JP2013109169A - Antireflection member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection member for reducing reflectance in a visible light region while securing translucency required for the antireflection member.SOLUTION: In an antireflection member where a hard coat layer, and a low refractive index layer are arranged on a transparent support in this order, the hard coat layer contains a light absorbing material that absorbs the light within 400-800 nm wavelength. The hard coat layer containing the light absorbing material offers light absorptivity within 400-800 nm wavelength and also 90% or more of total light transmittance.

Description

  The present invention relates to an antireflection member, and more particularly to an antireflection member applied to the surface of a display screen of a display (CRT display, plasma display, liquid crystal display, projection display, EL display, etc.).

  Conventionally, a film-like or plate-like antireflection member having an antireflection function is a cathode ray tube display (CRT), a plasma display panel (PDP), a liquid crystal display (LCD), a projection display, an electroluminescence display (ELD). Are used in various fields such as an anti-reflection treatment in a photolithography process, an anti-reflection treatment on the surface of a solar cell panel, and the like.

  The antireflection member is mainly used in which a hard coat layer and a low refractive index layer are provided in this order on a film-like or plate-like transparent support (see Patent Documents 1 and 2).

  A PET film or the like is mainly used as the transparent support, and the hard coat layer provided thereon is a coating having a higher hardness than the transparent support, and improves the hardness of the surface of the transparent support, such as a pencil. It prevents scratches caused by scratching with a heavy load. Further, it suppresses the generation of cracks in the low refractive index layer due to the bending of the transparent support, thereby improving the mechanical strength of the antireflection member. And the antireflective performance is provided by providing a low refractive index layer whose refractive index is lower than a transparent support body and a hard-coat layer on a hard-coat layer.

JP 2009-31769 A JP 2004-258267 A

  However, when the conventional antireflection member is bonded to the back surface of the transparent support or a substrate such as a glass plate, the contribution of reflected light from the back surface of the substrate is large, and the reflectance in the visible light region is increased. It was a factor. Further, in the general antireflection member in which one to three layers are laminated, the reflectance has a large wavelength dependency, and therefore, the transmitted color is colored, for example, the color reproducibility of an adherend display. It was a factor that damaged.

  Although various studies have been made on the reduction of reflectance, antireflection members are often required to have high transparency. Therefore, attention is focused on reducing the reflectance by absorbing light. This approach has not been made yet.

  In addition to the antireflection performance, the antireflection member may require various performances such as antistatic performance and anti-fingerprint properties, and a technology that can satisfy these performances simultaneously is required. .

  The present invention has been made in view of the circumstances as described above, and provides an antireflection member capable of reducing the reflectance in the visible light region while ensuring the transparency required for the antireflection member. It is an issue.

  In order to solve the above-described problems, the antireflection member of the present invention is an antireflection member in which a hard coat layer and a low refractive index layer are provided in this order on a transparent support. It contains a light-absorbing material that absorbs light in the range of 800 nm, has a light-absorbing property in the wavelength range of 400 to 800 nm by the hard coat layer containing this light-absorbing material, and has a total light transmittance. It is characterized by being 90% or more.

  In this antireflection member, the transmission chromaticity in the L * a * b * color system is preferably −1.0 ≦ a * ≦ 0 and 0 ≦ b * ≦ 1.0.

  In this antireflection member, the average luminous reflectance is preferably 1.0% or less.

  In this antireflection member, the hard coat layer preferably has a refractive index of 1.50 to 1.90.

  In this antireflection member, it is preferable that at least one oxide selected from titanium, aluminum, cerium, yttrium, zirconium, niobium, and antimony is contained in the hard coat layer as high refractive index particles.

  In this antireflection member, the hard coat layer preferably has antistatic properties.

  In this antireflection member, it is preferable that at least one oxide selected from indium, zinc, tin, and antimony is contained as conductive nanoparticles in the hard coat layer.

In this antireflection member, the sheet resistance of the hard coat layer is preferably 10 ¹⁴ Ω / □ or less.

  In this antireflection member, the refractive index of the low refractive index layer is preferably 1.30 to 1.45.

  In this antireflection member, it is preferable to have an antifouling layer on the surface of the low refractive index layer.

  According to the present invention, the reflectance in the visible light region can be reduced while ensuring the transparency required for the antireflection member.

FIG. 1 is a cross-sectional view showing an example of the antireflection member of the present invention. FIG. 2 is a cross-sectional view showing another example of the antireflection member of the present invention.

