JP2016218105A - Antireflective laminate and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflective laminate having high hardness and excellent scratch resistance and a method for manufacturing the antireflective laminate.SOLUTION: An antireflective laminate 1 comprises a transparent substrate 2, an anchor layer 3 formed on the transparent substrate 2 and containing an antioxidant, a high refractive index layer 4 formed on the anchor layer 3, and a low refractive index layer 5 formed on the high refractive index layer 4 and having a refractive index lower than that of the high refractive index layer 4, in which the anchor layer 3, the high refractive index layer 4 and the low refractive index layer 5 contain an ionization radiation-curable resin. The antireflective laminate has such a steel wool resistance determined by a steel wool resistance test that the laminate has no scratches under a load of 1000 g.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an antireflection laminate disposed on the surface of a display device or the like and a method for manufacturing the same.

  In general, in a display device such as a liquid crystal display device, a plasma display panel, an organic electroluminescence display device (hereinafter sometimes referred to as an organic EL display device), and electronic paper, reflection of external light is suppressed and visibility is improved. In order to enhance, an antireflection film is disposed on the surface of the display device. Further, since the antireflection film is disposed on the surface of a display device or the like, scratch resistance is required, and high surface hardness is required (Patent Document 1).

As the antireflection film, for example, a film in which a high refractive index layer and a low refractive index layer are laminated on a transparent substrate is used. In addition, as the antireflective film, there are known a high refractive index layer and a low refractive index layer in which an inorganic layer is laminated or in which an organic layer is laminated.
The inorganic layer has an advantage that an antireflection film having high strength, high hardness and excellent scratch resistance can be obtained. However, in the case of an inorganic layer, since a plurality of layers are laminated by a dry process such as a sputtering method or a vacuum evaporation method, there is a problem that productivity is lowered and manufacturing cost is increased. In particular, in the case of an antireflection film used for a large-area display device, the equipment becomes large and the cost increases. Further, in the case of the dry process, there is a problem that the in-plane distribution of the thickness of the antireflection layer varies, and the uniformity of the antireflection property is impaired.
On the other hand, the organic layer is advantageous in terms of productivity and cost, but has a problem of low scratch resistance and hardness as compared with the inorganic layer.
Therefore, when an organic layer is laminated as a high refractive index layer or a low refractive index layer, an antireflection film having high hardness and excellent scratch resistance similar to the case of an inorganic layer is required.

  In an antireflection film in which an organic layer is laminated as a high refractive index layer or a low refractive index layer on a transparent substrate, as a means for improving scratch resistance and hardness, for example, between a transparent substrate and a high refractive index layer A technique for providing an anchor layer has been proposed. However, although the scratch resistance and hardness are improved by forming the anchor layer, the actual situation is that sufficient scratch resistance and hardness are not obtained as compared with the case of the inorganic layer.

JP 2007-185824 A

  The present invention has been made in view of the above problems, and provides an antireflection laminate having high hardness and excellent scratch resistance when an organic layer is laminated on a transparent substrate, and a method for producing the same. The main purpose.

  As a result of intensive studies to solve the above problems, the inventors of the present invention include an ionizing radiation curable resin in which the anchor layer, the high refractive index layer, and the low refractive index layer are cured by irradiation with ionizing radiation such as ultraviolet rays and electron beams. In this case, it was found that the scratch resistance and hardness are improved by increasing the temperature of the heat treatment after curing by ionizing radiation irradiation. On the other hand, when the temperature of the heat treatment after curing by ionizing radiation is increased, the anchor layer, the high refractive index layer and the low refractive index layer are yellowed and applied as an antireflection laminate disposed on the surface of a display device, etc. It cannot be done. Therefore, the present inventors have further studied, and by including an antioxidant in the anchor layer, the temperature of the heat treatment can be increased without causing yellowing, and is highly hard and excellent in scratch resistance. The inventors have found that an antireflection film can be obtained, and have completed the present invention.

  That is, the present invention includes a transparent base material, an anchor layer formed on the transparent base material and containing an antioxidant, a high refractive index layer formed on the anchor layer, and the high refractive index layer. And a low refractive index layer having a lower refractive index than the high refractive index layer, wherein the anchor layer, the high refractive index layer and the low refractive index layer contain an ionizing radiation curable resin. An antireflection laminate is provided.

  According to the present invention, since the anchor layer contains an antioxidant, yellowing can be suppressed. Therefore, when manufacturing the antireflection laminate of the present invention, heat treatment after curing by ionizing radiation irradiation. Temperature can be increased, and scratch resistance and hardness can be improved.

  In addition, the antireflection laminate of the present invention preferably has a steel wool resistance determined by a steel wool resistance test with a load of 1000 g and no scratches. According to the present invention, scratch resistance similar to that of an antireflection laminate in which an inorganic layer is laminated on a transparent substrate can be realized.

