CN113448001B - Hard coating film, polarizing plate, hard coating film processed product, and display member - Google Patents

Hard coating film, polarizing plate, hard coating film processed product, and display member Download PDF

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Publication number
CN113448001B
CN113448001B CN202110794670.5A CN202110794670A CN113448001B CN 113448001 B CN113448001 B CN 113448001B CN 202110794670 A CN202110794670 A CN 202110794670A CN 113448001 B CN113448001 B CN 113448001B
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Prior art keywords
hard coating
film
coating film
meth
hard coat
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CN113448001A (en
Inventor
新纳干大
松井佑纪男
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Toppan Tomoegawa Optical Films Co Ltd
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Toppan Tomoegawa Optical Films Co Ltd
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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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness

Abstract

Provided are a hard coating film having high hardness, low curling properties and high bending properties, a polarizing plate using the hard coating film, a hard coating film processed product and a display member. A hard coating film (1) comprising a transparent substrate (2) and hard coating layers (3 a, 3 b) provided on both surfaces thereof, wherein the transparent substrate (2) has a thickness of 5 [ mu ] m to 40 [ mu ] m, the hard coating layers (3 a, 3 b) each have a thickness of 5 [ mu ] m to 30 [ mu ] m, the total volume of the hard coating layers (3 a, 3 b) is 40% or more of the total volume of the hard coating film (1), and the total thickness of the hard coating film (1) is 80 [ mu ] m or less.

Description

Hard coating film, polarizing plate, hard coating film processed product, and display member
The present application is a divisional application of application No. 2017800106173, application day 2017, 2/14, and application name "hard coating film, polarizing plate using the hard coating film, hard coating film processed product, display member".
Technical Field
The present application relates to a hard coating film for a display device, a polarizing plate using the hard coating film, a hard coating film processed product, and a display member.
Background
In display parts such as liquid crystal display panels and touch panels, hard coating films are used to improve surface hardness and scratch resistance. The hard coat film is obtained by forming a hard coat layer composed of a cured film of the resin composition on the surface of the transparent substrate. With the recent reduction in thickness and weight of display devices, the thickness of the hard coating film is also required to be reduced, and the thickness of the transparent substrate used for the hard coating film is also required to be reduced.
For example, patent document 1 describes: a curable resin composition for a hard coating, which comprises reactive silica fine particles having a reactive functional group on the surface, a polyfunctional monomer having 3 or more reactive functional groups in 1 molecule, and a reactive polymer having a specific molecular structure, is applied to one surface of a substrate and cured, thereby forming a hard coating having high hardness while forming a thin film.
Prior art literature
Patent literature
Patent document 1 Japanese patent application laid-open No. 2010-120991
Disclosure of Invention
Problems to be solved by the application
In the case of a composition in which a hard coating layer is provided only on one side of a substrate, such as the hard coating film described in patent document 1, it is sometimes necessary to thicken the film thickness of the curable resin composition for a hard coating layer in order to obtain a desired hardness. In this case, there are the following problems: the resulting hard coating film is too strong in curl and is inferior in usability when the hard coating film is further processed or used as a display member. In addition, when a hard coating layer is provided on one surface of a thin substrate having a thickness of 40 μm or less, the pencil hardness of the hard coating film tends to be poor due to the influence of the low-hardness substrate. In addition, there is a problem that a hard coating film having a hard coating layer provided on one surface thereof is weakened in bendability and the hard coating layer is liable to be broken.
Accordingly, an object of the present application is to provide a hard coating film having high hardness, low curling properties and high bending properties, a polarizing plate using the hard coating film, a hard coating film processed product and a display member.
Means for solving the problems
The present application relates to a hard coating film having hard coatings on both surfaces of a transparent substrate. The hard coating film according to the present application is characterized in that the transparent substrate has a thickness of 5 [ mu ] m to 40 [ mu ] m, the hard coating layers each have a thickness of 5 [ mu ] m to 30 [ mu ] m, the total volume of the hard coating layers is 40% or more of the total volume of the hard coating film, and the total thickness is 80 [ mu ] m or less.