  The present invention is described in detail below.

  FIG. 1 is a cross-sectional view showing an example of the antireflection member of the present invention.

  In this antireflection member 1, a transparent resin film or a transparent resin plate is used as the transparent support 2, and a hard coat layer 3 and a low refractive index layer 4 are formed on the surface of the transparent support 2 in this order.

  In the antireflection member 1 shown in FIG. 1, the low refractive index layer 4 is formed on one side of the transparent support 2 via the hard coat layer 3, but the hard coat layer is formed on both sides of the transparent support 2. The low refractive index layer 4 may be formed via 3.

  In the present invention, the hard coat layer 3 contains a light-absorbing material that absorbs light in the wavelength range of 400 to 800 nm, and the layer containing the light-absorbing material absorbs light in the wavelength range of 400 to 800 nm. Is given. The total light transmittance is 90% or more, preferably 92% or more.

  By imparting light absorption in this manner, in the present invention, the average luminous reflectance of the antireflection member 1 is preferably 1.0% or less, and more preferably 0.7% or less.

  And it can be set as the reflection preventing member 1 which does not impair light extraction efficiency, power consumption, etc. also in uses, such as a display.

  In the antireflection member 1 of the present invention, the transmission chromaticity in the L * a * b * color system is preferably −1.0 ≦ a * ≦ 0 and 0 ≦ b * ≦ 1.0. Thereby, the color tone can be neutralized while ensuring the transparency and low reflectivity necessary for the antireflection member.

  In the present invention, examples of the transparent support 2 include transparent resin films or transparent resin plates made of various organic polymers. Usually, organic polymers used as optical members are made of polyethylene resin, polypropylene resin, etc. from the viewpoints of optical properties such as transparency, refractive index, haze, and other physical properties such as impact resistance, heat resistance, and durability. Polyester resin such as polyolefin resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyamide resin such as nylon-6 and nylon-66, cellulose resin such as triacetyl cellulose, diacetyl cellulose, cellophane, polystyrene resin, polyvinyl chloride resin, polyimide Resin, polyvinyl alcohol resin, ethylene vinyl alcohol resin, acrylic resin, cycloolefin resin, or a copolymer of these organic polymers, etc., by molding these organic polymers or the like into a film or plate, Transparent resin film It can be produced Lum or transparent resin plate.

  Further, the transparent support 2 is prepared by using a known additive such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, an antioxidant, a flame retardant and the like in the above organic polymer. It may be manufactured.

  The transparent support 2 may be a single layer or a multilayer having a plurality of organic polymers laminated. Although the thickness of the transparent support body 2 is not specifically limited, It is preferable that it is 50-200 micrometers.

  In the present invention, the hard coat layer 3 is a film having a hardness higher than that of the transparent support 2, which improves the hardness of the surface of the transparent support 2, prevents scratches caused by scratching with a load such as a pencil, The occurrence of cracks in the low refractive index layer 4 due to the bending of the transparent support 2 is suppressed, and the mechanical strength of the antireflection member 1 is improved.

  The pencil hardness of the hard coat layer 3 is preferably H or higher, more preferably 2H or higher. In order to improve the hardness of the hard coat layer 3, a reactive curable resin, that is, a thermosetting resin and an ionizing radiation curable resin are used. The hard coat layer 3 is preferably formed using at least one of the mold resins as a hard coat material (a composition for forming a hard coat layer).

  As the thermosetting resin, for example, phenol resin, urea resin, diallyl phthalate resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, silicon resin, polysiloxane resin, or the like can be used.

  For example, a crosslinking agent, a polymerization initiator, a curing agent, a curing accelerator, and a solvent can be added to these thermosetting resins as necessary.

  When the hard coat layer 3 is formed using a thermosetting resin, it is preferable that the thermosetting resin is applied to the surface of the antireflection member 1 and then dried and cured by heating.

  As the ionizing radiation curable resin, those having an acrylate functional group are preferably used. Examples of ionizing radiation curable resins having an acrylate functional group include relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyenes. Resins, oligomers such as (meth) acrylates of polyfunctional compounds such as polyhydric alcohols, and prepolymers can be used.

  In addition, these oligomers and prepolymers may be mixed with monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, and N-vinylpyrrolidone as reactive diluents, or trimethylolpropane tri (meta ) Acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di What mix | blended polyfunctional monomers, such as (meth) acrylate and neopentyl glycol di (meth) acrylate, can be used.

