CN113352703B - Hard coating film and antireflection film - Google Patents
Hard coating film and antireflection film Download PDFInfo
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- CN113352703B CN113352703B CN202110665660.1A CN202110665660A CN113352703B CN 113352703 B CN113352703 B CN 113352703B CN 202110665660 A CN202110665660 A CN 202110665660A CN 113352703 B CN113352703 B CN 113352703B
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/006—Anti-reflective coatings
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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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- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
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- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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Abstract
Provided are a hard coating film having a layer structure that can be produced without increasing the number of lamination steps, and having metal oxide fine particles unevenly present on the surface of the hard coating film, and an antireflection film using the hard coating film. The hard coating film (10) is provided with a transparent base material (1) and a hard coating layer (2) laminated on the transparent base material (1). The hard coat layer (2) has a metal oxide-containing layer (3) which contains metal oxide fine particles and has a thickness of 0.6 to 20% of the thickness of the hard coat layer (2) on the air interface side. The amount of the metal element A derived from the metal oxide fine particles contained in the metal oxide-containing layer (3) is 50 times or more the amount of the metal element A derived from the metal oxide fine particles contained in the hard coat layer (2) except for the metal oxide-containing layer (3).
Description
The present application is a divisional application of applications having application numbers of 2018111836458, application dates of 2018, 10 and 11, and the title of "hard coat film and antireflection film".
Technical Field
The present invention relates to a hard coating film containing metal oxide fine particles in a hard coating layer, and an antireflection film using the hard coating film.
Background
In an optical film in which an optical functional layer is laminated on a transparent substrate, metal oxide microparticles are added to the optical functional layer, and the refractive index of an optical transparent layer is adjusted or antistatic properties or hardness are imparted to the optical transparent layer by the characteristics of the metal oxide microparticles. However, in an optical film in which metal oxide fine particles are dispersed in an optical functional layer, in order to sufficiently exhibit the characteristics of the metal oxide fine particles, it is necessary to add a large amount of metal oxide fine particles to an optical transparent layer, and in this case, there are problems such as deterioration in transparency of the optical functional layer and coloring of the optical functional layer.
As a method for solving this problem, it has been considered to additionally laminate a layer containing fine metal oxide particles on an optically functional layer laminated on a transparent substrate to reduce the amount of the fine metal oxide particles used, thereby improving transparency or coloring.
However, in the method of separately laminating a layer containing metal oxide fine particles on an optical functional layer, these problems of increase in manufacturing cost and reduction in productivity occur due to increase in the number of lamination steps.
Disclosure of Invention
Accordingly, an object of the present invention is to provide a hard coat film having a producible layer structure without increasing the number of lamination steps and having metal oxide fine particles unevenly distributed on the surface of the hard coat layer, and an antireflection film using the hard coat film.
The hard coating film according to the present invention is characterized in that: a hard coat layer is laminated on a transparent base material, the hard coat layer has a metal oxide-containing layer containing metal oxide fine particles and having a thickness of 0.6 to 20% of the thickness of the hard coat layer on the side of the air interface, and the amount of the metal element A derived from the metal oxide fine particles contained in the metal oxide-containing layer is 50 times or more the amount of the metal element A derived from the metal oxide fine particles contained in the hard coat layer except for the metal oxide-containing layer.
In addition, the antireflection film according to the present invention is characterized in that: the hard coat film has a normal reflectance of 0.1% or less, and reflection hues a and b are both ± 4% or less.
According to the present invention, a hard coat film having a producible layer structure without increasing the number of lamination steps and having metal oxide fine particles unevenly distributed on the surface of the hard coat layer, and an antireflection film using the hard coat film can be provided.
These and other objects, features, aspects and effects of the present invention will become more apparent from the following detailed description with reference to the accompanying drawings.
Brief description of the drawings
Fig. 1 is a schematic sectional view of a hard coating film according to embodiment 1.
Fig. 2 is a schematic cross-sectional view of an antireflection film according to embodiment 2.
Detailed Description
(embodiment 1)
Fig. 1 is a schematic sectional view of a hard coating film according to embodiment 1.
The hard coat film 10 has a hard coat layer 2 laminated on one surface of a transparent substrate 1.
