Antireflection substrate

Abstract

Provided is an antireflection substrate, which is an antireflection substrate in which (A) a substrate layer, (B) a hard coat layer, (C) a light absorbing layer, and (D) a low-refractive layer, which is a layer formed by curing a low-refractive resin composition containing an active energy ray-curable resin, hollow silica, and a fluorine-based compound with an active energy ray, are sequentially stacked, and the film thickness of the (C) light absorbing layer is 1 to 20 nm.

Description

TECHNICAL FIELD

[0001] The present application relates to an antireflection substrate, and particularly relates to an antireflection substrate having low apparent reflectance and excellent antifouling properties. BACKGROUND

[0002] In display applications such as smartphones, car navigation systems, and game consoles, materials having an antireflection function are used to prevent external light from being reflected.

[0003] Antireflection materials generally use optical interference technology. Optical interference generally uses an optical thin film that is thinner than the wavelength of visible light. In particular, to achieve an ultralow reflectance of 1.0% or less, a plurality of optical thin films need to be coated, and for example, an antireflection film having a 4-layer structure of Nb2O5-SiO2-Nb2O5-SiO2 on a close contact layer is known (Patent Documents 1 and 2). However, to form such a multilayer film, a plurality of film formation devices are required, and thus there is a problem of high cost. In addition, to be used for displays, an antifouling function is also required, and thus an antifouling layer needs to be provided on the outermost surface layer.

[0004] On the other hand, as a method of reducing the number of films and reducing apparent reflectance, a method of using a light-absorbing layer is known (Patent Documents 3 and 4). As the light-absorbing layer, titanium nitride, zirconium nitride, gold, silver, copper, or the like can be used, and a substance having a wavelength dispersion of the refractive index n being negative and a wavelength dispersion of the extinction coefficient k being positive is preferably used. By forming a film of a low refractive index such as SiO2 on these light-absorbing layers, a low apparent reflectance can be achieved even with 2 layers of coating. However, even with this method, when used for displays, an antifouling function is still required, and thus an antifouling layer needs to be provided on the outermost surface layer.

[0005] As a method of providing an antifouling layer on a light-absorbing layer, a method of coating an organosilane and fluorine on a light-absorbing layer is known (Patent Document 5). However, this method is heat-cured, and there is a problem of low productivity and the necessity of long-time heating to achieve stable physical properties.

[0006] To improve antireflection performance, the low-refractive-index layer is preferably low in refractive index. However, the refractive index of SiO2, which is generally used, is as high as 1.46, and it is difficult to achieve sufficient antireflection performance.

[0007] PRIOR ART DOCUMENTS

[0008] PATENT DOCUMENTS

[0009] Patent Document 1: Japanese Patent Application Laid-Open (JP-A) No. 2019-35969

[0010] Patent Document 2: Japanese Patent Application Laid-Open (JP-A) No. 2018-8431

[0011] Patent Document 3: Japanese Patent Application Laid-Open (JP-A) No. Hei 10-96801

[0012] Patent Literature 4: Japanese Patent Laid-Open No. 9-73001

[0013] Patent Literature 5: Japanese Patent Laid-Open No. 2002-341107 SUMMARY

[0014] PROBLEMS TO BE SOLVED BY THE INVENTION

[0015] The present application has been made to solve the above problems, and provides an antireflection substrate which realizes low visual reflection and antifouling properties with a small number of steps and layers.

[0016] MEANS OF SOLVING THE PROBLEMS

[0017] The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that the above problems can be solved by the present application described below. That is, the present application is as follows.

[0018] <1> An antireflection substrate which is an antireflection substrate in which the following (A), (B), (C) and (D) layers are sequentially laminated, wherein

[0019] (A) a substrate layer,

[0020] (B) a hard coat layer,

[0021] (C) a light absorbing layer, and

[0022] (D) a low refractive index layer which is a layer formed by curing a low refractive index resin composition containing an active energy ray-curable resin, hollow silica and a fluorine-based compound with an active energy ray,

[0023] The film thickness of the above (C) light absorbing layer is 1 to 20 nm.

[0024] <2> The antireflection substrate described in the above <1>, wherein the above (C) light absorbing layer is a layer formed of at least one selected from the group consisting of titanium nitride, titanium nitride oxide, zirconium nitride, gold, silver and copper.