The polarizing plate, the hard coating film processed product and the display component have the hard coating film.
Effects of the application
According to the present application, a hard coating film having high hardness, low curling property and high bending property, a polarizing plate using the hard coating film, a hard coating film processed product and a display member can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view of a hard coat film according to an embodiment.
Fig. 2 is a schematic diagram showing a test method (cylindrical winding test method) of the bending test.
Detailed Description
Fig. 1 is a schematic cross-sectional view of a hard coat film according to an embodiment.
The hard coat film 1 has hard coat layers 3a and 3b provided on both surfaces of a transparent substrate 2.
(transparent substrate)
The transparent substrate 2 is a film that is a matrix of the hard coat film 1. The transparent substrate 2 is not particularly limited as long as it is a film made of a material excellent in transparency and visible light transmittance, and for example, a film made of any one of cellulose triacetate, cyclic olefin polymer, cyclic olefin copolymer, acrylic polymer, polyethylene terephthalate, polyimide, and polycarbonate can be used.
The transparent substrate 2 has a thickness of 5 to 40 μm. If the thickness of the transparent substrate 2 is less than 5 μm, the transparent substrate 2 becomes too thin, and the hardness of the hard coating layer 3 and the strength of the hard coating film 1 are lowered. On the other hand, if the thickness of the transparent substrate 2 exceeds 40 μm, the hard coating film 1 becomes thicker, and thus the thinning of the display member using the hard coating film 1 is not facilitated.
(hard coating)
The hard coat layers 3a and 3b are formed by curing a composition for forming a hard coat layer containing at least an active energy ray curable resin such as ultraviolet rays or electron beams as a binder resin. At least one of the hard coat layers 3a and 3b is formed by curing a composition for forming a hard coat layer containing an active energy ray-curable resin and colloidal silica. If colloidal silica is contained in at least one of the hard coatings 3a and 3b, the pencil hardness of the hard coating film 1 can be made 7H or more. The hard coat layers 3a and 3b may be formed of an active energy ray-curable resin containing colloidal silica.
The thickness of the hard coat layers 3a and 3b is 5 to 30 μm. If the thickness of the hard coat layers 3a and 3b is less than 5 μm, the hardness of the hard coat layers 3a and 3b is insufficient. On the other hand, if the thickness of the hard coating layers 3a and 3b exceeds 30 μm, the thickness of the hard coating film 1 becomes thicker, and therefore, the thinning of the display member using the hard coating film 1 is not facilitated.
The colloidal silica is a component imparting hardness to the hard coat layer 3 a. As the colloidal silica, a colloidal silica having an average particle diameter of 80nm or less is used. If the average particle diameter of the colloidal silica exceeds 80nm, the transparency of the hard coating film is lowered. The lower limit of the average particle diameter of the colloidal silica is not particularly limited, and colloidal silica having an average particle diameter of 5nm or more can be suitably used.
The amount of colloidal silica added is set to 20 to 70 mass% of the total solid content contained in the composition for forming a hard coat layer. If the amount of colloidal silica added is less than 20 mass% of the resin solid content, the hardness of the hard coating layer 3a becomes insufficient. On the other hand, if the amount of colloidal silica added exceeds 70 mass% of the solid content of the resin, the hard coating becomes brittle, and as a result, the hardness is lowered.
As the colloidal silica, surface-modified colloidal silica surface-modified with active energy ray-reactive groups that are reactive by irradiation with active energy rays is preferably used. Such surface-modified colloidal silica is crosslinked by an active energy ray-curable resin used as a binder, and thus the hardness of the hard coat layer can be improved.