< transparent substrate >
The transparent substrate 1 is a film that serves as a base of the hard coating film 10, and is formed of a material having excellent transparency and visible light transmittance. As a material for forming the transparent substrate 1, polyolefin such as polyethylene and polypropylene, polyester such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyamide such as nylon 6 and nylon 66, triacetyl cellulose, polyimide, polyarylate, polycarbonate, polyacrylate, polyether sulfone, transparent resin such as polysulfone, or inorganic glass can be used. The thickness of the transparent substrate 1 is not particularly limited, but is preferably 10 μm to 200 μm.
< hard coating >
The hard coat layer 2 is formed from a cured film of a hard coating composition containing metal oxide fine particles, a binder, a photopolymerization initiator, and a solvent. A metal oxide-containing layer 3 in which metal oxide fine particles are unevenly distributed is formed on the surface (surface on the interface side with air) of the hard coat layer 2. The metal oxide-containing layer 3 is formed by: in the process of applying the hard coating composition to the transparent substrate 1 and drying the formed coating film, the metal oxide fine particles are unevenly deposited on the surface of the coating film, and the binder is cured in a state in which the metal oxide fine particles are unevenly deposited, thereby forming the metal oxide-containing layer 3. Here, in the present specification, the state in which the metal oxide fine particles are unevenly present in the hard coat layer 2 refers to a state in which: the metal oxide fine particles are locally present in a thickness in the range of 0.6% to 20% of the thickness of the hard coat layer 2, and the amount of the metal element a present from the metal oxide fine particles contained in the metal oxide containing layer 3 is 50 times or more the amount of the metal element a present from the metal oxide fine particles contained in a portion of the hard coat layer 2 other than the metal oxide containing layer 3. When the thickness of the metal oxide-containing layer 3 is less than 0.6% of the thickness of the hard coat layer 2, the characteristics of the metal oxide fine particles cannot be exhibited; when the thickness of the metal oxide containing layer 3 exceeds 20% of the thickness of the hard coat layer 2, the transparency of the hard coat film 10 is reduced. In addition, when the amount of the metal element a derived from the metal oxide fine particles contained in the metal oxide-containing layer 3 is less than 50 times the amount of the metal element a derived from the metal oxide fine particles contained in the portion of the hard coat layer 2 other than the metal oxide-containing layer 3, a state in which the metal oxide fine particles are sufficiently unevenly present cannot be obtained, and the characteristics of the metal oxide fine particles cannot be exhibited.
As the metal oxide fine particles, silicon oxide (SiO) may be used alone 2 ) Antimony doped tin oxide (ATO), phosphorus doped tin oxide (PTO), gallium doped tin oxide (GTO), zirconium oxide (ZrO) 2 ) And titanium oxide (TiO) 2 ) One or a combination of 2 or more of the above. By containing the 1 or more kinds of metal oxide fine particles described above in the hard coat layer 2 so that the metal compound fine particles are unevenly present in the metal oxide containing layer 3, the surface hardness of the hard coat layer 2 can be increased, or the metal oxide containing layer 3 can be made to function as a high refractive index layer having a relatively higher refractive index than other portions. When the metal oxide fine particles are dispersed throughout the hard coat layer, it is necessary to increase the amount of the metal oxide fine particles to be blended in order to exhibit the characteristics of the metal oxide fine particles, and in this case, there is a problem that transparency of the hard coat film 10 is impaired or the hard coat layer 2 is colored. However, if the metal oxide fine particles are unevenly present on the surface of the hard coat layer 2 within the thickness range of 0.6% to 20% of the thickness of the hard coat layer 2 as in the present embodiment, the properties of the metal oxide fine particles can be imparted to the hard coat layer 2 without increasing the amount of the metal oxide fine particles to be incorporated, and thus the transparency or color tone of the hard coat film 10 is not impaired.
The metal oxide fine particles are subjected to surface modification by the combination with the silane coupling agent. As the silane coupling agent, a silane coupling agent having one or more of an alkyl group, a vinyl group, an acryloyl group, and a methacryloyl group as a functional group can be used. When the metal oxide fine particles are surface-modified with a silane coupling agent having these functional groups, the silane coupling agent and a binder described later have poor surface tension. By causing a difference in surface tension between the silane coupling agent and the binder, the metal oxide fine particles can be deposited unevenly on the surface of the coating film in the coating film of the hard coating composition.