[0025] <3> The antireflection substrate described in the above <1> or <2>, wherein the film thickness of the above (C) light absorbing layer is 2 to 15 nm.

[0026] <4> The antireflection substrate described in any one of the above <1> to <3>, wherein the active energy ray-curable resin in the above (D) low refractive index layer contains a polyurethane (meth) acrylate component.

[0027] <5> The antireflection substrate described in any one of the above <1> to <4>, wherein the fluorine-based compound in the above (D) low refractive index layer contains a perfluoropolyether bond.

[0028] The antireflection substrate according to any one of <1> to <5> above, wherein the refractive index of the low refractive layer (D) at a wavelength of 550 nm is 1.45 or less.

[0029] The antireflection substrate according to any one of <1> to <6> above, wherein the apparent reflectance is 1.0% or less.

[0030] The antireflection substrate according to any one of <1> to <7> above, wherein the antireflection substrate does not contain an antifouling layer.

[0031] Effects of the Invention

[0032] By adopting the scheme of the present application, it is possible to produce an antireflection substrate imparted with antifouling properties without the need for separately performing antifouling coating. The antireflection substrate of the present application has the advantage of low apparent reflectance. DETAILED DESCRIPTION

[0033] Hereinafter, the present application will be described in detail with reference to Production Examples and Examples, but the present application is not limited to the Production Examples and Examples, and can be changed to any method as long as it is within the scope of the present application.

[0034] [Substrate Layer]

[0035] In the present application, the material constituting the substrate layer is not particularly limited, and a glass substrate, a metal substrate, or a plastic substrate can be used. In particular, regarding the plastic substrate, the types of compounds constituting it are various, and it can be used in various fields.

[0036] As the plastic substrate, it is preferable to contain a thermoplastic resin. The type of the thermoplastic resin is not particularly limited, and polycarbonate (PC) resin, acrylic resin such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cyclic olefin copolymer (COC), norbornene-containing resin, polyether sulfone, cellophane, and aromatic polyamide can be exemplified.

[0037] The polycarbonate resin contained in the base material layer is not particularly limited as long as it is a resin containing a -[O-R-OCO]- unit (R is an aliphatic group, an aromatic group, or a group including both aliphatic and aromatic groups, and has a linear structure or a branched structure) including a carbonate bond in a molecular main chain, and is preferably a polycarbonate having a bisphenol skeleton, and particularly preferably a polycarbonate having a bisphenol A skeleton or a bisphenol C skeleton. As the polycarbonate resin, a mixture or a copolymer of bisphenol A and bisphenol C can be used. By using a bisphenol C-based polycarbonate resin such as a polycarbonate resin of bisphenol C alone, a mixture of bisphenol C and bisphenol A, or a copolymer of bisphenol C and bisphenol A, the hardness of the base material layer can be increased.

[0038] Further, the viscosity average molecular weight of the polycarbonate resin is preferably 15,000 to 40,000, more preferably 20,000 to 35,000, and even more preferably 22,500 to 25,000.

[0039] In addition, the acrylic resin contained in the base material layer is not particularly limited, and various (meth)acrylate homopolymers represented by polymethyl methacrylate (PMMA) and methyl methacrylate (MMA), or copolymers of PMMA or MMA and another one or more monomers, and resins obtained by mixing a plurality of these resins can be cited, for example. Among these, a (meth)acrylate containing a cyclic alkyl structure that is excellent in low birefringence, low moisture absorption, and heat resistance is preferred. As examples of the (meth)acrylate resin as described above, ACRYPET (manufactured by Mitsubishi Rayon Co., Ltd.), DELPET (manufactured by Asahi Kasei Corporation), PARAPET (manufactured by KURARAY Co., Ltd.), and the like can be cited, but are not limited to these.

[0040] A two-layer product containing a polycarbonate resin and the above-described acrylic resin can also be used. By using a two-layer product containing a polycarbonate resin and the above-described acrylic resin, the surface hardness can be increased, and the thermoformability of the base material layer can be maintained.

