fine particles (Invention 4). .
- the hard coat film according to the above invention (Inventions 1 to 4) is preferably used as a flexible member constituting a flexible display (Invention 5).
- an adhesive layer is laminated on at least one main surface side of the base film (Invention 6).
- the hard coat film according to the present invention has bending resistance capable of withstanding repeated bending, and interference fringes are hardly generated.
- FIG. 1 is a cross-sectional view of a hard coat film according to an embodiment of the present invention.
- the hard coat film 1 according to the present embodiment includes a base film 2 and a hard coat layer 3 laminated on one main surface side (upper side in FIG. 1) of the base film.
- 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 polyimide film and the refractive index of the hard coat layer 3 is 0.04 or less in absolute value.
- the difference between the refractive index of the polyimide film and the refractive index of the hard coat layer 3 is 0.04 or less in absolute value, whereby the base film 2 of the hard coat layer 3 is obtained.
- the reflection of light at the interface with the surface of the hard coat layer 3 is suppressed, and interference with the reflected light on the surface of the hard coat layer 3 is less likely to occur, thereby suppressing the occurrence of interference fringes.
- 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 polyimide film and the refractive index of the hard coat layer 3 is preferably 0.03 or less in absolute value, particularly 0.02 or less. It is preferable.
- the thickness of the hard coat layer 3 is 0.5 ⁇ m or more and 10 ⁇ m or less.
- the thickness of the hard coat layer 3 exceeds 10 ⁇ m, the flexibility of the hard coat film 1 is lowered.
- the thickness of the hard coat layer 3 is less than 0.5 ⁇ m, the surface hardness of the hard coat layer 3 is lowered and the scratch resistance is poor. That is, when the thickness of the hard coat layer 3 is in the above range, the hard coat film 1 is excellent in bending resistance and scratch resistance.
- the thickness of the hard coat layer 3 is preferably 0.75 ⁇ m or more, and particularly preferably 1 ⁇ m or more. Further, the thickness of the hard coat layer 3 is preferably 8 ⁇ m or less, and particularly preferably 6 ⁇ m or less.
- 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 normally contained in polyimide may be modified with an aliphatic hydrocarbon, whereby the base film 2 has excellent adhesion to the hard coat layer 3.
- 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.
- unevenness may be applied to one or both sides as desired for the purpose of improving adhesion with a layer (hard coat layer 3 or an adhesive layer described later) provided on the surface.
- Surface treatment can be performed by a chemical 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 thickness of the polyimide film is preferably 300 ⁇ m or less as an upper limit, particularly preferably 90 ⁇ m or less, and more preferably 50 ⁇ m or less. Since 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 hard coat layer 3 of the hard coat film 1 according to this embodiment is laminated on one main surface side (upper side in FIG. 1) of the base film 2 and is higher than the hard coat film 1. Gives surface hardness.
- the refractive index of the hard coat layer 3 is preferably 1.40 or more as a lower limit, particularly preferably 1.45 or more, and more preferably 1.56 or more. Further, the refractive index of the hard coat layer 3 is preferably 1.85 or less as an upper limit, particularly preferably 1.80 or less, and further preferably 1.75 or less. When the refractive index of the hard coat layer 3 is in the above range, the difference from the refractive index of the polyimide film tends to be 0.04 or less in absolute value.
- the hard coat layer 3 is not particularly limited as long as it satisfies the above-described refractive index difference and has a predetermined hardness, but is preferably made of a material obtained by curing a composition containing an active energy ray-curable component. In particular, it is preferably made of a material obtained by curing a composition containing an active energy ray-curable component and transition metal oxide fine particles (hereinafter sometimes referred to as “hard coat layer composition”).
- the active energy ray-curable component As the active energy ray-curable component, the active energy ray-curable component is cured by irradiation with active energy rays to exhibit a predetermined hardness, and is described above in relation to the transition metal oxide fine particles. Those capable of achieving a refractive index difference are preferred.
- Specific active energy ray curable components include polyfunctional (meth) acrylate monomers, (meth) acrylate prepolymers, active energy ray curable polymers, etc., among which polyfunctional (meth) acrylates. It is preferably a monomer and / or a (meth) acrylate prepolymer, and more preferably a polyfunctional (meth) acrylate monomer.
- 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.
- dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, or a mixture thereof is preferable from the viewpoint of dispersibility of the transition metal oxide fine particles and scratch resistance.
- 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.
- the hard coat layer composition constituting the hard coat layer 3 of the present embodiment preferably contains transition metal oxide fine particles.
- the refractive index of the hard coat layer 3 can be brought close to the refractive index of the polyimide film, and the refractive index difference can be easily made 0.04 or less in absolute value.
- a high surface hardness can be imparted to the hard coat layer 3.
- transition metal oxide fine particles for example, fine particles of zirconium oxide, titanium oxide, tantalum oxide, zinc oxide, hafnium oxide, cerium oxide, niobium oxide and the like are preferable. These are used singly or in combination of two or more. Among these, it is possible to give a high refractive index to the hard coat layer 3 and it is difficult to improve the haze of the hard coat layer 3, and group 4 element oxide fine particles, specifically zirconium oxide fine particles and oxidized Titanium fine particles are particularly preferred.
- the crystal structure of the titanium oxide fine particles is not particularly limited, but is preferably a rutile type. By being a rutile type, deterioration with time of the hard coat layer 3 due to photocatalytic activity can be suppressed.
- Zirconium oxide fine particles and titanium oxide fine particles may be surface-treated.
- it may be covered with an oxide such as aluminum or silicon, or may be modified with an organic compound.
- the organic compound include polyol, alkanolamine, stearic acid, silane coupling agent, and titanate coupling agent.
- the shape of the transition metal oxide fine particles may be spherical or non-spherical.
- the average particle diameter of the transition metal oxide fine particles is preferably 1 nm or more as a lower limit, particularly preferably 3 nm or more, and more preferably 5 nm or more.
- the average particle diameter of the transition metal oxide fine particles is 1 nm or more, the dispersibility is improved and the obtained hard coat layer 3 has a higher surface hardness.
- the average particle diameter of the transition metal oxide fine particles is preferably 500 nm or less as an upper limit, particularly preferably 200 nm or less, and further preferably 50 nm or less.
- the average particle diameter of the transition metal oxide fine particles is 500 nm or less, light scattering hardly occurs in the obtained hard coat layer 3, and the transparency of the hard coat layer 3 is increased.
- the average particle diameter of the transition metal oxide fine particles is obtained by measuring the primary particle diameter by a zeta potential measurement method.
- the content of the transition metal oxide fine particles in the hard coat layer 3 of the present embodiment is preferably 5% by mass or more, particularly preferably 10% by mass or more, as a lower limit value in the hard coat layer 3. Furthermore, it is preferable that it is 40 mass% or more.
- the content of the transition metal oxide fine particles is 5% by mass or more, the refractive index of the hard coat layer 3 is easily brought close to the refractive index of the polyimide film, and high hardness is easily imparted to the hard coat layer 3. .
- the content of the transition metal oxide fine particles in the hard coat layer 3 is preferably 95% by mass or less, particularly preferably 85% by mass or less, and more preferably 75% by mass or less as an upper limit. Preferably there is.
- the refractive index of the hard coat layer 3 is easily brought close to the refractive index of the polyimide film as described above, and the hard coat layer composition is used. Layer formation is facilitated.
- a dispersant may be used in order to improve the dispersibility of the transition metal oxide fine particles in the hard coat layer composition.
- an acrylic resin is preferable from the viewpoint of compatibility with the active energy ray-curable component.
- the hard coat layer composition contains a photopolymerization initiator. Is preferred. 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 hard coat layer 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, particularly 0.1 mass. It is preferably at least 1 part by weight, and more preferably at least 1 part by weight. 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 hard coat layer composition constituting the hard coat layer 3 of the present embodiment may contain various additives in addition to the components described above.
- the 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 hard coat film 1 which concerns on this embodiment can be preferably manufactured with the following method.
- a composition for a hard coat layer containing an active energy ray-curable component is used.
- composition layer made of the composition for a hard coat layer is formed on one main surface of the base film 2.
- the composition for hard coat layer may be directly applied to one main surface of the substrate film 2 to form a composition layer, or after the composition for hard coat layer is applied to the cover sheet, A composition layer with a cover sheet may be bonded to one main surface of the base film 2.
- a desired resin film can be used as the cover sheet.