  The present invention also provides an anchor layer forming step in which an anchor layer is formed by applying an curable resin composition for an anchor layer containing an antioxidant on a transparent substrate, and curing the composition by irradiation with ionizing radiation. A high refractive index layer forming step of forming a high refractive index layer by applying a curable resin composition for a high refractive index layer and curing the composition by irradiation with ionizing radiation; and a low refractive index layer on the high refractive index layer A low refractive index layer forming step of forming a low refractive index layer having a refractive index lower than that of the high refractive index layer by applying a curable resin composition for application, curing by irradiation with ionizing radiation, performing a heat treatment A method for producing an antireflection laminate is provided.

  According to the present invention, by forming an anchor layer using a curable resin composition for an anchor layer containing an antioxidant, the temperature of the heat treatment after curing by ionizing radiation irradiation in the low refractive index layer forming step The scratch resistance and hardness can be improved.

  In the said invention, the coating film of the said curable resin composition for anchor layers is semi-hardened in the said anchor layer formation process, The coating film of the said curable resin composition for high refractive index layers in the said high refractive index layer formation process In the low refractive index layer forming step, the anchor layer curable resin composition coating film, the high refractive index layer curable resin composition coating film, and the low refractive index layer curable resin It is preferable to cure the coating film of the composition. This is because the adhesion of the anchor layer, the high refractive index layer and the low refractive index layer can be increased, and the scratch resistance and hardness can be further improved.

  In this invention, there exists an effect that it is possible to provide the antireflection laminated body which is high hardness and excellent in abrasion resistance, and its manufacturing method.

It is a schematic sectional drawing which shows an example of the reflection preventing laminated body of this invention. It is process drawing which shows an example of the manufacturing method of the reflection preventing laminated body of this invention. It is process drawing which shows the other example of the manufacturing method of the reflection preventing laminated body of this invention.

  Hereinafter, the antireflection laminate of the present invention and the production method thereof will be described in detail.

A. Antireflection laminate The antireflection laminate of the present invention includes a transparent substrate, an anchor layer formed on the transparent substrate and containing an antioxidant, and a high refractive index layer formed on the anchor layer. A low refractive index layer formed on the high refractive index layer and having a lower refractive index than the high refractive index layer, and the anchor layer, the high refractive index layer, and the low refractive index layer are ionized radiation cured. It is characterized by containing a resin.

The antireflection laminate of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of the antireflection laminate of the present invention. As illustrated in FIG. 1, the antireflection laminate 1 includes a transparent substrate 2, an anchor layer 3 formed on the transparent substrate 2 and containing an antioxidant, and a high layer formed on the anchor layer 3. It has a refractive index layer 4 and a low refractive index layer 5 formed on the high refractive index layer 4. The anchor layer 3, the high refractive index layer 4 and the low refractive index layer 5 all contain an ionizing radiation curable resin.

  Here, “ionizing radiation curable resin” refers to a resin cured by irradiation with ionizing radiation. “Ionizing radiation” refers to electromagnetic waves or charged particle beams having an energy quantum capable of polymerizing or cross-linking molecules. And charged particle beams such as ion beams.

  Here, when the anchor layer, the high refractive index layer and the low refractive index layer contain an ionizing radiation curable resin, the anchor layer, the high refractive index layer and the low refractive index layer are usually formed on a transparent substrate. Apply the curable resin composition for the anchor layer to form an anchor layer by irradiating with ionizing radiation, and then apply the curable resin composition for the high refractive index layer on the anchor layer and irradiate with ionizing radiation. After forming a high refractive index layer by curing with, after applying the curable resin composition for the low refractive index layer on the high refractive index layer and curing by irradiation with ionizing radiation to form the low refractive index layer Then, heat treatment is performed. If the temperature in this heat treatment is too high, the anchor layer, the high refractive index layer, and the low refractive index layer turn yellow, and cannot be applied as an antireflection laminate disposed on the surface of a display device or the like.

  On the other hand, in the present invention, since the anchor layer contains an antioxidant, yellowing due to heating can be suppressed, so that yellowing occurs when the antireflection laminate of the present invention is produced. Without this, the temperature of the heat treatment can be increased. When the temperature of the heat treatment increases, components such as the solvent, unreacted monomer and low molecular weight remaining in the anchor layer, high refractive index layer and low refractive index layer are removed, and the anchor layer, high refractive index layer and low refractive index layer are removed. Increasing the density of polymer components and the like in the refractive index layer increases the entanglement between the molecular chains, so that the adhesion between the anchor layer, the high refractive index layer, and the low refractive index layer can be improved. Therefore, it is possible to improve the scratch resistance and hardness of the antireflection laminate of the present invention.