[0041] Further, an additive can be contained in the base material layer as a component other than the thermoplastic resin. For example, at least one additive selected from the group consisting of a heat stabilizer, an antioxidant, a flame retardant, a flame retardant aid, an ultraviolet absorber, a release agent, and a colorant, and the like. Further, an antistatic agent, an optical brightener, an antifog agent, a flowability improver, a plasticizer, a dispersant, an antibacterial agent, and the like can also be added to the base material layer.

[0042] [Hard Coat Layer]

[0043] In the present application, a hard coat layer is provided on the substrate layer. For example, a material obtained by performing hard coating on a thermoplastic resin constituting the substrate layer can be used. As a method of forming the hard coat layer, a method of applying a hard coat composition containing an active energy ray-curable resin, drying, and then curing using an active energy ray; a method of applying a thermosetting composition containing a thermosetting compound, drying, and then curing by heating can be employed. Among these, the method of applying a hard coat composition containing an active energy ray-curable resin, drying, and then curing using an active energy ray is preferred.

[0044] The active energy ray-curable resin can be used as long as it is a compound containing a functional group having active energy ray-curing properties, and is preferably a resin containing a polyurethane (meth)acrylate component. The polyurethane (meth)acrylate contains a polymer of a resin material including a polyurethane (meth)acrylate derived from a polyol, an isocyanate, and a (meth)acrylate, and a (meth)acrylate. That is, a mixture of a polyurethane (meth)acrylate derived from a polyol, an isocyanate, and a (meth)acrylate, and a (meth)acrylate is preferred.

[0045] An additive for improving properties can be added to the hard coat composition. For example, a fluorine-based additive, a silicone-based additive, which can impart stain resistance and sliding properties, an inorganic particle component for improving scratch resistance, and the like can be used.

[0046] [Light-absorbing layer]

[0047] In the present application, a light-absorbing layer is provided on the hard coat layer. As a material constituting the light-absorbing layer, a metal such as gold, silver, copper, nickel, chromium, tin, palladium, and alloys thereof, titanium nitride, zirconium nitride, hafnium nitride, silicon nitride, aluminum nitride, metal nitride such as titanium nitride, iron oxide, chromium oxide, nickel oxide, and the like can be used. Among these, at least one selected from the group consisting of titanium nitride, titanium nitride, zirconium nitride, gold, silver, and copper is preferably used. By using these, a low apparent reflectance in a wide wavelength range can be achieved.

[0048] The film formation of the light-absorbing layer is preferably performed by Dry film formation. As a method of Dry film formation, CVD, PVD can be used, but PVD is generally used. As a method of PVD, evaporation, sputtering are widely used. Devices for evaporation, sputtering are sold by a plurality of device manufacturers such as ULVAC Corporation, SHINCRON Corporation, OPTORUN Corporation.

[0049] The film thickness of the light absorbing layer is preferably 1 to 40 nm, more preferably 1 to 20 nm, further more preferably 2 to 20 nm, still further preferably 2 to 15 nm, and particularly preferably 3 to 10 nm. When the film thickness is too thin, the reflectance reduction effect is poor, and when the film thickness is too thick, the transmittance is sometimes significantly reduced. In the present application, the film thickness of the light absorbing layer can be measured by the method described in the Examples below.

[0050] A close contact layer can also be provided between the light absorbing layer and the hard coat layer. As the close contact layer, for example, SiO2, SiO x , SiN x , Al2O3, AlO x , AlN x , or the like can be provided. These close contact layers are formed by dry film formation, and typically, evaporation or sputtering is used.

[0051] The film thickness of the close contact layer is preferably 1 to 10 nm, and more preferably 2 to 5 nm. When the film thickness is too thin, the close contact effect is poor, and when the film thickness is too thick, the optical properties are sometimes affected.

[0052] [Low refractive index layer]

[0053] In the present application, a low refractive index layer is provided on the light absorbing layer. The low refractive index layer in the present application is a layer formed by curing a low refractive index resin composition containing an active energy ray-curable resin, hollow silica, and a fluorine-based compound with an active energy ray. In the present application, the low refractive index resin composition preferably contains a silicone-based compound and a photopolymerization initiator in addition to the active energy ray-curable resin, the hollow silica, and the fluorine-based compound.