The amount of the metal oxide fine particles (the metal oxide fine particles to which the silane coupling agent is bonded) is set to 0.2 to 10 mass% when the total solid content of the hard coating composition is taken as 100 mass%. When the amount of the metal oxide fine particles to be blended is less than 0.2 mass% of the total solid content of the hard coating composition, the metal oxide fine particles are too small to exhibit the characteristics of the metal oxide fine particles. On the other hand, if the amount of the metal oxide fine particles added exceeds 10 mass% of the total solid content of the hard coating composition, the metal oxide fine particles become excessive, and the thickness of the metal oxide-containing layer exceeds 20% of the thickness of the hard coating layer 2, which impairs the transparency of the hard coating film 10.
As the binder, an active energy ray-curable resin which is polymerized and cured by irradiation with an active energy ray such as ultraviolet ray or electron beam can be used. The viscosity of the binder before curing is preferably 100Pa · s or less. When the binder having a viscosity of 100Pa · s or less before curing is used, the nonuniform deposition rate of the metal fine particles can be increased, and the production efficiency of the hard coating film 10 can be improved. The surface tension of the binder is preferably 40mN/m or more. When a binder having a surface tension of 40mN/m or more is used, the difference in surface tension between the binder and the silane coupling agent becomes large, and thus metal oxide fine particles can be deposited unevenly on the surface of a coating film in the process of drying the coating film of the hard coating composition.
Specifically, as the binder, for example, a monofunctional, 2-functional, or 3-or more functional (meth) acrylate monomer can be used. In the present specification, "(meth) acrylate" is a general term for both acrylate and methacrylate, and "(meth) acryloyl" is a general term for both acryloyl and methacryloyl.
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, hexadecyl (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 (meth) phenoxy acrylate, propylene oxide-modified (meth) acrylate, phenoxy phenol (meth) acrylate, ethylene oxide-modified nonyl phenol (meth) acrylate, propylene oxide-modified nonylphenol (meth) acrylate, methoxydiethylene glycol (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 hydrogen phthalate, 2- (meth) acryloyloxypropylhexahydrophthalate, 2- (meth) acryloyloxypropyltetrahydrophthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, and an adamantane (meth) acrylate derivative ester such as an adamantane acrylate having a 1-valent mono (meth) acrylate derived from 2-adamantane or adamantane glycol.
Examples of the 2-functional (meth) acrylate compound include di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butylene glycol 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, and hydroxypivalyl di (meth) acrylate.
Examples of the 3-or more-functional (meth) acrylate compound include: tri (meth) acrylates such as trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, tri 2-hydroxyethyl isocyanurate tri (meth) acrylate, and glycerin tri (meth) acrylate, and 3-functional (meth) acrylate compounds such as pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, and ditrimethylolpropane tri (meth) acrylate; or a polyfunctional (meth) acrylate compound having 3 or more functions 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.; or a polyfunctional (meth) acrylate compound obtained by substituting a part of these (meth) acrylates with an alkyl group or epsilon-caprolactone.
As the active energy ray-curable resin, urethane (meth) acrylate can be used. Examples of the urethane (meth) acrylate include: urethane (meth) acrylate obtained by reacting an isocyanate monomer or prepolymer with a polyester polyol to obtain a product and then reacting a (meth) acrylate monomer having a hydroxyl group with the product.
Examples of the urethane (meth) acrylate 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.
Among the active energy ray-curable resins, a 2-or more-functional (meth) acrylate is preferably used. By using a resin having 2 or more (meth) acryloyl groups as a binder, the hardness of the hard coat layer 2 can be increased.
The active energy ray-curable resin may be used in 1 kind, or 2 or more kinds may be used in combination. In the composition for forming a hard coat layer, the active energy ray-curable resin may be a monomer or an oligomer partially polymerized.
The photopolymerization initiator to be added to the hard coat composition is not particularly limited, and for example, 2,2-ethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, dibenzoyl, benzoin methyl ether, benzoin ethyl ether, p-chlorobenzophenone, p-methoxybenzophenone, michler's ketone, acetophenone, 2-chlorothioxanthone, and the like can be used. Of these, 1 kind may be used alone, or 2 or more kinds may be used in combination.