The active energy ray-curable resin is a resin polymerized and cured by irradiation with active energy rays such as ultraviolet rays and electron beams, and (meth) acrylate monomers having a monofunctional function, a 2-function, or 3-function or more can be used, for example. In the present specification, "(meth) acrylate" is a generic term for both acrylate and methacrylate, and "(meth) acryl" is a generic term for both acryl and methacryl.
Examples of the monofunctional (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, octadecyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate, phenoxy (meth) acrylate, ethylene oxide modified phenoxy (meth) acrylate, propylene oxide modified (meth) acrylate, nonylphenoxy (meth) acrylate, nonylphenol (meth) acrylate, and nonylphenol (meth) acrylate Propylene oxide modified nonylphenol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, 2- (meth) acryloyloxypropyl tetrahydrophthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, adamantyl acrylate having monovalent mono (meth) acrylates derived from 2-adamantane, adamantane diol, and the like.
Examples of the 2-functional (meth) acrylate compound include di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, and the like.
Examples of the 3-functional or higher (meth) acrylate compound include 3-functional (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, tri (meth) acrylate such as tri 2-hydroxyethyl isocyanurate tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, etc., or 3-functional (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate, etc., and polyfunctional (meth) acrylate compounds in which a part of these (meth) acrylates is substituted with an alkyl group or epsilon-caprolactone.
In addition, as the active energy ray-curable resin, urethane (meth) acrylate may be used. Examples of the urethane (meth) acrylate include those obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer with a (meth) acrylate monomer having a hydroxyl group.
Examples of urethane (meth) acrylates include pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate isophorone diisocyanate urethane prepolymer, and the like.
The active energy ray-curable resin may be used singly or in combination. The active energy ray-curable resin may be a monomer or a partially polymerized oligomer in the composition for forming a hard coat layer.
In the active energy ray-curable resin, the reactive polymer having a weight average molecular weight of 8000 to 15000 is preferably contained in a proportion of 10 to 40 mass% of the solid content of the active energy ray-curable resin. By blending the reactive polymer as a part of the active energy ray-curable resin, curling of the hard coat film can be suppressed.
As the reactive polymer having a weight average molecular weight of 8000 to 15000, a polymer compound in which a plurality of (meth) acryl groups or (meth) acryl groups are bonded to the main chain can be used. Examples of the polymer compounds include BEAMSET371, BEAMSET371MLV, BEAMSETDK, BEAMSETDK2, BEAMSETDK3 (manufactured by Kagaku Kogyo Co., ltd.), and SMP220A, SMP-250A, SMP-360A, SMP-550A (manufactured by Kagaku Kogyo Co., ltd.). The double bond equivalent of these reactive polymers is from 200 to 600g/mol.
A photopolymerization initiator may be added to the composition for forming a hard coat layer. Examples of the photopolymerization initiator include 2, 2-ethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, dibenzoyl, benzoin methyl ether, benzoin ethyl ether, p-chlorobenzophenone, p-methoxybenzophenone, millerone, acetophenone, and 2-chlorothioxanthone. These may be used alone or in combination of two or more.
In addition, a suitable solvent may be added to the composition for forming a hard coat layer. Examples of the solvent include ethers such as dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1, 4-dioxane, 1, 3-dioxolane, 1,3, 5-trioxane, tetrahydrofuran, anisole, and phenetole; ketones such as acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, and methylcyclohexanone; and esters such as ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-pentyl acetate, and γ -butyrolactone; cellosolves such as methyl cellosolve, butyl cellosolve and cellosolve acetate. These may be used alone or in combination of two or more.
As other additives, an antifouling agent, a surface modifier, a leveling agent, a refractive index modifier, a photosensitizer, and a conductive material may be added to the composition for forming a hard coat layer.