[0054] The active energy ray-curable resin can be any compound containing a functional group having an active energy ray-curing ability, and is preferably a resin containing a polyurethane (meth)acrylate component. The polyurethane (meth)acrylate contains a polymer of a resin material containing a polyurethane (meth)acrylate derived from a polyol, an isocyanate, and a (meth)acrylate, and a (meth)acrylate. That is, it is preferably a mixture of a polyurethane (meth)acrylate derived from a dehydration condensation reaction of a polyol, an isocyanate, and a (meth)acrylate, and a (meth)acrylate.

[0055] Hollow silica is characterized by having air inside the silica and a low refractive index. As the hollow silica, for example, THRULYA (trade name) manufactured by Showa Denko K.K. is commercially available, but is not limited thereto.

[0056] The hollow silica is preferably mixed at a ratio of activated energy ray-curable resin / hollow silica = 90 / 10 to 10 / 90 (mass %), and more preferably at a ratio of 80 / 20 to 20 / 80 (mass %). When the content of the hollow silica is too much, the scratch resistance is reduced, and when it is too little, the refractive index becomes high, and sometimes sufficient antireflection performance cannot be obtained.

[0057] The fluorine-based compound preferably uses a compound having a perfluoropolyether bond. These compounds can use a synthetic product, but a commercial product can also be easily obtained. For example, the MEGAFACE RS series of DIC Corporation, the KY series of SHIN-ETSU CHEMICAL CO., LTD., the OPTOOL series of Daikin Industries, Ltd., and the like can be used.

[0058] The content of the fluorine-based compound is preferably 1 to 30 mass % in the low refractive index resin composition, and more preferably 5 to 20 mass %.

[0059] The silicone-based compound preferably uses a compound having a polyalkylsiloxane bond. These compounds can use a synthetic product, but a commercial product can also be easily obtained. For example, the KP series of SHIN-ETSU SILICONE CO., LTD., the BYK series of BYK-CHEMIE JAPAN Co., Ltd., the TEGO Glide series of EVONIK, and the like can be used.

[0060] As for the fluorine compound and the silicone-based compound, they can also be used in mixture.

[0061] Further, the low refractive index resin composition has activated energy ray-curing property, and more preferably has ultraviolet ray-curing property. Therefore, the low refractive index resin composition preferably contains a photopolymerization initiator. As the photopolymerization initiator, Omnirad 184 (formerly IRGACURE 184) of IGM Resins B.V. Co., Ltd. (1-hydroxy-cyclohexyl-phenyl-ketone), Omnirad 1173 (old IRGACURE 1173) (2-hydroxy-2-methyl-1-phenyl-propane-1-ketone), Omnirad TPO H (old IRGACURE TPO) (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), Omnirad 819 (old IRGACURE 819) (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide), Esacure ONE of Lamberti Co., Ltd. (oligomer (2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone), and the like are preferably used.

[0062] The mixture of the active energy ray-curable resin, the hollow silica, and the fluorine-based compound (and the preferably added silicone-based compound, the photopolymerization initiator) is generally used after being diluted with an organic solvent. As the organic solvent, toluene, xylene, ethyl acetate, propyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, methanol, ethanol, isopropanol, butanol, diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, hexane, heptane, octane, decane, dodecane, propylene glycol monomethyl ether, 3-methoxybutanol, and the like can be exemplified.

[0063] The organic solvent is preferably used in an amount of 0.5 to 10 mass% of the solid content in the low-refractive resin composition, and more preferably in an amount of 1 to 5 mass%. When the amount of the organic solvent is too large, the control of the film thickness becomes difficult, and when the amount is too small, the appearance can sometimes be deteriorated.

[0064] For example, the mixture of the active energy ray-curable resin, the hollow silica, the fluorine-based compound, and the photopolymerization initiator is diluted with an organic solvent, coated in a prescribed manner, and then the organic solvent is dried, and then cured by an active energy ray, whereby a low-refractive layer can be formed. During the drying of the organic solvent, the fluorine-based compound having a small surface free energy is precipitated to the surface layer, and thus the antifouling function can be exhibited even without intentionally forming an antifouling layer.

[0065] The coating can be performed by a conventional method. For example, it can be performed by a bar coater, a spin coater, a gravure coater, a comma coater, a die coater, or the like.