In addition, a solvent is preferably blended in the hard coating composition. By blending a solvent in the hard coating composition to reduce the viscosity, the nonuniform deposition rate of the metal oxide fine particles can be increased. It is preferable to use a solvent having a vapor pressure of 10kPa or less at 20 ℃, and it is more preferable to use a solvent having a vapor pressure of 5kPa or less at 20 ℃. By using a solvent having a vapor pressure of 10kPa or less, more preferably 5kPa or less at 20 ℃, an increase in the viscosity of the coating film in the drying step of the coating film of the hard coating composition can be suppressed, and thus the rate of uneven deposition of the metal oxide fine particles can be increased.
Examples of the solvent include ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, 1,4-dioxane, polyethylene glycol monomethyl ether, and the like; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methylcyclohexanone; esters such as ethyl acetate, n-propyl acetate, n-butyl acetate, n-pentyl acetate, and the like. Of these, 1 species may be used alone, or 2 or more species may be mixed and used. Of these, polyethylene Glycol Monomethyl Ether (PGME) is preferably used as the solvent. When PGME is used as the solvent, the non-uniform deposition of the metal oxide fine particles can be promoted as compared with the case of using other solvents.
As other additives, an antifouling agent, a surface conditioner, a leveling agent, a refractive index adjuster, a photosensitizer, a conductive material, and the like may be added to the hard coating composition.
The hard coat film 10 according to the present embodiment can be produced by: the hard coating composition is applied to at least one surface of the transparent substrate 1, and after the coating film is dried, the coating film is cured by ultraviolet irradiation. As described above, in the step of drying the coating film of the hard coating composition, the metal oxide fine particles are unevenly deposited on the surface of the coating film by the difference in surface tension between the silane coupling agent bound to the metal oxide fine particles and the binder. By curing the binder in this state, a metal oxide-containing layer in which metal oxide fine particles are unevenly present is formed.
The method for applying the coating liquid is not particularly limited, and a known wet coating method can be used. As a method for curing the coating film of the coating liquid, for example, ultraviolet irradiation or electron beam irradiation can be employed. In the case of ultraviolet irradiation, a high-pressure mercury lamp, a halogen lamp, a xenon lamp, a melting lamp, or the like can be used. The ultraviolet irradiation dose is usually about 100 to 800mJ/cm 2 。
As described above, in the present embodiment, the metal oxide-containing layer 3 in which the metal oxide fine particles are unevenly distributed in the thickness of 0.6% to 20% of the hard coat layer 2 is formed on the surface of the hard coat layer 2, and thus the hard coat film 10 excellent in transparency can be obtained while exhibiting the characteristics of the metal oxide fine particles. In addition, since the metal oxide-containing layer 3 can be formed in the primary hard coat layer forming step of drying and curing after the hard coating composition is applied to the transparent substrate 1, a step of additionally forming the metal oxide-containing layer 3 is not required, which is advantageous also in terms of production cost and production efficiency.
(embodiment 2)
Fig. 2 is a schematic cross-sectional view of an anti-reflection film according to embodiment 2.
The antireflection film 20 is obtained by further laminating a low refractive index layer 4 on the hard coat layer 2 of the hard coat film 10 according to embodiment 1. The antireflection film 20 has a normal reflectance of 0.1% or less, and both of reflection color tones a and b are-4 to + 4. Here, a and b are color coordinates a and b of reflected light in the color system. Therefore, in the antireflection film 20 according to the present embodiment, regular reflection is sufficiently suppressed, and the color is also neutral.
The low refractive index layer 4 may be formed by: a coating liquid containing a binder such as an active energy ray-curable resin and, if necessary, inorganic fine particles is applied onto the hard coat layer 2, and the coating film is cured by photopolymerization. The binder or additive used in the coating liquid is not particularly limited, and a known material can be suitably used. The coating method of the coating liquid is not particularly limited, and a known wet coating method can be used. As a method for curing the coating film of the coating liquid, for example, ultraviolet irradiation or electron beam irradiation can be employed. In the case of ultraviolet irradiation, a high-pressure mercury lamp, a halogen lamp, a xenon lamp, a melting lamp, or the like can be used. The ultraviolet irradiation dose is usually about 100 to 800mJ/cm 2 。
The antireflection film 20 according to the present embodiment is configured such that: the metal oxide-containing layer 3 formed at the surface of the hard coat layer 2 is used as a high refractive index layer, and a low refractive index layer composed of a material having a lower refractive index than the metal oxide-containing layer is formed on the metal oxide-containing layer 3. As described in embodiment 1, since the metal oxide-containing layer 3 is formed by unevenly distributing the metal oxide fine particles on the surface of the hard coat layer 2, the hard coat layer 2 has excellent transparency. Therefore, according to the present embodiment, reflected light is sufficiently suppressed, and the antireflection film 20 excellent in color and transparency can be obtained.