- surface or both surfaces of these resin films was peel-processed with the peeling agent can also be used.
- the composition layer is formed by preparing a coating liquid containing the composition for a hard coat layer and, if desired, further a solvent, applying this to the base film 2 or the cover sheet, and drying.
- Application of the coating solution may be performed 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. Drying can be performed, for example, by heating at 40 to 180 ° C. for about 30 seconds to 5 minutes.
- 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.
- composition layer is cured to form the hard coat layer 3 by irradiating the composition layer with active energy rays.
- 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 hard coat layer 3 having a high surface hardness is effectively formed without being inhibited by oxygen.
- a cover sheet is newly laminated on the composition layer, or the base film 2 and the laminate of the composition layer are placed in an atmosphere having a low oxygen concentration, preferably in 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 has excellent bending resistance capable of withstanding repeated bending. Can be determined.
- the hard coat film 1 according to the present embodiment has the smallest diameter among the mandrels in which no cracks or peeling occurred in the hard coat layer 3 in the bending resistance test by the cylindrical mandrel method according to JIS K5600-5-1.
- the mandrel diameter (minimum mandrel diameter) is preferably 14 mm or less, particularly preferably 6 mm or less, and further preferably 4 mm or less.
- the hard coat film 1 according to the present embodiment does not add micro-order fine particles to prevent interference fringes, but the difference in refractive index between the hard coat layer 3 and the base film 2. It is solved by making it smaller. 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 second hard coat layer 4 may be laminated (the code
- the scratch resistance on the other main surface side of the base film 2 is improved, and the hard coat layer 3 is cured and contracted by the second hard coat layer 4. Curing shrinkage of the hard coat film 1A can be suppressed.
- the second hard coat layer 4 may be made of the same material as the hard coat layer 3 described above, or may be made of a different material.
- the thickness of the second hard coat layer 4 may be the same thickness as the hard coat layer 3 described above, or may be a different thickness.
- 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. However, the hard coat layer 3 and the second hard coat layer 4 may be cured simultaneously, or the composition layer of the hard coat layer 3 (or the second hard coat layer 4) is formed and cured. Thereafter, a composition layer of the second hard coat layer 4 (or hard coat layer 3) may be formed and cured.
- an adhesive layer 5 is laminated on the other main surface side of the base film 2 in the hard coat film 1 (the surface opposite to the surface on which the hard coat layer 3 is laminated).
- symbol of the hard coat film shown in FIG. 3 is described as "1B.”
- an adhesive layer may be laminated on the side of the second hard coat layer 4 opposite to the base film 2 side in the hard coat film 1A.
- 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 1B 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 according to this embodiment may be laminated with other layers such as an adhesive layer, a barrier layer, a conductive layer, a low reflection layer, an easy printing layer, and an antifouling layer.
- the hard coat films 1, 1A and 1B according to the above embodiment are, for example, flexible displays in various electronic devices, particularly mobile electronic devices, specifically, liquid crystal displays (LCD), It can be preferably used as a flexible member for the surface layer (protective film) or intermediate layer of various flexible displays such as an organic EL display (OELD) and an electronic paper module (film-shaped electronic paper).
- LCD liquid crystal displays
- OELD organic EL display
- electronic paper module film-shaped electronic paper
- another layer may be interposed between the base film 2 in the hard coat films 1, 1 ⁇ / b> A, 1 ⁇ / b> B and the hard coat layer 3, the second hard coat layer 4, or the adhesive layer 5.
- 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, the polyimide film A with a film thickness of 25 micrometers was obtained by cooling to normal temperature under vacuum. When measured with respect to the polyimide film A, 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 type 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.
- 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 dipentaerythritol hexaacrylate as an active energy ray-curable component (in terms of solid content; the same applies hereinafter) and surface-modified zirconium oxide fine particles as transition metal oxide fine particles (product name “ZRMIBK15WT% ⁇ manufactured by CIK Nanotech Co., Ltd.”) F85 ", average particle size: 15 nm) in a mixed solvent in which 150 parts by mass of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator were mixed with methyl isobutyl ketone and cyclohexanone at a mass ratio of 1: 1. The mixture was stirred and mixed to obtain a coating liquid for the hard coat layer composition.
- a coating liquid of the hard coat layer composition is applied using a Mayer bar, and is heat-dried at 70 ° C. for 1 minute. A composition layer of the composition was formed.