  In general, in an antireflection laminate, the high refractive index layer and the low refractive index layer are thinner than the anchor layer, so that the anchor layer contains an antioxidant, so that the anchor layer and the high refractive index layer have a high refractive index. The effect of suppressing yellowing due to heating of the layer and the low refractive index layer can be sufficiently obtained.

  In the present invention, the anchor layer, the high refractive index layer, and the low refractive index layer all contain an ionizing radiation curable resin and can be formed by a wet process, and a uniform layer can be easily formed even in a large area. can do. Therefore, it is possible to obtain an inexpensive antireflection laminate having excellent antireflection properties.

  Hereinafter, each configuration in the antireflection laminate of the present invention will be described.

1. Anchor layer The anchor layer in the present invention is formed on a transparent substrate and contains an ionizing radiation curable resin and an antioxidant. By forming the anchor layer, the adhesion of the high refractive index layer and the low refractive index layer to the transparent substrate can be enhanced.

  As a refractive index of an anchor layer, it is preferable that it is more than the refractive index of a transparent base material, and it is preferable that it is below the refractive index of a high refractive index layer. Further, the refractive index of the anchor layer is preferably small in the difference from the refractive index of the transparent base material, and specifically, the difference from the refractive index of the transparent base material is preferably within 0.03. Within 0.02, especially within 0.01. In this case, it can suppress that light reflects in the interface of an anchor layer and a transparent base material.

  The antioxidant used in the anchor layer is not particularly limited as long as it can suppress the color change of the anchor layer due to heat, particularly yellowing, and can obtain a transparent anchor layer. Antioxidants can be used. Examples thereof include phenolic, amine-based, sulfur-based and phosphorus-based antioxidants. Of these, phenolic antioxidants are preferred. Specific examples include hindered phenol Irganox 1010 (manufactured by BASF Japan).

  The content of the antioxidant in the anchor layer is not particularly limited as long as it can suppress the color change of the anchor layer due to heating, particularly yellowing, and obtain an anchor layer having transparency. It is preferable to be within the range of mass% to 5 mass%. If the content of the antioxidant is too small, a sufficient antioxidant effect may not be obtained. Moreover, when there is too much content of antioxidant, the bleed-out of antioxidant will arise and there exists a possibility that the adhesiveness of an anchor layer and a high refractive index layer may be impaired.

The ionizing radiation curable resin used for the anchor layer should be capable of obtaining an anchor layer that has adhesion to the transparent base material and the high refractive index layer, has transparency, and satisfies the above refractive index. There is no particular limitation. For example, an ultraviolet curable resin or an electron beam curable resin can be used. Specifically, the same ionizing radiation curable resin used for a low refractive index layer and a high refractive index layer described later can be used.
For example, acrylic resin etc. are mentioned, Specifically, urethane acrylate, epoxy acrylate, polyester acrylate, polyol acrylate, polyether acrylate, melamine acrylate, etc. are mentioned.

  The content of the ionizing radiation curable resin in the anchor layer is appropriately set according to the target hardness, strength, refractive index, and the like.

  The anchor layer may contain a filler. This is because the hardness of the anchor layer can be increased. As the filler, both inorganic and organic can be used. Examples of the inorganic filler include fine particles such as silica, alumina, titania, zirconia, zinc oxide, tin oxide, and indium tin oxide, glass beads, and glass fibers. As the organic filler, for example, resin beads can be used, and specific examples include acrylic beads, urethane beads, nylon beads, silicone beads, silicone rubber beads, and polycarbonate beads.

The average particle size of the filler is preferably in the range of, for example, 5 nm to 50 nm, and more preferably in the range of 5 nm to 40 nm, and particularly preferably in the range of 5 nm to 30 nm. When the average particle size of the filler is within the above range, the transparency of the anchor layer is not impaired, and a good filler dispersion state is obtained. On the other hand, if the average particle size of the filler is too small, handling becomes difficult, and if it is too large, the effect of increasing the hardness may not be sufficiently obtained. If the average particle size of the filler is within the above range, the average particle size may be either the primary particle size or the secondary particle size, and the fillers may be continuous in a chain shape.
Here, the average particle diameter of the filler refers to an average value of 20 particles observed by a transmission electron microscope (TEM) photograph of a cross section of the anchor layer.

  The shape of the filler is not particularly limited, and examples thereof include a spherical shape, a chain shape, and a needle shape.

  The filler content in the anchor layer is appropriately set according to the target hardness, strength, refractive index, and the like.

Further, when an ultraviolet curable resin is used as the ionizing radiation curable resin, the anchor layer may contain a photopolymerization initiator. As a photoinitiator, it can select from a general thing suitably.
Moreover, the anchor layer may contain various additives as needed.