Examples
Hereinafter, examples in which the hard coat film and the antireflection film of the present invention are specifically implemented will be described.
(examples 1 to 12 and 14 and comparative examples 1 to 6)
As the transparent substrate, a triacetyl cellulose film having a thickness of 60 μm was used. A hard coating composition having a composition shown in tables 1 to 3 below was applied to one surface of a transparent substrate, and dried at a temperature described in tables 1 to 3. Subsequently, an ultraviolet irradiation apparatus was used at 150mJ/cm 2 The coating film is cured by ultraviolet irradiation at the irradiation dose of (2) to form a hard coating film, thereby obtaining a hard coating film. The coating amount of the hard coating composition was set so that the film thickness after curing became 5.0 μm.
(example 13)
A hard coating composition having a composition shown in table 2 was applied to one surface of a transparent substrate in the same manner as in example 1, and dried at a temperature described in table 2 below. Subsequently, the coating film was cured by an ultraviolet irradiation apparatus in the same manner as in example 1, to form a hard coat layer.
Next, a low refractive index layer forming composition having the following composition was applied to the hard coat layer of the obtained hard coat film, and dried. Subsequently, an ultraviolet irradiation apparatus was used at 200mJ/cm 2 The coating film is cured by ultraviolet irradiation at the irradiation dose of (2) to form a low refractive index layer, thereby obtaining an antireflection film. The amount of the low refractive index layer forming composition applied was set so that the film thickness after curing became 100 nm.
[ composition for Forming Low refractive index layer ]
8.5 parts by weight of a porous silica fine particle dispersion (average particle diameter: 75nm; solid content: 20%; solvent: methyl isobutyl ketone)
オプツール AR-110 (solid content 15%; solvent methyl isobutyl ketone) made by ダイキン, engineering , 5.6 parts by weight
0.4 part by weight of pentaerythritol triacrylate
0.07 part by weight of a polymerization initiator (イルガキュア "; チバ. スペシャリティ. ケミカルズ (manufactured by LTD.)
1.7 parts by weight of a leveling agent (RS-77, manufactured by DIC Ltd.)
Methyl isobutyl ketone 83.73 parts by weight
The hard coat films and the antireflection films obtained in the examples and comparative examples were evaluated for the ratio of the thickness of the metal oxide-containing layer to the thickness of the hard coat layer, the presence ratio of the metal element in the metal oxide-containing layer, transparency, mahalanobis hardness, and pencil hardness by the following methods.
< ratio of thickness of Metal oxide-containing layer to thickness of hard coat layer >
Cross-sectional images of the hard coat film or the antireflection film obtained in each example and each comparative example were obtained using a Scanning Transmission Electron Microscope (STEM), and the thickness of the metal oxide-containing layer and the hard coat layer was measured from the obtained cross-sectional images. More specifically, first, a cross-sectional image of the film is obtained by STEM, and on the obtained cross-sectional image, a layer containing metal oxide fine particles and a layer not containing metal oxide fine particles are identified, and the thickness of the layer formed of the hard coating composition on the transparent substrate (the total thickness of the layer containing metal oxide fine particles and the layer not containing metal oxide fine particles) and the thickness of the metal oxide containing layer are measured. Then, the ratio of the thickness of the metal oxide-containing layer to the thickness of the layer formed on the transparent substrate from the hard coating composition was calculated.
< Presence ratio of Metal element in Metal oxide-containing layer >
Cross-sectional images of the hard coat film or the antireflection film obtained in each example and each comparative example were obtained using a Scanning Transmission Electron Microscope (STEM), and the layer containing the metal oxide fine particles and the layer containing no metal oxide fine particles were identified in the obtained cross-sectional images. The layer containing the metal oxide fine particles and the layer not containing the metal oxide fine particles, which were identified in the obtained hard coating film or antireflection film, were each subjected to energy dispersive X-ray analysis, and the ratio of the amount of the metal element contained in the metal oxide-containing layer (metal element derived from the metal oxide fine particles) to the amount of the metal element contained in the hard coating layer other than the metal oxide-containing layer (metal element derived from the metal oxide fine particles) was calculated.