[0066] The low-refractive resin composition is diluted with an organic solvent, coated, dried, and cured by an active energy ray, whereby a low-refractive layer can be obtained. As the active energy ray, ultraviolet rays, near-ultraviolet rays, visible rays, or the like can be used, but among these, ultraviolet rays are most conventionally used.

[0067] The refractive index of the low-refractive layer at 550 nm is preferably 1.45 or less, more preferably 1.42 or less, and even more preferably 1.40 or less. The lower the refractive index, the higher the antireflection performance. In addition, the lower the refractive index, the thinner the light-absorbing layer can be made, and thus the transmittance is improved. In the present application, the method for measuring the refractive index can employ the method described in the Examples below.

[0068] The antireflection substrate of the present application preferably has a visual reflectance of 1.0% or less, more preferably 0.9% or less, and particularly preferably 0.8% or less. When the visual reflectance is 1.0% or less, the effect of improving the visual recognition is good, and thus is preferred. In the present application, the method for measuring the visual reflectance can employ the method described in the Examples below.

[0069] The transmittance of the antireflection substrate of the present application is preferably 50% or more, more preferably 70% or more. The appearance is good when the transmittance is in the above range, and thus is preferred. In the present application, the method for measuring the light transmittance can employ the method described in the Examples below.

[0070] Examples

[0071] The present application will be described more specifically below using examples. However, the present application is not limited to the examples below, and arbitrary changes can be made within the scope of the gist of the present application.

[0072] <Reflectance (apparent reflectance)>

[0073] Using SD6000 manufactured by Nippon Densho Kogyo Co., Ltd., the reflectance was measured in accordance with JIS Z 8722-2009. At the time of measurement, in order to prevent reflection from the back surface (substrate layer side) of the film from each example, the opposite surface of the coated surface was subjected to a black spray treatment, and then the reflectance was measured. Specifically, under a light source of standard light source D65 defined by the International Commission on Illumination (CIE), the reflectance was measured by the SCI method in which the direct reflection light and the diffuse reflection light were measured together. Using the thus measured reflectance, the apparent reflectance as the reflection stimulus value Y prescribed by JIS Z8701 was calculated.

[0074] <Transmittance>

[0075] Using spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation, the transmittance for light of wavelength 550 nm was measured.

[0076] <Fingerprint rub-off test>

[0077] After 2 μl of oleic acid was dropped as an artificial fingerprint liquid on the test piece, and the spread was pressed with a silicone pad, a cloth was put on to pass completely over the artificial fingerprint liquid. This operation was repeated, and the evaluation was 0 if the fingerprint was rubbed off in 5 times or less, and the evaluation was X if 6 times or more were required.

[0078] <Haze>

[0079] Using a haze meter (product name: HM-150) manufactured by Murakami Color Research Laboratory Co., Ltd., the haze (%) was measured in accordance with JIS-K-7136.

[0080] <Thickness of light absorbing layer>

[0081] The film thickness of the light absorbing layer was measured using a contact-type step meter (Dektak XT manufactured by Bruker). A portion of the glass substrate was masked during the film formation of the light absorbing layer, and the step difference between the unformed portion and the formed portion was measured as the film thickness. In addition, when the film thickness of the light absorbing layer was measured for the antireflection substrate after the formation of multiple layers, a method of observing the film profile using a transmission electron microscope after the ion beam processing and measuring the film thickness can be used.

[0082] As the substrate, in Examples 1 to 5 and Comparative Examples 1 to 3, a hard coat film (product name: MRF08U (manufactured by Mitsubishi Gas Chemical Company, Inc.)) on which a hard coat treatment was performed using a polyurethane acrylate-based hard coat composition (B-1) described below on the PMMA side of a 2-layer film of polycarbonate (PC) and polymethyl methacrylate (PMMA) was used. In Example 6, a hard coat film on which a polyurethane acrylate-based hard coat treatment was performed in the same manner as described above on a film (product name: COSMOSHINE A4100 (manufactured by Toyobo Co., Ltd.), thickness: 188 μm) composed of polyethylene terephthalate (PET) was used. In Example 7, a hard coat film on which a polyurethane acrylate-based hard coat treatment was performed in the same manner as described above on a film (product name: TD80UL (manufactured by FUJIFILM Corporation), thickness: 80 μm) composed of triacetyl cellulose (TAC) was used.