  Furthermore, in order to make the ionizing radiation curable resin into an ultraviolet curable resin, it is preferable to add a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones, benzophenones, α-amyloxime esters, thioxanthones, and the like.

  Moreover, you may use a photosensitizer with a photoinitiator. Examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone. When the hard coat layer 3 is formed using an ultraviolet curable resin that undergoes a photopolymerization reaction, for example, the ultraviolet curable resin can be applied to the surface of the transparent support 2 and dried, and then cured by ultraviolet irradiation.

  The hard coat layer 3 preferably has a refractive index close to that of the transparent support 2, and from the standpoint of reducing the reflectivity, the refractive index of the hard coat layer 3 is practically 1.50 to 1.90. (Equivalent to the refractive index of the polyester film 1) is preferable.

  If the film thickness of the hard coat layer 3 is 1 to 2 μm or more, sufficient strength can be obtained.

  Further, in order to increase the refractive index of the hard coat layer 3 and improve the antireflection performance, it is possible to add high refractive index particles, that is, ultrafine particles of a metal or metal oxide having a high refractive index to the hard coat layer material. it can. As the high refractive index particles, for example, particles having a refractive index of 1.6 or more and a particle size of 0.5 to 200 nm can be used. From the viewpoint of reducing the reflectance of the antireflection member 1, it is preferable to adjust the blending amount of the high refractive index particles to 5 to 70% by volume with respect to the hard coat layer 3.

As the ultrafine particles of a metal or metal oxide having a high refractive index, for example, particles of at least one oxide selected from titanium, aluminum, cerium, yttrium, zirconium, niobium, and antimony can be used. Specifically, for example, ZnO (refractive index 1.90), TiO ₂ (refractive index 2.3 to 2.7), CeO ₂ (refractive index 1.95), Sb ₂ O ₅ (refractive index 1.71). ), SnO ₂ , ITO (refractive index 1.95), Y ₂ O ₃ (refractive index 1.87), La ₂ O ₃ (refractive index 1.95), ZrO ₂ (refractive index 2.05), Al ₂ Fine powders such as O ₃ (refractive index 1.63) can be used.

  The hard coat layer 3 is preferably imparted with antistatic properties to ensure antistatic properties and anti-dust adhesion properties as the antireflection member 1. In order to impart antistatic properties to the hard coat layer 3, for example, the hard coat layer 3 can contain conductive nanoparticles.

As the conductive nanoparticles, for example, ultrafine particles having a particle size of 0.5 to 200 nm made of conductive metal or metal oxide can be used. Specifically, for example, particles of at least one oxide selected from indium, zinc, tin, and antimony can be used. Preferably, indium oxide (ITO), tin oxide (SnO ₂ ), antimony / tin are used. Ultrafine particles of oxide (ATO), lead / titanium oxide (PTO), and antimony oxide (Sb ₂ O ₅ ) are used.

From the viewpoint of obtaining the antistatic property of the hard coat layer 3, the sheet resistance is preferably 10 ¹⁴ Ω / □ or less. Note that the lower the sheet resistance of the hard coat layer 3, the more the antistatic property is improved. Therefore, the lower limit is not particularly limited, but the sheet resistance of the hard coat layer 3 is substantially 10 because there is a limit in reducing the sheet resistance. ⁶ Ω / □ or more. Further, the sheet resistance value of the hard coat layer 3 can be adjusted by the blending amount of the conductive nanoparticles and the like, for example, the blending amount of the conductive nanoparticles is 5 to 70% by mass with respect to the hard coat layer 3. Can be adjusted as follows.

  The surface of the hard coat layer 3 is preferably subjected to a surface treatment before the low refractive index layer 4 is formed. Examples of such surface treatment include physical surface treatment such as plasma discharge treatment, corona treatment and flame treatment, and chemical surface treatment with a coupling agent, acid, alkali and the like. By performing such a surface treatment, wettability and adhesion between the hard coat layer 3 and the low refractive index layer 4 can be improved.

  The light-absorbing material blended in the hard coat layer 3 is preferably a cyanine dye or a phthalocyanine dye in consideration of the material of the hard coat layer 3 or the like. For example, the light absorption wavelength range of the cyanine dye is 400 to 600 nm, and the light absorption wavelength range of the phthalocyanine dye is 600 to 800 nm.

  Although these compounding quantities are not specifically limited, For example, about cyanine pigment | dye, Adeka GPX301 is 0.005-0.01 mass% with respect to the whole quantity of the hard-coat layer 3, About phthalocyanine pigment | dye, Nippon Catalysts TX-EX-609K can be blended in an amount of 0.002 to 0.006% by mass with respect to the total amount of the hard coat layer 3.