< transparency >
The hard coat films and the antireflection films obtained in the examples and comparative examples were visually observed for their transparency, and whether the transparency was good or not was evaluated. "O" in the table indicates good transparency.
< Ma hardness >
The mahalanobis hardness was measured by using picodenator (registered trademark) HM 500 manufactured by "フィッシャー, インストルメンツ".
< Pencil hardness >
A2H Mitsubishi Uni pencil (available from Mitsubishi type Co., ltd.) and a Kremen type scratch tester (HA-301, available from テスター and Co., ltd.) were used, and a scratch test was carried out under a load of 500g, and changes in appearance due to scratches were visually observed. The rubbing test was performed 5 times, and the number of times no scratch was observed was set as an evaluation value of pencil hardness.
In addition, the antireflection film of example 13 was measured for the normal reflectance and the reflection color tone. Lead-free vinyl tape No.21 made by "daily super" was attached to the coated back surface side of the antireflection film, and then the regular reflectance was measured using a spectrophotometer (U-4100; manufactured by "corporation). Further, the reflected color tone was evaluated by irradiating light from the front surface side (hard coating side or low refractive index layer side) at an incident angle of 5 ° using a spectrophotometer (U-4100; "manufactured by japan corporation) and using color coordinates a and b of the reflected light in a L a b color system.
In examples 1 to 14, since the thickness of the metal oxide-containing layer was in the range of 0.6% to 20% of the thickness of the hard coat layer, and the amount of the metal element derived from the metal oxide fine particles contained in the metal oxide-containing layer was 50 times or more the amount of the metal element derived from the metal oxide fine particles contained in the portion of the hard coat layer other than the metal oxide-containing layer, the state in which the metal oxide fine particles were locally present on the surface side of the hard coat layer was achieved, and the transparency was also good. In addition, in the antireflection film according to example 13, the regular reflectance was sufficiently suppressed, and the color was also neutral.
In contrast, in comparative examples 1 to 4, since any one of the functional group of the silane coupling agent, the surface tension of the binder, the viscosity of the binder before curing, and the vapor pressure of the solvent at 20 ℃ does not satisfy the conditions of the present invention, the metal oxide fine particles are present in a dispersed manner in the thickness range of 50% to 90% of the thickness of the hard coating layer, and the metal oxide-containing layer as in examples 1 to 14 cannot be formed. That is, although metal oxide fine particles are also added, a high refractive index layer having a relatively high refractive index cannot be formed inside the hard coat layer by the action of the metal oxide fine particles.
In comparative example 5, although the metal oxide fine particles were unevenly present on the surface of the hard coat layer, the thickness of the metal oxide-containing layer exceeded 20% of the thickness of the hard coat layer due to an excessive amount of the metal oxide fine particles added, whitening occurred in the entire hard coat layer, and transparency was significantly impaired.
In comparative example 6, although the metal oxide fine particles were unevenly present on the surface of the hard coat layer, the thickness of the metal oxide-containing layer was less than 0.6% of the thickness of the hard coat layer because the amount of the metal oxide fine particles added was too small, and it was not possible to form a high refractive index layer having a relatively high refractive index by the action of the metal oxide fine particles.
As described above, it can be confirmed that: according to the present invention, the metal oxide fine particles are unevenly present on the surface of the hard coat layer, whereby a hard coat film having an optical functional layer (high refractive index layer) to which the characteristics of the metal oxide fine particles are imparted and excellent in transparency can be obtained. In addition, it was confirmed that: according to the present invention, by laminating a low refractive index layer having a lower refractive index than the metal oxide-containing layer on the hard coat layer, an antireflection film having sufficiently suppressed regular reflection and excellent transparency and color can be obtained.
The present invention is useful as an optical film such as a hard coat film or an antireflection film used in an image display device or the like.
Although the present invention has been described in detail, the foregoing description is in all aspects illustrative of the present invention and is not intended to limit the scope thereof. It goes without saying that various modifications or alterations may be made without departing from the scope of the invention.