The hard coat film 1 according to the present embodiment can be formed by the following method: the coating liquid of the composition for forming a hard coating layer is coated on both sides of a transparent substrate by a wet coating method in a roll-to-roll manner, and the coating film is irradiated with active energy rays such as an electron beam or ultraviolet rays to cure the active energy raysThe resin is cured. As the wet coating method, known methods such as a flow coating method, a spray coating method, a roll coating method, a gravure roll coating method, an air knife coating method, a blade coating method, a wire knife coating method, a reverse coating method, a transfer roll coating method, a micro gravure coating method, a contact coating method, a casting coating method, a slot die coating method, a calender coating method, and a die coating method can be used. In addition, in the case where the coating film is cured by ultraviolet irradiation, when ultraviolet irradiation is employed, a high-pressure mercury lamp, a halogen lamp, a xenon lamp, a fusia lamp, or the like may be used. The ultraviolet irradiation amount is generally 100 to 800mJ/cm 2 Left and right.
In the hard coat film 1 according to the present embodiment, the layers in which the hard coat layers 3a and 3b are provided on both sides of the transparent substrate 2 are employed, and the thickness of the transparent substrate 2 is 5 to 40 μm, the film thicknesses of the hard coat layers 3a and 3b are each 5 to 30 μm, the total of the volumes of the hard coat layers 3a and 3b is 40% or more of the total volume of the hard coat film 1, and the total thickness of the hard coat film 1 is 80 μm or less. In general, when a thin transparent substrate 2 having a thickness of 40 μm or less is used, pencil hardness is deteriorated due to the influence of the transparent substrate 2 having low hardness. In contrast, in the present embodiment, the hard coating layers 3a and 3b are laminated on both surfaces of the transparent substrate 2, and the volume ratio of the transparent substrate 2 is reduced, whereby the influence of the transparent substrate 2 having low hardness can be reduced, and the hardness of the hard coating film 1 can be improved. Specifically, the composition has the following excellent hardness characteristics: the surface of the hard coating film 1 has a pencil hardness of 7H or more and an ultra-fine indentation hardness of 450N/mm at a depth of 50nm from the surface 2 The above.
In addition, by providing the hard coat layers 3a and 3b on both sides of the transparent substrate 2, curling (tilting) of the hard coat film 1 is suppressed, and resistance to bending is also improved. Specifically, the hard coat film 1 according to the present embodiment was cut into square with a square of 100mm square to prepare a sample, and when the sample was placed on a flat surface, the heights of the films at the four corners were 20mm or less. In addition, when the hard coat film 1 according to the present embodiment is bent, no crack is generated in any of the hard coat layers 3a and 3b when the bending diameter of the bent portion is 10mm or more. As described above, the hard coating film 1 according to the present embodiment has an ultra-high hardness (pencil hardness of 7H or more), suppresses curling, and is excellent in bendability.
As described above, according to the present embodiment, the hard coating layers 3a and 3b are laminated on both surfaces of the transparent base material 2 at the above thickness, whereby the hard coating film 1 having all of high hardness, low curling property, and high bending property can be realized.
(other modifications)
Note that, any of the hard coat layers of the hard coat film 1 according to the present embodiment may be subjected to hemming (black frame) printing or an adhesive layer may be provided, to thereby produce a hard coat film processed product. The hard coat film processed product may include both the hemming print and the adhesive layer, or may include the hemming print or the adhesive layer alone.
The polarizing plate may be formed using the hard coat film 1 according to the present embodiment or the hard coat film processed product. Specifically, a polarizing plate can be formed by laminating a polarizing film on any one of the hard coating layers 1 shown in fig. 1. The polarizing film is obtained by, for example, adsorbing and aligning iodine or a dye to a polyvinyl alcohol film.