  In the present invention, the low refractive index layer 4 is a layer having a smaller refractive index than the transparent support 2 and the hard coat layer 3, and a low refractive index coating agent is applied to the surface of the hard coat layer 3. Can be formed.

  The low refractive index layer 4 preferably has a refractive index of 1.30 to 1.45, more preferably 1.30 to 1.40. The thickness d of the low refractive index layer 4 is preferably nd = λ / 4, where n is the refractive index of the low refractive index layer 4 and λ is the wavelength of incident light. Specifically, the thickness of the low refractive index layer 4 is preferably 50 to 200 nm, and more preferably 80 to 120 nm.

  When the binder material itself has a low refractive index, the low refractive index coating agent can be prepared as a single binder material, but it can also be prepared by blending low refractive index particles in the binder material.

  As the binder material, for example, a hydrolyzate of silicon alkoxide, or a polymer (UV curable resin, thermosetting resin) having a saturated hydrocarbon or polyether as a main chain can be used. Moreover, what has a structural unit containing a fluorine atom in these molecules can also be used.

As the silicon alkoxide of the binder material, for example, a compound represented by R _m Si (OR ′) _n can be used. Here, R and R ′ represent an alkyl group having 1 to 10 carbon atoms, m and n each represents an integer, and m + n is 4.

  Examples of such compounds include tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-butoxy. Silane, tetrapentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxy Silane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethyl Roxy silane, dimethyl butoxy silane, methyl dimethoxy silane, methyl diethoxy silane, hexyl trimethoxy silane, etc. can be used, and oligomers and polymers having these as a basic skeleton, or copolymers of at least two of these Can be used.

  The silicon alkoxide binder material can be prepared by dissolving the above silicon alkoxide in a suitable solvent and hydrolyzing it.

  Examples of the solvent include alcohols such as isopropyl alcohol, methanol and ethanol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as toluene and xylene, and halogenated carbons. Hydrogen can be used. These may be used alone or in combination of two or more.

The silicon alkoxide is dissolved in the above solvent so that the silicon alkoxide is 100% hydrolyzed and condensed, and is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass in terms of SiO ₂ generated. To do. When the silicon alkoxide concentration is too low, the formed sol film may not exhibit the desired characteristics sufficiently. On the other hand, when the silicon alkoxide concentration is too high, it becomes difficult to form a transparent and homogeneous film. There is.

Water more than the amount necessary for hydrolysis is added to this solution, and preferably stirred at a temperature of 15 to 35 ° C., more preferably 22 to 28 ° C., preferably 0.5 to 10 hours, more preferably 2 to 5 hours. I do. A catalyst is preferably used for the hydrolysis, and as the catalyst, for example, an acid such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid or the like can be used. These acids are preferably added as an aqueous solution of 0.001 to 20.0 N, more preferably 0.005 to 5.0 N, and water in the aqueous solution can be used as water for hydrolysis. The SiO ₂ sol thus obtained is a colorless and transparent liquid, is a stable solution having a pot life of about 1 month, has good wettability with respect to the substrate, and is excellent in coating suitability.

  A reactive organosilicon compound or a partial hydrolyzate thereof may be added to the hydrolyzate of silicon alkoxide. As such a reactive organosilicon compound, a plurality of groups that react and crosslink by heat or ionizing radiation, for example, an organosilicon compound having a molecular weight of 5000 or less having a polymerizable double bond group can be used.

  Specifically, for example, one-end vinyl functional polysilane, both-end vinyl functional polysilane, one-end vinyl-functional polysiloxane, both-end vinyl-functional polysiloxane, or a vinyl-functional polysilane obtained by reacting these compounds, vinyl A functional polysiloxane or the like can be used.

  The polymer having a saturated hydrocarbon or polyether as the main chain as the binder material is preferably crosslinked.

  The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. Moreover, in order to obtain the polymer of the binder material bridge | crosslinked, it is preferable to use the monomer which has two or more ethylenically unsaturated groups.

  As monomers having two or more ethylenically unsaturated groups, for example, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, tri Methylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexane Esters of polyhydric alcohols such as tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate and (meth) acrylic acid; 1,4-divinylbenzene, 4-biphenyl Le benzoic acid-2-acryloyl ethyl ester, 1,4-divinylbenzene and derivatives thereof divinyl cyclohexanone; divinyl sulfone vinyl sulfone; methylenebisacrylamide acrylamide can be used, such as methacrylamide.

  Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the polymer of the binder material by the reaction of a crosslinkable functional group. Examples of such crosslinkable functional groups include isocyanate groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, carboxyl groups, methylol groups, and active methylene groups. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester, and urethane can also be used as a monomer for introducing a crosslinked structure. In addition, you may use the functional group which shows crosslinkability as a result of a decomposition reaction like a block isocyanate group.

  As the polymer having a polyether as a main chain, for example, a polymer synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound can be used.

  As a polymerization initiator used for the polymerization reaction and crosslinking reaction of the polymer of the binder material, for example, a thermal polymerization initiator or a photopolymerization initiator can be used.

  Examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums can be used.

  Further, in order to impart antifouling property to the low refractive index layer 4, a part of the binder material may be replaced with a water-repellent or oil-repellent material. The water- and oil-repellent materials generally include wax-based materials, and it is particularly desirable to contain a fluorine-containing compound. By blending the fluorine-containing compound, the surface of the low refractive index layer 4 is protected from dirt, and the removal of attached dirt, fingerprints and the like is improved. Furthermore, the frictional resistance of the surface can be reduced, and the effect of improving wear resistance can be expected.

  The low refractive index particles blended in the binder material preferably have a refractive index of 1.5 or less, more preferably 1.20 to 1.45.

  The average particle size of the low refractive index particles is preferably 0.5 to 200 nm. When the average particle size is larger than 200 nm, light is irregularly reflected by Rayleigh scattering in the obtained low refractive index layer 4, and the low refractive index layer 4 looks whitish and its haze value may increase. When the thickness is 0.5 nm or less, the dispersibility of the low refractive index particles decreases, and aggregation occurs in the liquid of the low refractive index coating agent.

  Further, the addition amount of the low refractive index particles is preferably 20 to 99% by volume with respect to the total amount of the low refractive index layer 3 in consideration of lowering the refractive index, surface hardness, wear resistance and the like.

  As the low refractive index particles, for example, hollow particles such as silica fine particles and hollow silica fine particles, or fluoride fine particles such as magnesium fluoride, lithium fluoride, aluminum fluoride, calcium fluoride, and sodium fluoride can be used. it can. These may be used alone or in combination of two or more. These low refractive index particles can be subjected to a surface treatment for imparting compatibility with a resin or the like of the binder material.

  The hollow particles are fine particles having a cavity surrounded by an outer shell. The refractive index of the hollow particles themselves is preferably 1.20 to 1.45, and the refractive index of the hollow particles can be measured by the method described in JP-A No. 2001-233611.

  As a hollow particle, the hollow particle currently disclosed by Unexamined-Japanese-Patent No. 2001-233611 can be used, for example.

As a material constituting the outer shell of the hollow particles, for example, SiO ₂ , SiO _x , TiO ₂ , TiO _x , SnO ₂ , CeO ₂ , Sb ₂ O ₅ , ITO, ATO, Al ₂ O _{3 and the} like alone, Or the thing of the form of the mixture of any combination of these materials can be used. Further, a composite oxide of any combination of these materials may be used. Note that SiO _x is preferably SiO ₂ when fired in an oxidizing atmosphere.

  Low refractive index coating agents include, for example, dip coating, spin coating, spray coating, roll coating, gravure roll coating, reverse coating, transfer roll coating, micro gravure coating, cast coating, calendar coating It can be coated on the hard coat layer 3 subjected to the surface treatment by a liquid phase method such as a method or a die coating method. After coating, the solvent in the coating film is volatilized by heating and drying, and then the coating film is cured by heating, humidification, ultraviolet irradiation, electron beam irradiation, etc., and the low refractive index layer 4 can be formed.

  In the present invention, the antifouling layer 5 can be formed on the surface of the low refractive index layer 4 as shown in FIG. 2 in order to further improve the antifouling property and fingerprint removability of the antireflection member. Since the thickness of the antifouling layer 5 does not affect the optical characteristics, it is preferable to set it to 30 nm or less.

  The antifouling layer 5 can be formed, for example, by covering it with a silicone compound or a fluorine-containing compound and chemically bonding it to the surface of the low refractive index layer 4. In addition, as a material for forming the antifouling layer 5, a reactive material such as a fluorine compound having an alkoxysilano group or a reactive silicone oil improves wear resistance, chemical resistance, and aging resistance. It is preferable because it can be used.