[0083] Low-refractive resin composition (A-1)

[0084] To form the low-refractive layer, a curable low-refractive coating was prepared as follows.

[0085] First, dry air was introduced into a 5-neck flask equipped with a stirrer, a thermometer, a cooler, a monomer dropping funnel, and a dry air inlet tube to dry the system. Then, 58.9 parts by mass of 2,2,3,3-tetrafluoro-l,4-butanediol (C4DIOL manufactured by Exfluor Research Corporation), 279.8 parts by mass of pentaerythritol triacrylate, 0.5 parts by mass of dibutyl tin laurate as a polymerization catalyst, and 500 parts by mass of methyl ethyl ketone as a solvent were added to the 5-neck flask, and the temperature was raised to 60°C. Then, 161.3 parts by mass of isophorone diisocyanate was added, and the reaction was performed at 60 to 70°C. After confirming that all of the isocyanate residues in the reactants were consumed by infrared absorption spectroscopy, the reaction was terminated, and a 6-functional polyurethane acrylate oligomer was obtained.

[0086] Further, acrylic acid 2-(2-vinyloxyethoxy)ethyl (VEEA) was mixed at a ratio of 90 / 10 (mass%) of the polyurethane acrylate liquid / VEEA with respect to the polyurethane acrylate oligomer (polyurethane acrylate liquid).

[0087] For the liquid component of the resin material thus obtained, hollow silica (THRULYA 4320 manufactured by Nippon Shokubai Co., Ltd.) was mixed so as to reach a ratio of 50 / 50 (mass%) of the resin material / hollow silica in terms of solid content. Further, for the low-refractive coating material (resin material + hollow silica) thus obtained, 5 mass% of 1-hydroxy-cyclohexyl-phenyl-ketone (I-184 manufactured by BASF) as a photopolymerization initiator, 10 mass% of MEGAFACE RS-90 (manufactured by DIC: a substance in which a solid content is 10 mass% and diluted with solvent MEK) as a fluorine-based compound, and 10 mass% of BYK-UV3575 (modified polydimethylsiloxane-based surfactant manufactured by BYK-CHEMIE) were added respectively, and they were dissolved, solvent (propylene glycol monomethyl ether) was added, and the concentration was adjusted so as to reach 1.5 mass% of solid content. Note that the amounts of the additives are described in mass% with respect to 100 mass% of the solid content of the low-refractive coating material.

[0088] Hard coat composition (B-1)

[0089] Polyurethane acrylate UN-954 (manufactured by Konishi Industry Co., Ltd.) as a hard coat paint, 5 mass% of 1-hydroxy-cyclohexyl-phenyl-ketone (I-184 manufactured by BASF) as a photoinitiator, 1 mass% of BYK-3550 (manufactured by BYK-CHEMIE·JAPAN Co., Ltd.) as a leveling agent, and solvent (propylene glycol monomethyl ether) were added, and the concentration was adjusted so as to reach 30 mass% of solid content. Note that the amounts of the additives are described in mass% with respect to 100 mass% of the solid content of the hard coat paint.

[0090] The low-refractive resin composition (A-1) was coated on a glass plate, dried at 100°C for 2 minutes, and subjected to UV curing with a cumulative light amount of 400 mJ / cm 2 UV curing was performed, and a low-refractive layer was formed. The refractive index of the low-refractive layer at 550 nm was measured using a spectroscopic ellipsometer (AutoSE manufactured by Horiba Ltd.), and the result was 1.38. Further, the refractive index of the hard coat composition (B-1) was measured by the same method as described above, and the result was 1.50.

[0091] (Example 1)

[0092] On the surface of the above-mentioned substrate (product name: MRF08U) on which the hard coat treatment was performed, copper was deposited by sputtering to a film thickness of 3.0 nm to form a light absorbing layer. Thereafter, a low refractive index resin composition (A-1) was applied onto the light absorbing layer using a bar coater to a film thickness after drying and UV curing of 100 nm, and after drying at 100°C for 2 minutes, UV curing was performed with a cumulative light amount of 400 mJ / cm 2 UV curing was performed to form a low refractive index layer, and an antireflection substrate was produced. The obtained antireflection substrate was measured for apparent reflectance and transmittance, and the apparent reflectance was 0.60% and the transmittance was 87%. The result of the fingerprint removal test was O.