Claims (7)
1. A hard coating film in which a hard coat layer is laminated on a transparent substrate, characterized in that,
wherein the hard coat layer has a portion in which the metal oxide fine particles bonded with the silane coupling agent are unevenly distributed on the air interface side of the hard coat layer, and the thickness of the portion in which the metal oxide fine particles are unevenly distributed in the hard coat layer is 0.6 to 20% of the thickness of the hard coat layer,
the amount of the metal element derived from the metal oxide fine particles contained in the portion where the metal oxide is unevenly distributed is 50 times or more the amount of the metal element derived from the metal oxide fine particles contained in the portion other than the portion where the metal oxide is unevenly distributed in the hard coat layer,
the metal oxide fine particles are one or more selected from the group consisting of antimony-doped tin oxide, phosphorus-doped tin oxide, gallium-doped tin oxide, zirconium oxide, and titanium oxide,
the transparent base material is formed of one material selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, nylon 6, nylon 66, triacetyl cellulose, polyimide, polyarylate, polycarbonate, polyacrylate, polyethersulfone, and polysulfone.
2. The hard coating film according to claim 1, wherein the hard coating layer is formed from a cured film of a hard coating composition containing the metal oxide fine particles, a binder, a photopolymerization initiator, and a solvent,
the content ratio of the metal oxide fine particles is 0.2 to 10 mass% when the total solid content of the hard coating composition is taken as 100 mass%,
a silane coupling agent having one or more organic chains selected from the group consisting of alkyl groups, vinyl groups, acryl groups and methacryl groups bonded to the surface of the metal oxide fine particles,
the adhesive has a viscosity of 100 pas or less before curing and a surface tension of 40mN/m or more,
the vapor pressure of the solvent at 20 ℃ is 10kPa or less.
3. The hard coating film according to claim 2, wherein the solvent is polyethylene glycol monomethyl ether.
4. A hard coating film in which a hard coat layer is laminated on a transparent substrate, characterized in that,
wherein the fine silica particles bonded with the silane coupling agent are unevenly present on the air interface side of the hard coat layer in the hard coat layer, the thickness of the portion of the hard coat layer where the fine silica particles are unevenly present is 0.6 to 20% of the thickness of the hard coat layer,
the amount of silicon elements derived from the fine silicon oxide particles contained in the portion where the silicon oxide is unevenly distributed is 50 times or more the amount of silicon elements derived from the fine silicon oxide particles contained in the portion other than the portion where the silicon oxide is unevenly distributed in the hard coat layer,
the transparent substrate is formed of one material selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, nylon 6, nylon 66, triacetyl cellulose, polyimide, polyarylate, polycarbonate, polyacrylate, polyethersulfone, and polysulfone.
5. The hard coating film according to claim 4, wherein the hard coat layer is formed from a cured film of a hard coating composition containing the silicon oxide fine particles, a binder, a photopolymerization initiator, and a solvent,
the content ratio of the silica fine particles is 0.2 to 10 mass% when the total solid content of the hard coating composition is taken as 100 mass%,
a silane coupling agent having one or more organic chains selected from the group consisting of alkyl groups, vinyl groups, acryl groups and methacryl groups bonded to the surface of the silica fine particles,
the adhesive has a viscosity of 100 pas or less before curing and a surface tension of 40mN/m or more,
the vapor pressure of the solvent at 20 ℃ is 10kPa or less.
6. The hard coating film according to claim 5, wherein the solvent is polyethylene glycol monomethyl ether.
7. An antireflection film comprising the hard coat film according to any one of claims 1 to 6 and a low refractive index layer laminated on the hard coat layer of the hard coat film,
the normal reflectance is 0.1% or less, and both the reflected hues a and b are-4 to + 4.
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| JP2017200464A JP7071813B2 (en) | 2017-10-16 | 2017-10-16 | Hardcourt film manufacturing method and antireflection film manufacturing method |
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| CN201811183645.8A CN109666319B (en) | 2017-10-16 | 2018-10-11 | Hard coating film and antireflection film |
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| KR20190042448A (en) | 2019-04-24 |
| TWI671199B (en) | 2019-09-11 |
| KR102137453B1 (en) | 2020-07-24 |
| JP2019074643A (en) | 2019-05-16 |
| TW201917020A (en) | 2019-05-01 |
| CN113352703A (en) | 2021-09-07 |
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