  The antifouling layer 5 is prepared by, for example, diluting a long chain fluoroalkylsilane coating material “XC98-2472” manufactured by Momentive Co., Ltd. to a solid content of 0.2% using a diluting solvent IPA (isopropanol). After being applied to the surface of the low refractive index layer 4 with a wire bar coater # 10 so as to be, it can be formed by drying at 120 ° C. for 3 minutes.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all.

<Example 1>
As the polyester film 1, a polyethylene terephthalate (PET) film “A4300 (thickness: 100 μm)” manufactured by Toyobo Co., Ltd. was used.

As a hard coat material for the hard coat layer, an acrylic ultraviolet curable resin (“Seika Beam PET-HC301” manufactured by Dainichi Seika Kogyo Co., Ltd., active ingredient (solid content) 60 mass%) is used as a high refractive index particle. Titanium oxide particles (Taika Co., Ltd. “760T”, dispersion solvent: toluene, solid content 48% by mass) 30% by mass, cyanine dye (GPX-301 manufactured by Adeka Co., Ltd.) as a light absorbing material 0.005 mass %, 0.002% by mass of phthalocyanine dye (manufactured by Wako Pure Chemical Industries, Ltd., tetrabenztetraazaporphyrin) was added and mixed with a disper. The hard coat material (mixed solution) was applied onto the polyester film 1 with a wire bar coater # 10, dried at 80 ° C. for 5 minutes, and then cured by UV irradiation (500 mJ / cm ² ).

  Next, a low refractive index material was applied to the surface of the hard coat layer to form a low refractive index layer. The low refractive index material was obtained by adding 356 parts by mass of methanol to 208 parts by mass of tetraethoxysilane, adding 18 parts by mass of water and 18 parts by mass of 0.01N hydrochloric acid aqueous solution, and mixing them with a disper to obtain a mixed solution. Thereafter, this mixed liquid was stirred in a thermostatic bath at 25 ° C. for 2 hours, and a silicone resin having a weight average molecular weight adjusted to 850 was used as a binder material. As low refractive index particles, hollow silica IPA (isopropanol) dispersion sol of low refractive index nanoparticles (“Suriria CS-60IPA” manufactured by Catalytic Chemical Industry Co., Ltd., solid content 20% by mass) is 40 of the total amount of the silicone resin matrix. A low refractive index material was prepared by blending with a silicone resin in an amount of volume% and then diluting with methanol so that the total solid content was 1.5 mass%.

  After applying this low refractive index material to the surface of the hard coat layer with a wire bar coater # 10 so as to have a film thickness of 100 nm, it is dried at 120 ° C. for 15 minutes to form a low refractive index layer to prevent reflection. A member was prepared.

<Example 2>
As a hard coat material for the hard coat layer, an acrylic ultraviolet curable resin (“Seika Beam PET-HC301” manufactured by Dainichi Seika Kogyo Co., Ltd., active ingredient (solid content) 60 mass%) is used as a high refractive index particle. Titanium oxide particles (Taika Co., Ltd. "760T", dispersion solvent: toluene, solid content 48% by mass) 30% by mass, cyanine dye (GPX-301 manufactured by Adeka Co., Ltd.) 0.01 mass as a light absorbing material %, Phthalocyanine dye (manufactured by Wako Pure Chemical Industries, Ltd., tetrabenztetraazaporphyrin) was added in an amount of 0.006% by mass and mixed with a disper. Otherwise, an antireflection member was produced in the same manner as in Example 1.

<Example 3>
As a hard coat material for the hard coat layer, an acrylic UV curable resin (“Seika Beam PET-HC301” manufactured by Dainichi Seika Kogyo Co., Ltd., active ingredient (solid content) 60% by mass) is used as a light absorbing material. Cyanine dye (GPA-301 manufactured by Adeka Co., Ltd.) was added in an amount of 0.005% by mass, and phthalocyanine dye (manufactured by Wako Pure Chemical Industries, Ltd., tetrabenztetraazaporphyrin) was added in an amount of 0.002% by mass and mixed with a disper. Otherwise, an antireflection member was produced in the same manner as in Example 1.