[0093] (Example 2)

[0094] On the surface of the above-mentioned substrate (product name: MRF08U) on which the hard coat treatment was performed, titanium nitride was deposited by sputtering to a film thickness of 6.0 nm to form a light absorbing layer. Thereafter, a low refractive index resin composition (A-1) was applied onto the light absorbing layer using a bar coater to a film thickness after drying and UV curing of 100 nm, and after drying at 100°C for 2 minutes, UV curing was performed with a cumulative light amount of 400 mJ / cm 2 UV curing was performed to form a low refractive index layer, and an antireflection substrate was produced. The obtained antireflection substrate was measured for apparent reflectance and transmittance, and the apparent reflectance was 0.75% and the transmittance was 80%. The result of the fingerprint removal test was O.

[0095] (Example 3)

[0096] On the surface of the above-mentioned substrate (product name: MRF08U) on which the hard coat treatment was performed, titanium nitride was deposited by sputtering to a film thickness of 3.6 nm to form a light absorbing layer. Thereafter, a low refractive index resin composition (A-1) was applied onto the light absorbing layer using a bar coater to a film thickness after drying and UV curing of 85 nm, and after drying at 100°C for 2 minutes, UV curing was performed with a cumulative light amount of 400 mJ / cm 2 UV curing was performed to form a low refractive index layer, and an antireflection substrate was produced. The obtained antireflection substrate was measured for apparent reflectance and transmittance, and the apparent reflectance was 0.49% and the transmittance was 85.6%. The result of the fingerprint removal test was O.

[0097] (Example 4)

[0098] On the surface of the above-mentioned substrate (product name: MRF08U) on which the hard coat treatment was performed, titanium nitride was deposited by sputtering to a film thickness of 6.4 nm to form a light absorbing layer. Thereafter, the low-refractive-index resin composition (A-1) was applied onto the light absorbing layer using a bar coater to a film thickness of 85 nm after drying and UV curing, and after drying at 100°C for 2 minutes, the low-refractive-index layer was formed by UV curing to a cumulative light amount of 400 mJ / cm 2 The low-refractive-index layer was formed by UV curing to produce an antireflection substrate. The visual reflectance and the transmittance of the obtained antireflection substrate were measured, and the visual reflectance was 0.50% and the transmittance was 82.2%. The result of the fingerprint removal test was O.

[0099] (Example 5)

[0100] On the surface of the above-mentioned substrate (product name: MRF08U) on which the hard coat treatment was performed, titanium nitride was deposited by sputtering to a film thickness of 11.3 nm to form a light absorbing layer. Thereafter, the low-refractive-index resin composition (A-1) was applied onto the light absorbing layer using a bar coater to a film thickness of 85 nm after drying and UV curing, and after drying at 100°C for 2 minutes, the low-refractive-index layer was formed by UV curing to a cumulative light amount of 400 mJ / cm 2 The low-refractive-index layer was formed by UV curing to produce an antireflection substrate. The visual reflectance and the transmittance of the obtained antireflection substrate were measured, and the visual reflectance was 0.50% and the transmittance was 82.2%. The result of the fingerprint removal test was O.

[0101] (Example 6)

[0102] On the surface of the above-mentioned PET substrate (product name: COSMOSHINE A4100) on which the hard coat treatment was performed, titanium nitride was deposited by sputtering to a film thickness of 6.4 nm to form a light absorbing layer. Thereafter, the low-refractive-index resin composition (A-1) was applied onto the light absorbing layer using a bar coater to a film thickness of 85 nm after drying and UV curing, and after drying at 100°C for 2 minutes, the low-refractive-index layer was formed by UV curing to a cumulative light amount of 400 mJ / cm 2 The low-refractive-index layer was formed by UV curing to produce an antireflection substrate. The visual reflectance and the transmittance of the obtained antireflection substrate were measured, and the visual reflectance was 0.50% and the transmittance was 82.2%. The result of the fingerprint removal test was O.