  The anchor layer may have irregularities on the surface opposite to the transparent substrate. Thereby, the adhesiveness of an anchor layer and a high refractive index layer can be improved. The height difference and the pitch of the unevenness may be adjusted as appropriate as long as the adhesiveness with the high refractive index layer can be enhanced. The irregularities may be regularly arranged or irregularly arranged.

  The thickness of the anchor layer is not particularly limited as long as it can increase the adhesion of the high refractive index layer and the low refractive index layer to the transparent substrate. For example, by making the anchor layer thicker than the high refractive index layer and the low refractive index layer, the adhesion of the high refractive index layer and the low refractive index layer to the transparent substrate can be enhanced. Specifically, from the viewpoint of adhesion, the thickness of the anchor layer is preferably in the range of 0.3 μm to 10 μm.

  Here, the “thickness” of each member refers to a thickness obtained by a general measurement method. Thickness measurement methods include, for example, a stylus type method of calculating the thickness by tracing the surface with a stylus and detecting an unevenness, an optical method of calculating the thickness based on the spectral reflection spectrum, etc. Can do. Specifically, the thickness can be measured using a stylus thickness meter P-15 manufactured by KLA-Tencor Corporation. In addition, as thickness, the average value of the thickness measurement result in the several location of the member used as object may be used.

As a formation method of an anchor layer, the method of apply | coating the curable resin composition for anchor layers containing antioxidant on a transparent base material, and making it harden | cure by irradiation of ionizing radiation is mentioned.
In addition, since it forms in the below-mentioned "B. manufacturing method of an antireflection laminated body" about the formation method of an anchor layer, description here is abbreviate | omitted.

2. Low Refractive Index Layer The low refractive index layer in the present invention is formed on the high refractive index layer, contains an ionizing radiation curable resin, and has a lower refractive index than the high refractive index layer.

  The refractive index of the low refractive index layer may be lower than the refractive index of the high refractive index layer and lower than the refractive index of the transparent substrate. Specifically, the refractive index of the low refractive index layer is preferably in the range of 1.2 to 1.4.

  Here, the “refractive index” of each member refers to the refractive index with respect to light having a wavelength of 550 nm. The method for measuring the refractive index is not particularly limited, and examples thereof include a method of calculating from a spectral reflection spectrum, a method of measuring using an ellipsometer, and an Abbe method. An example of the ellipsometer is UVSEL manufactured by Joban-Evon. Specifically, the refractive index can be measured with DF1030R manufactured by Techno Synergy.

  The low refractive index layer is not particularly limited as long as it satisfies the above refractive index and has transparency. For example, a layer containing an ionizing radiation curable resin, an ionizing radiation curable resin, and a low refractive index fine particle. The thing etc. which contain are mentioned. Among these, since the refractive index can be easily adjusted, the low refractive index layer preferably contains an ionizing radiation curable resin and low refractive index fine particles.

  The ionizing radiation curable resin used for the low refractive index layer is not particularly limited as long as it satisfies the above refractive index and can obtain a transparent low refractive index layer. And from the viewpoint of film strength and the like. As the ionizing radiation curable resin, for example, an ultraviolet curable resin or an electron beam curable resin can be used. Among these, an ultraviolet curable resin is preferable.

Specific examples of the ionizing radiation curable resin include JP2013-142817A, JP2012-150226A, JP2011-170208A, JP2009-86360A, and JP2008-9347A. And the like used in the low refractive index layer described in the above.
The ionizing radiation curable resin may be a fluorine-based resin containing fluorine. This is because antifouling properties can be imparted to the low refractive index layer. Further, the refractive index can be lowered. Moreover, the fluorine resin may contain silicon.
The low refractive index layer may contain an antifouling agent. As the antifouling agent, a fluorine-based compound or a silicon-based compound can be used. Specifically, examples of the antifouling agent include those described in JP2012-150226A.

  The low refractive index fine particles are not particularly limited as long as the refractive index is lower than that of the ionizing radiation curable resin and a low refractive index layer satisfying the above refractive index can be obtained. Any of the systems can be used. Among these, hollow particles and porous particles are preferably used because of their low refractive index. Examples of the hollow particles and the porous particles include porous silica particles, hollow silica particles, porous polymer particles, and hollow polymer particles.

Further, the low refractive index fine particles may be subjected to a surface treatment. By applying surface treatment to the low refractive index fine particles, the affinity with ionizing radiation curable resin and solvent is improved, the dispersion of the low refractive index fine particles becomes uniform, and the aggregation of the low refractive index fine particles is less likely to occur. A decrease in the transparency of the refractive index layer, a coating property of the curable resin composition for the low refractive index layer, and a decrease in the coating strength of the curable resin composition for the low refractive index layer can be suppressed.
Examples of the surface-treated low refractive index fine particles include those described in JP2013-142817A and JP2008-9348A.