The hard coat film 1 or the hard coat film processed product according to the present embodiment can be used for forming a display member such as an antireflection film or an antiglare film used in an image display device. An antireflection film can be formed by providing an antireflection layer formed by laminating a plurality of layers having different refractive indices on the hard coat layer 3a or 3b shown in fig. 1. The antireflection film is a film of: the light reflected at the surface of the transparent substrate through the antireflection layer and the light reflected at the surface of the antireflection layer are canceled by interference, thereby suppressing reflection. As an example of the structure of the antireflection film, a film obtained by laminating a hard coat layer, a high refractive index layer, and a low refractive index layer having a lower refractive index than the high refractive index layer in this order on the transparent substrate 2 is given. A medium refractive index layer having a lower refractive index than the high refractive index layer but a higher refractive index than the low refractive index layer may be further provided between the hard coat layer and the high refractive index layer. The antiglare film is such a film: the reflection of external light is reduced and glare is prevented by scattering external light by fine irregularities formed on the surface. Antiglare films can be made, for example, by: fine particles such as resin particles (organic fillers) are added to the hard coat layer 3a or 3b, thereby forming fine irregularities on the surface.
In addition, a layer having an antireflection function or an antiglare function may be combined with the polarizing plate. Specifically, a polarizing film is bonded to one of the hard coat layers 3a and 3b, and an antireflection layer is provided on the other, whereby a polarizing plate having an antireflection function can be configured. Alternatively, a polarizing film is bonded to either one of the hard coat layers 3a and 3b, and resin particles are added to the other, whereby a polarizing plate having an antiglare function can be constituted.
The hard coat film 1 or the hard coat film processed product according to the present embodiment can be used in combination with a liquid crystal panel or the like to construct a display device. Examples of the structure of the display device include an antireflection film, a polarizing plate, a liquid crystal panel, a polarizing plate, and a backlight unit, each of which uses the hard coat film 1 according to the present embodiment or the hard coat film processed product described above, stacked in this order from the viewing side. Further, a touch sensor may be further stacked, so that a display device with the touch sensor may be configured.
The hard coat film 1 or the hard coat film processed product according to the present embodiment can be used as an optical functional film used for a display device such as a smart phone, a tablet computer, a notebook computer, or the like, or a display device (touch panel) with a touch sensor. Examples of the optical functional film include the polarizing film, the antireflection film, and the antiglare film described above, in addition to the hard coat film. Specifically, the hard coat film according to the present embodiment can be used as a film provided on the outermost surface of a display panel of a liquid crystal display device or the like, or as a film provided on the outermost surface of a touch panel, or as an intermediate film provided between a touch sensor and a display panel in a touch panel assembled by direct bonding or air gap.
The polarizing plate and the hardThe processed product of the mass coating film and the display part are provided with the hard coating film 1, and the pencil hardness of the surface is more than 7H, and the ultra-tiny indentation hardness at the position with 50nm distance from the surface is 450N/mm 2 The above excellent hardness characteristics. The polarizing plate, the hard coating film processed product, and the display member were cut into square shapes of 100mm square to prepare samples, and when the samples were placed on a flat surface, the heights of the films at the four corners were 20mm or less. In addition, when the polarizing plate, the hard coating processed product, and the display member are bent, no crack is generated in any of the hard coatings 3a and 3b when the bending diameter of the bending portion is 10mm or more.
Examples
Hereinafter, examples embodying the present application will be described.
A composition for forming a hard coat layer was applied by a bar coating method to the surface of a transparent substrate made of cellulose Triacetate (TAC) and dried, and then irradiated with a metal halide lamp at an irradiation dose of 200mJ/m 2 Ultraviolet rays were irradiated to cure the coating film, thereby obtaining a hard coating film.
Composition for Forming hard coating layer
Resin material
PE-3A (pentaerythritol triacrylate), CORELATER CHEMICAL CORPORATION … mass portion
UA-306H (pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer), kyowa Kagaku Co., ltd. … parts by mass
UB/EB curable resin BEAMSET371, qichuan chemical Co., ltd. … parts by mass
Colloidal silica: MEK-ST (average particle diameter 15 nm), dissan (Kogyo Co., ltd.) … parts by mass
Polymerization initiator: irgacure184 (1-hydroxycyclohexyl phenyl ketone), BASF corporation … parts by mass
Solvent: methyl isobutyl ketone … mass parts
The thickness of the transparent substrates, the thickness of the hard coating layers, the total thickness of the hard coating layers, and the volume ratio of the hard coating layers according to examples 1 to 9 and comparative examples 1 to 6 are shown in table 1. In comparative examples 1, 2, 5 and 6, the hard coat layer was formed on only one surface of the transparent substrate, and in other examples, the hard coat layer was formed on both surfaces of the transparent substrate.