<Example 4>
As a hard coat material for the hard coat layer, an acrylic ultraviolet curable resin (“Seika Beam PET-HC301” manufactured by Dainichi Seika Kogyo Co., Ltd., active ingredient (solid content) 60 mass%) is used as a high refractive index particle. 60% by mass of titanium oxide particles (Tyca Co., Ltd. “760T”, dispersion solvent: toluene, solid content 48% by mass), and 0.005 mass of cyanine dye (GPX-301 manufactured by Adeka Co., Ltd.) as a light absorbing material %, 0.002% by mass of phthalocyanine dye (manufactured by Wako Pure Chemical Industries, Ltd., tetrabenztetraazaporphyrin) was added and mixed with a disper. Otherwise, an antireflection member was produced in the same manner as in Example 1.

<Example 5>
As a hard coat material for the hard coat layer, an acrylic ultraviolet curable resin (“Seika Beam PET-HC301” manufactured by Dainichi Seika Kogyo Co., Ltd., active ingredient (solid content) 60 mass%) is used as a high refractive index particle. 20% by mass of titanium oxide particles (Take Co., Ltd. “760T”, dispersion solvent: toluene, solid content 48% by mass), ATO particles (“ELCOM P-special product A” manufactured by JGC Catalysts & Chemicals Co., Ltd.) as antistatic particles Dispersion solvent: 20% by mass of MEK / toluene (4/1), solid content of 30% by mass), 0.005% by mass of cyanine dye (GPX-301 manufactured by Adeka Co., Ltd.) as a light-absorbing material, phthalocyanine dye ( 0.002 mass% of Wako Pure Chemical Industries, Ltd., tetrabenztetraazaporphyrin) was added and mixed with a disper. Otherwise, an antireflection member was produced in the same manner as in Example 1.

<Example 6>
The hard coat layer and the low refractive index layer were produced in the same manner as in Example 1. As an antifouling material for the antifouling layer, Momentive's long-chain fluoroalkylsilane coating material “XC98-2472” is diluted to 0.2% solids using a diluting solvent IPA (isopropanol), and this mixed solution is used as a membrane. After applying to the surface of the low refractive index layer with a wire bar coater # 10 so as to have a thickness of 5 nm, an antifouling layer was formed by drying at 120 ° C. for 3 minutes to prepare an antireflection member.

<Example 7>
In the preparation of the material for the low refractive index layer, hollow silica IPA (isopropanol) dispersion sol of low refractive index nanoparticles (Catalyst Kasei Kogyo Co., Ltd. “Thruria CS-60IPA”, solid content 20 mass%) is added to the entire silicone resin matrix. An antireflective member was produced in the same manner as in Example 1 except that it was added to the silicone resin in an amount of 60% by volume.

<Example 8>
In the preparation of the material for the low refractive index layer, hollow silica IPA (isopropanol) dispersion sol of low refractive index nanoparticles (Catalyst Kasei Kogyo Co., Ltd. “Thruria CS-60IPA”, solid content 20 mass%) is added to the entire silicone resin matrix. An antireflection member was produced in the same manner as in Example 1 except that it was blended with the silicone resin in an amount of 20% by volume.

<Comparative Example 1>
In the preparation of the hard coat material, Examples were used except that a cyanine dye (GPX-301 manufactured by Adeka Co., Ltd.) and a phthalocyanine dye (manufactured by Wako Pure Chemical Industries, Ltd., tetrabenztetraazaporphyrin) were not added as light absorbing materials. In the same manner as in Example 1, an antireflection member was produced.

<Comparative example 2>
In the preparation of the hard coat material, 0.01% by mass of cyanine dye (GPX-301 manufactured by Adeka Co., Ltd.) and 0.07% phthalocyanine dye (manufactured by Wako Pure Chemical Industries, Ltd., tetrabenztetraazaporphyrin) are used as light absorbing materials. An antireflection member was produced in the same manner as in Example 1 except that 02% by mass was added.

<Comparative Example 3>
In the preparation of the hard coat material, 0.005% by mass of cyanine dye (TYKA-235 manufactured by Adeka Co., Ltd.) and phthalocyanine dye (manufactured by Wako Pure Chemical Industries, Ltd., tetrabenztetraazaporphyrin) are used as light absorbing materials. An antireflection member was produced in the same manner as in Example 1 except that 002% by mass was added.

<Comparative example 4>
In the preparation of the hard coat material, 0.005% by mass of cyanine dye (GPX-301 manufactured by Adeka Co., Ltd.), Cu phthalocyanine dye (manufactured by Wako Pure Chemical Industries, Ltd., Cu tetrabenztetraazaporphyrin, PG7) as a light absorbing material ) Was added in the same manner as in Example 1 except that 0.002 mass% was added.