  The low refractive index fine particles may be reactive fine particles having a photocurable group on the surface thereof.

  Specific examples of the low refractive index fine particles include JP2013-142817A, JP2012-150226A, JP2011-170208A, JP2009-86360A, and JP2008-9347A. And the like used in the low refractive index layer described in the above.

The average particle diameter of the low refractive index fine particles is not limited as long as a low refractive index layer having a uniform thickness can be formed. For example, it is preferably in the range of 5 nm to 200 nm, and more preferably in the range of 5 nm to 100 nm. In particular, it is preferably within the range of 10 nm to 80 nm. When the average particle diameter of the low refractive index fine particles is within the above range, the transparency of the low refractive index layer is not impaired, and a good dispersion state of the low refractive index fine particles can be obtained. If the average particle size of the low refractive index fine particles is within the above range, the average particle size may be either the primary particle size or the secondary particle size, and the low refractive index fine particles are connected in a chain. May be.
Here, the average particle diameter of the low refractive index fine particles refers to an average value of 20 particles observed by a transmission electron microscope (TEM) photograph of a cross section of the low refractive index layer.

  The shape of the low refractive index fine particles is not particularly limited, and examples thereof include a spherical shape, a chain shape, and a needle shape.

  The contents of the ionizing radiation curable resin and the low refractive index fine particles in the low refractive index layer are appropriately set so that the refractive index of the entire low refractive index layer satisfies the above refractive index.

  When an ultraviolet curable resin is used as the ionizing radiation curable resin, the low refractive index layer may contain a photopolymerization initiator. As a photoinitiator, it can select from a general thing suitably.

  The low refractive index layer may contain various additives according to desired physical properties. Examples of additives include a dispersion aid, a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an adhesion improver, an antioxidant, a leveling agent, a thixotropic agent, and a cup. A ring agent, a plasticizer, an antifoamer, a filler, etc. are mentioned.

  The thickness of the low refractive index layer varies depending on the refractive index, but is preferably in the range of 50 nm to 200 nm from the viewpoint of reducing reflection in the visible light region.

Examples of the method for forming the low refractive index layer include a method in which a curable resin composition for the low refractive index layer is applied and cured by irradiation with ionizing radiation.
In addition, since it describes in the below-mentioned "B. manufacturing method of an antireflection laminated body" about the formation method of a low refractive index layer, description here is abbreviate | omitted.

3. High Refractive Index Layer The high refractive index layer in the present invention is formed on the anchor layer, contains an ionizing radiation curable resin, and has a higher refractive index than the low refractive index layer.

  The refractive index of the high refractive index layer may be higher than the refractive index of the low refractive index layer and higher than the refractive index of the transparent substrate. Specifically, the refractive index of the high refractive index layer is preferably in the range of 1.5 to 1.7.

  The high refractive index layer is not particularly limited as long as it satisfies the above refractive index and has transparency. For example, a layer containing ionizing radiation curable resin, ionizing radiation curable resin, and high refractive index fine particles are used. The thing etc. which contain are mentioned. Among these, since the refractive index can be easily adjusted, the high refractive index layer preferably contains an ionizing radiation curable resin and high refractive index fine particles.

  The ionizing radiation curable resin used for the high refractive index layer is not particularly limited as long as it satisfies the above refractive index and can obtain a transparent high refractive index layer. And from the viewpoint of film strength and the like. Examples of the ionizing radiation curable resin include an ultraviolet curable resin and an electron beam curable resin. Among these, an ultraviolet curable resin is preferable.

  Specifically, examples of the ionizing radiation curable resin include those used for the high refractive index layer described in JP2013-142817A, JP2012-150226A, JP2011-170208A, and the like. be able to.

The high refractive index fine particles are not particularly limited as long as the refractive index is higher than that of the ionizing radiation curable resin and a high refractive index layer satisfying the above refractive index can be obtained. The refractive index of the fine particles is preferably about 1.5 to 2.8.
Examples of such high refractive index fine particles include metal oxide fine particles, specifically, zirconium oxide, antimony oxide, antimony tin oxide, indium tin oxide, phosphorus tin compound, gallium zinc oxide, β-Al ₂ O ₅ , γ-Al ₂ O ₅ , barium titanate, titanium oxide, cerium oxide, tin oxide, aluminum zinc oxide, gallium zinc oxide, zinc antimonate, and the like can be given.

The high refractive index fine particles may be surface-treated. By subjecting the high refractive index fine particles to surface treatment, the affinity with ionizing radiation curable resin and solvent is improved, the dispersion of the high refractive index fine particles becomes uniform, and the high refractive index fine particles are less likely to aggregate. Decrease in the transparency of the refractive index layer, applicability of the curable resin composition for the high refractive index layer, and decrease in the coating strength of the curable resin composition for the high refractive index layer can be suppressed.
Examples of the surface-treated high refractive index fine particles include those described in JP2013-142817A.