[0103] (Example 7)

[0104] On the surface of the TAC substrate (product name: TD80UL) subjected to the hard coat treatment described above, titanium nitride was deposited by sputtering to a film thickness of 6.4 nm to form a light absorbing layer. Thereafter, a low-refractive-index resin composition (A-1) was applied to the light absorbing layer using a bar coater to a film thickness after drying and UV curing of 85 nm, and after drying at 100°C for 2 minutes, UV curing was performed to a cumulative light amount of 400 mJ / cm 2 UV curing was performed to form a low-refractive-index layer, and an antireflection substrate was produced. The obtained antireflection substrate was measured for apparent reflectance and transmittance, and the apparent reflectance was 0.40% and the transmittance was 82.3%. The result of the fingerprint removal test was O.

[0105] (Comparative Example 1)

[0106] On the surface of the substrate (product name: MRF08U) subjected to the hard coat treatment described above, copper was deposited by sputtering to a film thickness of 4.0 nm to form a light absorbing layer. Thereafter, SiO2was deposited on the light absorbing layer by sputtering to a film thickness of 58 nm, and an antireflection substrate was produced. The obtained antireflection substrate was measured for apparent reflectance and transmittance, and the apparent reflectance was 0.80% and the transmittance was 80%. The result of the fingerprint removal test was X.

[0107] (Comparative Example 2)

[0108] On the surface of the substrate (product name: MRF08U) subjected to the hard coat treatment described above, a low-refractive-index resin composition (A-1) was applied to a film thickness after drying and UV curing of 100 nm using a bar coater, and after drying at 100°C for 2 minutes, UV curing was performed to a cumulative light amount of 400 mJ / cm 2 UV curing was performed to form a low-refractive-index layer, and an antireflection substrate was produced. The obtained antireflection substrate was measured for apparent reflectance and transmittance, and the apparent reflectance was 1.42% and the transmittance was 93.6%. The result of the fingerprint removal test was O.

[0109] (Comparative Example 3)

[0110] On the surface of the substrate (product name: MRF08U) subjected to the hard coat treatment described above, titanium nitride was deposited by sputtering to a film thickness of 21.1 nm to form a light absorbing layer. Thereafter, a low-refractive-index resin composition (A-1) was applied to the light absorbing layer using a bar coater to a film thickness after drying and UV curing of 85 nm, and after drying at 100°C for 2 minutes, UV curing was performed to a cumulative light amount of 400 mJ / cm 2 UV curing was performed to form a low-refractive-index layer, and an antireflection substrate was produced. The obtained antireflection substrate was measured for apparent reflectance and transmittance, and the apparent reflectance was 14.12% and the transmittance was 42.1%. The result of the fingerprint removal test was O.

[0111] The results of Examples 1 to 7 and Comparative Examples 1 to 3 are shown in Table 1 below.

[0112] [Table 1]

[0113]

Claims

1. An anti-reflection substrate, characterized by: being an anti-reflection substrate in which the following (A), (B), (C) and (D) layers are sequentially laminated, (A) a substrate layer, (B) a hard coat layer, (C) a light absorbing layer, and (D) a low refractive index layer which is a layer formed by curing a low refractive index resin composition containing an active energy ray-curable resin, hollow silica and a fluorine-based compound by an active energy ray, the (C) light absorbing layer has a film thickness of 2 to 15 nm, the (C) light absorbing layer is formed by Dry film formation selected from CVD and PVD, the active energy ray-curable resin in the (D) low refractive index layer contains a polyurethane (meth) acrylate component, and the fluorine-based compound in the (D) low refractive index layer contains a perfluoropolyether bond.

2. The anti-reflection substrate according to claim 1, characterized in that: the (C) light absorbing layer is a layer formed from at least one selected from the group consisting of titanium nitride, titanium nitride oxide, zirconium nitride, gold, silver and copper.

3. The anti-reflection substrate according to claim 1 or 2, characterized in that: the (D) low refractive index layer has a refractive index of 1.45 or less at a wavelength of 550 nm.

4. The anti-reflection substrate according to claim 1 or 2, characterized in that: the apparent reflectance is 1.0% or less.

5. The anti-reflection substrate according to claim 1 or 2, characterized in that: it does not contain a stain-proof layer. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​

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