  The following measurements were performed on the antireflection members of Examples and Comparative Examples.

[Haze]
Based on JISK7361-1997, the haze was measured using the turbidimeter (Nippon Denshoku Co., Ltd. NDH-2000) for the antireflection film.

[Total light transmittance]
The total light transmittance was measured based on JISK7361-1997 using a turbidimeter (Nippon Denshoku Co., Ltd., NDH-2000) for the antireflection film.

[Minimum reflectance]
After rubbing the surface of the transparent support (lowermost surface in FIG. 1) with sandpaper and applying a matte black paint, use a spectrophotometer ("U-4100" manufactured by Hitachi High-Technologies Corporation) The reflectance (5 ° relative reflectance) was measured.

[Average luminous reflectance]
After rubbing the surface of the transparent support (lowermost surface in FIG. 1) with sandpaper and applying a matte black paint, using a spectrophotometer ("U-4100" manufactured by Hitachi High-Technologies Corporation), JIS Based on R-3106, the average luminous reflectance (5 ° relative reflectance) was measured.
[Transparent chromaticity]

The transmission chromaticity of the antireflection film was measured using a spectrocolorimeter (Konica Minolta Holdings, Inc., CM3600D) under 10-degree field of view and C light source conditions.
[Sheet resistance]

Electrodes were installed on the surface of the antireflection film, and sheet resistance was measured based on JIS K6911 using an insulation resistance measuring instrument (R8340A manufactured by Advantest Corporation).
[Fingerprint removal]

  After the fingerprint is attached to the surface of the antireflection film to stain the surface, it is wiped 50 times with BEMCOT-S2 (Asahi Kasei Fibers Co., Ltd.). Thereafter, the film was visually observed from a distance of 40 cm from the antireflection film to evaluate the degree of fingerprint removal.

  The measurement results are shown in Tables 1 and 2.

  From Table 1 and Table 2, in Example 1 in which a light-absorbing material is blended in an appropriate amount into the hard coat material, the minimum reflectance and the average luminous reflectance are low, and the total light transmittance is high. An antireflection member having transparency and low reflectance was obtained. In consideration of the practicality of the antireflection member, one guideline is a total light transmittance of 90% or more and an average luminous reflectance of 1.0% or less.

  Further, by setting the transmission chromaticity in the L * a * b * color system to be −1.0 ≦ a * ≦ 0 and 0 ≦ b * ≦ 1.0, the transparency and low reflection required for the antireflection member are required. The color tone could be neutral while ensuring the characteristics.

  On the other hand, in Comparative Example 1, since the light-absorbing material was not blended with the hard coat material, the minimum reflectance and the average luminous reflectance were high. Although Comparative Examples 2-4 mix | blended the light absorptive material, since it deviated from the appropriate quantity, the total light transmittance fell.

DESCRIPTION OF SYMBOLS 1 Antireflection member 2 Transparent support 3 Hard coat layer 4 Low refractive index layer 5 Antifouling layer

Claims (10)

  In the antireflection member in which a hard coat layer and a low refractive index layer are provided in this order on a transparent support, the hard coat layer contains a light-absorbing material that absorbs light within a wavelength range of 400 to 800 nm, An antireflection member having light absorption in a wavelength range of 400 to 800 nm by the hard coat layer containing the light absorbing material and having a total light transmittance of 90% or more.   2. The antireflection member according to claim 1, wherein the transmission chromaticity in the L * a * b * color system is −1.0 ≦ a * ≦ 0 and 0 ≦ b * ≦ 1.0.   The antireflection member according to claim 1, wherein an average luminous reflectance is 1.0% or less.   4. The antireflection member according to claim 1, wherein the refractive index of the hard coat layer is 1.50 to 1.90.   5. The hard coat layer contains at least one oxide selected from titanium, aluminum, cerium, yttrium, zirconium, niobium, and antimony as high refractive index particles. The antireflection member according to 1.   The antireflection member according to claim 1, wherein the hard coat layer has antistatic properties.   The antireflection member according to any one of claims 1 to 6, comprising at least one oxide selected from indium, zinc, tin, and antimony as conductive nanoparticles in the hard coat layer. . 8. The antireflection member according to claim 1, wherein the hard coat layer has a sheet resistance of 10 ¹⁴ Ω / □ or less.   The antireflective member according to claim 1, wherein a refractive index of the low refractive index layer is 1.30 to 1.45.   The antireflection member according to claim 1, further comprising an antifouling layer on a surface of the low refractive index layer.

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