  The high refractive index fine particles may be reactive fine particles having a photocurable group on the surface thereof.

The average particle diameter of the high refractive index fine particles is not limited as long as a high refractive index layer having a uniform thickness can be formed, and is preferably in the range of 5 nm to 200 nm, for example, in the range of 5 nm to 100 nm. In particular, it is preferably within the range of 10 nm to 80 nm. If the average particle diameter of the high refractive index fine particles is within the above range, the transparency of the high refractive index layer is not impaired, and a good dispersion state of the high refractive index fine particles can be obtained. As long as the average particle size of the high refractive index fine particles is within the above range, the average particle size may be either the primary particle size or the secondary particle size, and the high refractive index fine particles are connected in a chain. May be.
Here, the average particle diameter of the high refractive index fine particles refers to an average value of 20 particles observed by a transmission electron microscope (TEM) photograph of a cross section of the high refractive index layer.

  The shape of the high refractive index fine particles is not particularly limited, and examples thereof include a spherical shape, a chain shape, and a needle shape.

  The contents of the ionizing radiation curable resin and the high refractive index fine particles in the high refractive index layer are appropriately set so that the refractive index of the entire high refractive index layer satisfies the above refractive index.

  When an ultraviolet curable resin is used as the ionizing radiation curable resin, the high refractive index layer may contain a photopolymerization initiator. Moreover, the high refractive index layer may contain various additives according to desired physical properties. In addition, about a photoinitiator and various additives, it can be made the same as that of the said low-refractive-index layer.

  The thickness of the high refractive index layer varies depending on the refractive index, but is preferably in the range of 50 nm to 200 nm.

Examples of the method for forming the high refractive index layer include a method in which a curable resin composition for the high refractive index layer is applied and cured by irradiation with ionizing radiation.
In addition, since it describes in the below-mentioned "B. manufacturing method of an antireflection laminated body" about the formation method of a high refractive index layer, description here is abbreviate | omitted.

4). Middle Refractive Index Layer In the present invention, a middle refractive index layer may be formed between the high refractive index layer and the low refractive index layer, or between the anchor layer and the high refractive index layer. The medium refractive index layer in the present invention contains an ionizing radiation curable resin, and has a refractive index lower than that of the high refractive index layer and higher than that of the low refractive index layer.

  The refractive index of the medium refractive index layer may be lower than the refractive index of the high refractive index layer and higher than the refractive index of the low refractive index layer. Specifically, the refractive index of the middle refractive index layer is preferably in the range of 1.45 to 1.65.

  The medium refractive index layer is not particularly limited as long as it satisfies the above refractive index and has transparency. For example, a layer containing an ionizing radiation curable resin, an ionizing radiation curable resin, and a high refractive index fine particle. The thing etc. which contain are mentioned. Specifically, the same material as the high refractive index layer can be used.

  The thickness of the medium refractive index layer varies depending on the refractive index, but is preferably in the range of 50 nm to 200 nm.

Examples of the method for forming the middle refractive index layer include a method in which a curable resin composition for the middle refractive index layer is applied and cured by irradiation with ionizing radiation.
The method for forming the middle refractive index layer will be described in “B. Method for producing antireflection laminate” described later, and thus the description thereof is omitted here.

5. Transparent substrate The transparent substrate used in the present invention supports an anchor layer, a high refractive index layer, and a low refractive index layer.
Examples of the material for the transparent substrate include resin and glass.
The transparent substrate may or may not have flexibility.
The thickness of the transparent substrate is appropriately selected according to the use of the antireflection laminate.
Moreover, in this invention, the transparent base material which has heat resistance is preferable. This is because heat resistance is required when performing the heat treatment. Therefore, in the present invention, glass is more preferable than resin.

6). Antireflection laminate The antireflection laminate of the present invention has scratch resistance. As the scratch resistance, the steel wool resistance determined by a steel wool resistance test is preferably no damage at a load of 1000 g, more preferably no damage at a load of 1200 g, especially no damage at a load of 1700 g.
Here, the steel wool resistance test is a test in which the surface of the antireflective laminate on the low refractive index layer side is rubbed 10 times with a predetermined load using # 1000 steel wool and visually evaluated for scratches. is there.

  The antireflection laminate of the present invention can be used for display devices such as liquid crystal display devices, plasma display panels, organic EL display devices, inorganic EL display devices, and electronic paper. Examples of the use of the antireflection laminate of the present invention include a mobile phone, a tablet terminal, a personal computer, a television, a digital signage, and a wearable terminal. The antireflection laminate of the present invention can also be used for antireflection of the surface of, for example, a solar cell, an optical lens, or a window glass.