- the composition layer of the hard coat layer composition is cured by irradiating ultraviolet rays from the above composition layer side under the following conditions to form a hard coat layer (thickness: 3 ⁇ m) to obtain a hard coat film.
- Conveyor speed 1.2m / min ⁇ UV irradiation under nitrogen atmosphere (oxygen concentration 1% or less)
- Examples 2 to 8, Comparative Examples 1 to 5 Except for changing the type and composition of each component constituting the hard coat layer composition, the thickness of the hard coat layer, and the type and thickness of the base film as shown in Table 1, the same as in Example 1 A hard coat film was produced.
- the refractive index of the hard coat layer was measured using a spectroscopic ellipsometer (product name “M-2000” manufactured by JA Woollam Co., Ltd.) under the conditions of a measurement wavelength of 589 nm and a measurement temperature of 25 ° C. It measured according to 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, excellent in flex resistance, and were less likely to cause interference fringes.
- 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.
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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)に積層されたハードコート層3とを備えて構成される。 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. The
(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、ハードコートフィルム1に高い表面硬度を付与する。 (1-2) Hard Coat Layer The
活性エネルギー線硬化性成分としては、活性エネルギー線の照射により硬化して所定の硬度を発揮し、かつ遷移金属酸化物微粒子との関係で前述した屈折率差を達成できるものが好ましい。 (1-2-1) Active energy ray-curable component As the active energy ray-curable component, the active energy ray-curable component is cured by irradiation with active energy rays to exhibit a predetermined hardness, and is described above in relation to the transition metal oxide fine particles. Those capable of achieving a refractive index difference are preferred.
本実施形態のハードコート層3を構成するハードコート層用組成物は、遷移金属酸化物微粒子を含有することが好ましい。遷移金属酸化物微粒子を含有することで、ハードコート層3の屈折率を上記ポリイミドフィルムの屈折率に近づけることができ、屈折率差を絶対値で0.04以下にし易くすることができる。また、ハードコート層3に高い表面硬度を付与することもできる。 (1-2-2) Transition metal oxide fine particles The hard coat layer composition constituting the
活性エネルギー線硬化性成分を硬化させるための活性エネルギー線として紫外線を用いる場合には、上記ハードコート層用組成物は、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。 (1-2-3) Photopolymerization initiator When ultraviolet rays are used as the active energy ray for curing the active energy ray-curable component, the hard coat layer composition contains a photopolymerization initiator. Is preferred. 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.
本実施形態のハードコート層3を構成するハードコート層用組成物は、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 hard coat layer composition constituting the
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。本方法では、一例として、活性エネルギー線硬化性成分を含有するハードコート層用組成物を使用するものとする。 (2) Manufacturing method of hard coat film The
(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
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、繰り返しの屈曲に耐え得る耐屈曲性に優れるものであるが、その屈曲の度合いについては、最小マンドレル直径により判断することができる。 (3-2) Minimum Mandrel Diameter As described above, the
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、ハードコート層3と基材フィルム2との屈折率差を小さくす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。 (3-3) Image Sharpness 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。 (3-4) Haze Value From the viewpoint of displaying a clearer image when applied to a display, the haze value of 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、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。 (3-5) 60 ° Glossiness 60 ° glossiness (gloss value) based on JIS Z8741-1997 of the
上記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(ハードコート層3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、第2のハードコート層4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)。この第2のハードコート層4が積層されることで、基材フィルム2の他方の主面側における耐擦傷性が向上するとともに、当該第2のハードコート層4の硬化収縮によりハードコート層3の硬化収縮を相殺し、ハードコートフィルム1Aのカールを抑制することができる。 (4) Other Embodiment-1
On the other main surface side 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(ハードコート層3が積層された面とは反対側の面側)には、図3に示すように、粘着剤層5が積層されてもよい(図3に示すハードコートフィルムの符号を「1B」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1Bを所望の被着体に簡易に貼付することができる。なお、同様に、ハードコートフィルム1Aにおける第2のハードコート層4の基材フィルム2側とは反対側に、粘着剤層が積層されてもよい。 (5) Other embodiment-2
As shown in FIG. 3, an
本実施形態に係るハードコートフィルム1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。 (6) Other embodiment-3
The
以上の実施形態に係るハードコートフィルム1,1A,1B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)または中間層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。 (7) Use of hard coat film The
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] (
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 type 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”).