TABLE 1
In addition, the evaluation results of pencil hardness, microhardness, curl and bending test of the hard coating films according to examples 1 to 9 and comparative examples 1 to 6 are also shown in table 1. The pencil hardness, microhardness, curl and bend test shown in table 1 were measured and evaluated as follows.
[ Pencil hardness ]
The pencil hardness of the hard coat surface was measured according to JIS K5400-1900 using a pencil (uni, mitsubishi pencil Co., ltd.) and a Clemens scratch tester (HA-301, tex Mitsu co., ltd.). The test was repeated while changing the hardness of the pencil, and the change in appearance due to the scratch was visually observed, and the maximum hardness at which no scratch was observed was regarded as an evaluation value.
[ micro hardness ]
The ultra-fine indentation hardness was measured at a depth of 50nm from the surface of the hard coating layer using an ultra-fine indentation hardness tester (nanoIndexter SA2, MTS Systems Co.). In the measurement, a triangular pyramid indenter having a radius of curvature of the tip of 100nm and an angle of 80℃was used as the indenter, and the pressing speed was set to 2.0nm/s.
[ curl ]
The thus-produced hard coat film was cut into a square of 10cm square, and a sample was produced, placed on a plane, and the vertical distance from the plane to the tip of the angle 4 was measured as the height at which the angle 4 was set up. The smaller the measured value, the smaller the curl.
[ bending test ]
Fig. 2 is a schematic diagram showing a test method of the bending test (cylindrical winding test). First, a band of 100mm (width direction of film) ×30mm (longitudinal direction of film) was cut out from the produced hard coat film, thereby producing a sample. Next, as shown in fig. 2, the fabricated sample was wound around a stainless steel cylinder for evaluation (diameter 1 to 40mm (every 1 mm)), and held by hand for 5 seconds. At this time, for the sample in which the hard coating layer was formed on only one surface of the transparent substrate, the hard coating layer was wound toward the outside (that is, the surface of the transparent substrate without the hard coating layer was wound so as to be in contact with the stainless steel cylinder for evaluation). Next, the sample peeled from the stainless steel cylinder for evaluation was lifted to a position 10cm away from the three-wavelength fluorescent lamp, and the presence or absence of cracks at the wound position was visually observed. When the crack was confirmed, the diameter of the cylinder was made large by one step (1 mm) and the same test was performed. The minimum diameter of the stainless steel cylinder for evaluation when no crack was generated in the hard coat layer was used as an evaluation value for the bending test.
As shown in table 1, in examples 1 to 9, it was confirmed that a hard coating film having all of good pencil hardness, minute indentation hardness, curl, and bendability was obtained by providing hard coating layers on both surfaces of a transparent substrate, setting the thickness of the transparent substrate to 5 to 40 μm, setting the thickness of the hard coating layers to 5 to 30 μm, setting the total volume of the hard coating layers to 40% or more of the total volume of the hard coating film, and setting the total thickness of the hard coating film to 80 μm or less.
In contrast, comparative examples 1 and 2 were constituted by a layer having a hard coat layer provided only on one surface of a transparent substrate, and the volume ratio of the hard coat layer was less than 40%, so that the pencil hardness was low and the curl was extremely large.
In comparative examples 3 and 4, the hard coat layer was provided on both sides of the transparent substrate, but the volume ratio of the hard coat layer was less than 40%, and therefore the pencil hardness was low. In addition, in comparative example 4, the thickness of the transparent substrate was more than 40 μm, and the total thickness of the hard coat film was also more than 80 μm, whereby the bendability (resistance to bending) was low.