7). Production Method The antireflection laminate of the present invention is preferably produced by a method for producing an antireflection laminate described later. That is, in the present invention, since the anchor layer contains an antioxidant, yellowing due to heat can be suppressed. Therefore, in the method for producing an antireflection laminate described later, heating after curing by irradiation with ionizing radiation. The treatment temperature can be increased, and scratch resistance and hardness can be improved.

B. Manufacturing method of antireflection laminate The manufacturing method of the antireflection laminate of the present invention comprises applying a curable resin composition for an anchor layer containing an antioxidant on a transparent substrate, and curing it by irradiation with ionizing radiation. An anchor layer forming step for forming an anchor layer, and forming a high refractive index layer by applying a curable resin composition for a high refractive index layer on the anchor layer and curing it by irradiation with ionizing radiation Applying a curable resin composition for a low refractive index layer on the high refractive index layer, curing by irradiation with ionizing radiation, heat treatment, low refractive index having a refractive index lower than that of the high refractive index layer And a low refractive index layer forming step for forming a refractive index layer.

The manufacturing method of the antireflection laminated body of this invention is demonstrated with reference to drawings.
2A to 2F are process diagrams showing an example of a method for producing an antireflection laminate of the present invention. First, as shown in FIGS. 2 (a) to 2 (b), the anchor layer curable resin composition 3 a is applied on the transparent substrate 2 and cured by irradiation with ionizing radiation 10 to form the anchor layer 3. . Next, as shown in FIGS. 2 (c) to 2 (d), the high refractive index layer curable resin composition 4 a is applied on the anchor layer 3, and cured by irradiation with ionizing radiation 10 to form a high refractive index layer. 4 is formed. Next, as shown in FIGS. 2 (e) to 2 (f), the low refractive index layer curable resin composition 5 a is applied on the high refractive index layer 4, cured by irradiation with ionizing radiation 10, and heat treatment. (Not shown) to form the low refractive index layer 5.

  In the present invention, by forming an anchor layer using a curable resin composition for an anchor layer containing an antioxidant, yellowing due to heating can be suppressed, so in the low refractive index layer forming step The temperature of the heat treatment after curing by ionizing radiation irradiation can be increased without causing yellowing. Therefore, the adhesion of the anchor layer, the high refractive index layer and the low refractive index layer can be enhanced, and an antireflection laminate having high hardness and excellent scratch resistance can be obtained.

  In the present invention, since the anchor layer, the high refractive index layer, and the low refractive index layer are all formed by a wet process, a uniform layer can be easily formed even in a large area. Therefore, it is possible to produce an antireflection laminate having excellent antireflection properties at low cost.

  3A to 3F are process diagrams showing another example of the method for producing an antireflection laminate of the present invention. First, as shown to Fig.3 (a)-(b), the curable resin composition 3a for anchor layers is apply | coated on the transparent base material 2, and it is made to semi-cure by irradiation of the ionizing radiation 10, and is a semi-hardened state. The coating film 3b of the curable resin composition for anchor layer is formed. Next, as shown in FIGS. 3C to 3D, the high refractive index layer curable resin composition 4a is applied onto the coating film 3b of the semi-cured anchor layer curable resin composition. And semi-cured by irradiation with ionizing radiation 10 to form a coating film 4b of the curable resin composition for a high refractive index layer in a semi-cured state. Next, as shown in FIG. 3 (e), a low refractive index layer curable resin composition 5a is applied onto the coating film 4b of the high refractive index layer curable resin composition in a semi-cured state, and ionized. Coating film 3b of curable resin composition for anchor layer semi-cured by irradiation of radiation 10, coating film 4b of curable resin composition for high refractive index layer semi-cured, and curable resin for low refractive index layer The coating film of the composition 5a is completely cured. Thereafter, heat treatment is performed (not shown), and the anchor layer 3, the high refractive index layer 4, and the low refractive index layer 5 are formed as shown in FIG.

  Thus, in the present invention, the anchor layer curable resin composition coating film is semi-cured in the anchor layer forming step, and the high refractive index layer curable resin composition coating film is formed in the high refractive index layer forming step. Semi-cured, coating film of curable resin composition for anchor layer, coating film of curable resin composition for high refractive index layer and coating of curable resin composition for low refractive index layer in low refractive index layer forming step It is preferred to cure the film. Thereby, the adhesiveness of an anchor layer, a high refractive index layer, and a low refractive index layer can further be improved. Therefore, the scratch resistance and hardness can be further improved.

  Hereinafter, each process in the manufacturing method of the reflection preventing laminated body of this invention is demonstrated.