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の配合割合を変更すると共に、得られたポリイミド塗工液の濃度を調整する以外、製造例1と同様の作製方法を行うことにより、膜厚が15μm、b*が2.25、屈折率が1.70、波長550nmにおける透過率が87%のポリイミドフィルムBを得た(測定方法は上記の通り)。 [Production Example 2] (Preparation of base film 2)
In a N, N-dimethylacetamide solvent, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, biphenyltetracarboxylic dianhydride, and 2,2-bis (3,4- By changing the blending ratio of dicarboxyphenyl) hexafluoropropanoic dianhydride and adjusting the concentration of the obtained polyimide coating solution, the same production method as in Production Example 1 was performed, so that the film thickness was 15 μm. , B * was 2.25, the refractive index was 1.70, and the transmittance at a wavelength of 550 nm was 87% (polyimide film B was obtained as described above).
活性エネルギー線硬化性成分としてのジペンタエリスリトールヘキサアクリレート100質量部(固形分換算;以下同じ)と、遷移金属酸化物微粒子としての表面修飾酸化ジルコニウム微粒子(CIKナノテック社製,製品名「ZRMIBK15WT%-F85」,平均粒径:15nm)150質量部と、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、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 dipentaerythritol hexaacrylate as an active energy ray-curable component (in terms of solid content; the same applies hereinafter) and surface-modified zirconium oxide fine particles as transition metal oxide fine particles (product name “ZRMIBK15WT% − manufactured by CIK Nanotech Co., Ltd.”) F85 ", average particle size: 15 nm) in a mixed solvent in which 150 parts by mass of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator were mixed with methyl isobutyl ketone and cyclohexanone at a mass ratio of 1: 1. The mixture was stirred and mixed to obtain a coating liquid for the hard coat layer composition.
<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) Thereafter, the composition layer of the hard coat layer composition is cured by irradiating ultraviolet rays from the above composition layer side under the following conditions to form a hard coat layer (thickness: 3 μm) to obtain a hard coat film. It was.
<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 (
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、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 8, Comparative Examples 1 to 5]
Except for changing the type and composition of each component constituting the hard coat layer composition, the thickness of the hard coat layer, and the type and thickness of the base film as shown in Table 1, the same as in Example 1 A hard coat film was produced.
A:ジペンタエリスリトールヘキサアクリレート
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12モル導入)
C:表面修飾酸化ジルコニウム微粒子(CIKナノテック社製,製品名「ZRMIBK15WT%-F85」,平均粒径:15nm)
D:表面修飾酸化チタン微粒子(テイカ社製,製品名「ND139」,平均粒径:10nm)
E:1-ヒドロキシシクロヘキシルフェニルケトン
PI-25:ポリイミドフィルムA
PI-15:ポリイミドフィルムB
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) Details of the abbreviations and the like described in Table 1 are as follows.
A: Dipentaerythritol hexaacrylate B: Ethylene oxide-modified dipentaerythritol hexaacrylate (12 mol of ethylene oxide introduced)
C: Surface-modified zirconium oxide fine particles (CIK Nanotech, product name “ZRMIBK15WT% -F85”, average particle size: 15 nm)
D: Surface-modified titanium oxide fine particles (manufactured by Teika, product name “ND139”, average particle size: 10 nm)
E: 1-hydroxycyclohexyl phenyl ketone PI-25: Polyimide film A
PI-15: Polyimide film B
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 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).
上記で測定した基材フィルムの屈折率から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 hard coat layer from the refractive index of the base film 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について、円筒型マンドレル屈曲試験機(コーテック社製)を用いて、JIS K5600-5-1に準拠したマンドレル試験を実施した。当該マンドレル試験は、ハードコートフィルムのハードコート層を外側にして行った。ハードコート層にクラックや剥がれ等の不具合が発生しなかったマンドレルのうち直径が最小のマンドレルの直径(最小マンドレル直径)を求めた。結果を表2に示す。 [Test Example 4] (Mandrel test)
The hard coat films produced in the examples and comparative examples were subjected to a mandrel test in accordance with JIS K5600-5-1 using a cylindrical mandrel bending tester (Cotec). The mandrel test was conducted with the hard coat layer of the hard coat film on the outside. The diameter of the mandrel having the smallest diameter (minimum mandrel diameter) among the mandrels in which no defects such as cracks and peeling occurred in the hard coat layer was determined. 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、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、ハードコート層を外側にして、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 “Surface body no-load U-shaped stretch tester DLDMMLH-FS”) was used with the hard coat layer on the outside. 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…ハードコート層
4…第2のハードコート層
5…粘着剤層 1, 1A, 1B ...