In comparative examples 5 and 6, the hard coat layer was provided on only one surface of the transparent substrate, and the thickness of the transparent substrate was greater than 40 μm, and the total thickness of the hard coat layer was also greater than 80 μm, so that the curl increased and the bendability (resistance to bending) decreased. In comparative example 5, since the volume ratio of the hard coat layer was less than 40%, the pencil hardness was also low. In comparative example 6, the pencil hardness was increased by increasing the film thickness of the hard coat layer, but the curl became extremely large.
From the above, it was confirmed that the present application can provide a hard coating film having all of high hardness, low curling property and high bending property.
Industrial applicability
The hard coat film according to the present application can be used for image display devices and the like.
Description of the reference numerals
1 hard coating film
2 transparent substrate
3a, 3b hard coating

Claims (10)

1. A hard coating film comprising a transparent substrate and a hard coating layer provided on both surfaces of the transparent substrate, characterized in that,
the transparent substrate has a thickness of 5 μm to 40 μm,
the hard coating layers each have a thickness of 5 μm to 30 μm,
the total volume of the hard coating layer is 40% or more of the total volume of the hard coating film, and,
the total thickness of the hard coating film is 80 μm or less,
the transparent substrate is cellulose triacetate,
The hard coat layer is a cured film of a composition containing a (meth) acrylate monomer, a urethane (meth) acrylate, a reactive polymer having a weight average molecular weight of 8000 to 15000 and a double bond equivalent weight of 200 to 600g/mol,
the reactive polymer having a weight average molecular weight of 8000 to 15000 is a polymer compound having a plurality of (meth) acryl groups or (meth) acryl groups bonded to a main chain,
the reactive polymer having a weight average molecular weight of 8000 to 15000 is contained in a proportion of 10 to 40 mass% of the solid content of the composition,
the hardness of the pencil is more than 7H,
the ultra-fine indentation hardness at a position 50nm deep from the surface was 450N/mm 2 The above-mentioned steps are carried out,
the height of the 4-corner film of the sample obtained by cutting the hard coating film into 100mm square is 20mm or less,
when the bending is performed with a bending diameter of 10mm or more, no crack is generated.
2. The hard coat film according to claim 1, wherein,
the hard coating layer on one surface of the transparent substrate contains colloidal silica and ultraviolet curing resin,
the hard coat layer on the other surface of the transparent substrate contains an ultraviolet curable resin.
3. The hard coat film according to claim 2, wherein,
the average particle diameter of the colloidal silica is 80nm or less,
the hard coating layer on the one surface of the transparent substrate contains 20 to 70 mass% of the colloidal silica,
the colloidal silica is surface-treated colloidal silica having ultraviolet-reactive groups on the surface.
4. A polarizing plate having the hard coat film according to claim 1.
5. The polarizing plate according to claim 4, wherein,
the hardness of the pencil is more than 7H,
the ultra-fine indentation hardness at a position 50nm deep from the surface was 450N/mm 2 The above-mentioned steps are carried out,
the 4-angle film of the sample obtained by cutting the polarizing plate into square of 100mm has a standing height of 20mm or less,
when the bending is performed with a bending diameter of 10mm or more, no crack is generated.
6. A display member having the polarizing plate according to claim 4.
7. A hard coating film processed product obtained by providing an adhesive layer on one surface of the hard coating film according to claim 1.
8. A hard coating film processed product obtained by providing a printed layer and an adhesive layer on one surface of the hard coating film according to claim 1.
9. The hard coat film processed article according to claim 7 or 8, wherein,
the hardness of the pencil is more than 7H,
the ultra-fine indentation hardness at a position 50nm deep from the surface was 450N/mm 2 The above-mentioned steps are carried out,
the height of the 4-corner film of the sample obtained by cutting the hard coating processed product into 100mm square is 20mm or less,
when the bending is performed with a bending diameter of 10mm or more, no crack is generated.
10. A display member having the hard coat film processed product according to claim 7 or 8.
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