Claims (6)
- 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、
前記ポリイミドフィルムの屈折率と前記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、
前記ハードコート層の厚さが、0.5μm以上、10μm以下である
ことを特徴とするハードコートフィルム。 A hard coat film comprising a base film and a hard coat layer laminated on at least one main surface side of the base film,
The base film is a polyimide film;
The difference between the refractive index of the polyimide film and the refractive index of the hard coat layer is 0.04 or less in absolute value,
The hard coat film has a thickness of 0.5 μm or more and 10 μm or less. - 前記ハードコート層の屈折率が、1.40以上、1.85以下であ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 hard coat film according to claim 1, wherein a refractive index of the hard coat layer is 1.40 or more and 1.85 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または2に記載のハードコートフィルム。 The hard coat film according to claim 1 or 2, wherein the polyimide film has a thickness of 5 µm or more and 300 µm or less.
- 前記ハードコート層が、活性エネルギー線硬化性成分と、遷移金属酸化物微粒子と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1~3のいずれか一項に記載のハードコートフィルム。 The hard coat layer is made of a material obtained by curing a composition containing an active energy ray-curable component and transition metal oxide fine particles. Hard coat film.
- 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1~4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 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1~5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 5, wherein an adhesive layer is laminated on at least one main surface side of the base film.
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JP2017507030A JP6291128B1 (en) | 2016-08-23 | 2016-08-23 | Flexible display |
CN201680088557.2A CN109642964A (en) | 2016-08-23 | 2016-08-23 | Hard coat film |
KR1020197005851A KR102610461B1 (en) | 2016-08-23 | 2016-08-23 | hard coat film |
PCT/JP2016/074566 WO2018037488A1 (en) | 2016-08-23 | 2016-08-23 | Hard coat film |
TW106114770A TWI773671B (en) | 2016-08-23 | 2017-05-04 | Flexible display with repeated bending |
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JP2019217647A (en) * | 2018-06-15 | 2019-12-26 | 大日本印刷株式会社 | Laminated body, polyimide film, surface material for display, touch panel member, liquid crystal display device, organic electroluminescence display device, method for producing polyimide film, method for producing laminated body, and method for producing surface material for display |
JP2020074019A (en) * | 2020-01-08 | 2020-05-14 | 株式会社ダイセル | Antireflection film |
KR20200080036A (en) * | 2018-12-26 | 2020-07-06 | 동우 화인켐 주식회사 | Hard coating film and flexible display window including the same |
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KR102612459B1 (en) | 2017-10-27 | 2023-12-08 | 어플라이드 머티어리얼스, 인코포레이티드 | Flexible cover lens membranes |
KR20230043240A (en) | 2018-05-10 | 2023-03-30 | 어플라이드 머티어리얼스, 인코포레이티드 | Replaceable cover lens for flexible display |
JP2021536030A (en) | 2018-08-14 | 2021-12-23 | アプライド マテリアルズ インコーポレイテッドApplied Materials, Incorporated | Multi-layer wet and dry hard coat for flexible cover lenses |
KR102274527B1 (en) * | 2018-11-20 | 2021-07-07 | 주식회사 엘지화학 | A laminate structure for manufacturing flexible device and a process for manufacturing flexible device using same |
KR20200066828A (en) | 2018-12-03 | 2020-06-11 | 에스케이아이이테크놀로지주식회사 | Hard coating film and method of preparing the same |
JP7404407B2 (en) | 2019-06-26 | 2023-12-25 | アプライド マテリアルズ インコーポレイテッド | Flexible multilayer cover lens laminate for foldable display |
KR102341198B1 (en) | 2020-04-02 | 2021-12-20 | 동우 화인켐 주식회사 | Hard coating film and image display device using the same |
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CN109642964A (en) | 2019-04-16 |
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