1. Anchor layer forming step The anchor layer forming step in the present invention is a step in which an anchor layer is formed by applying a curable resin composition for an anchor layer containing an antioxidant on a transparent substrate and curing it by irradiation with ionizing radiation. It is.

  The anchor layer curable resin composition contains, for example, a resin component, an antioxidant, various additives, and a solvent. The solvent is not particularly limited as long as each component can be dissolved or dispersed, and is appropriately selected.

Examples of the method for applying the curable resin composition for the anchor layer include a die coating method, a spin coating method, a dip coating method, a roll coating method, a gravure printing method, an offset printing method, and a silk screen printing method.
After application of the anchor layer curable resin composition, the anchor layer may be dried to remove the solvent.

  Examples of the method for curing the coating film of the curable resin composition for anchor layer include irradiation with ionizing radiation such as ultraviolet rays and electron beams.

  In the anchor layer forming step, the coating film of the curable resin composition for the anchor layer is semi-cured, and in the high refractive index layer forming step described later, the coating film of the curable resin composition for the high refractive index layer is semi-cured. The coating film of the curable resin composition for the anchor layer, the coating film of the curable resin composition for the high refractive index layer, and the coating film of the curable resin composition for the low refractive index layer in the low refractive index layer forming step described later May be completely cured. That is, the curable resin composition for the high refractive index layer is applied in a semi-cured state of the curable resin composition for the anchor layer, and the curable resin composition for the high refractive index layer is semi-cured. The curable resin composition for the low refractive index layer is applied in the state, the coating film of the curable resin composition for the anchor layer, the coating film of the curable resin composition for the high refractive index layer, and the curable resin for the low refractive index layer. The coating film of the composition may be completely cured. In this case, the adhesion of the anchor layer, the high refractive index layer, and the low refractive index layer can be enhanced, and the scratch resistance and hardness can be further improved.

  What is necessary is just to adjust the irradiation amount of ionizing radiation in order to semi-harden the coating film of the curable resin composition for anchor layers. As the irradiation amount of ionizing radiation, when the curable resin composition for a high refractive index layer is applied onto the coating film of the curable resin composition for an anchor layer in a semi-cured state, the curable resin composition for the anchor layer is What is necessary is just the irradiation amount which can semi-cure the coating film of the curable resin composition for anchor layers to such an extent that a coating film does not melt | dissolve in the solvent contained in the curable resin composition for high refractive index layers. Specifically, it is preferable that the irradiation amount of ionizing radiation is about 1/10 to 1/4 of the complete curing irradiation amount of the coating film of the anchor layer curable resin composition. When the irradiation amount of ionizing radiation is too small, when the curable resin composition for a high refractive index layer is applied onto the coating film of the curable resin composition for an anchor layer in a semi-cured state, the curable resin composition for the anchor layer The resulting coating film is dissolved in the solvent contained in the curable resin composition for the high refractive index layer, the interface between the anchor layer and the high refractive index layer becomes unclear, and the antireflection function may be lowered. Moreover, when there is too much irradiation amount of ionizing radiation, there exists a possibility that the effect which improves the adhesiveness of an anchor layer and a high refractive index layer may not fully be acquired.

Here, “completely cured” means a state in which all of the ionizing radiation reactive groups in the curable resin composition have reacted and the coating film of the curable resin composition has been completely cured.
Further, the “complete curing exposure amount” refers to the minimum exposure amount necessary for completely curing the coating film of the curable resin composition.

More specifically, the ionizing radiation dose is appropriately adjusted according to the composition of the anchor layer curable resin composition, the thickness of the coating film, and the like. For example, the application of the anchor layer curable resin composition If semi-curing the film by ultraviolet irradiation, exposure of ultraviolet rays is preferably ² ~80mJ / cm 2 of about 20 mJ ^/ cm.

  Further, when forming an anchor layer having irregularities on the surface, for example, after applying and drying the curable resin composition for anchor layer on a transparent substrate, the irregularity-forming substrate or irregularity-forming roll is applied to the coating film. And a method of peeling the unevenness forming substrate or the unevenness forming roll, and a method of polishing the anchor layer surface.

  Since the other points of the anchor layer are described in detail in the above “A. Antireflection laminate”, description thereof is omitted here.

2. High refractive index layer forming step In the high refractive index layer forming step in the present invention, a high refractive index layer is formed by applying a curable resin composition for a high refractive index layer on an anchor layer and curing it by irradiation with ionizing radiation. It is a process.

  The curable resin composition for a high refractive index layer contains, for example, a resin component, high refractive index fine particles, various additives, and a solvent. The solvent is not particularly limited as long as each component can be dissolved or dispersed. For example, JP 2013-142817 A, JP 2012-150226 A, JP 2011-170208 A, and the like. And those used for forming the high refractive index layer described in (1).

The method for forming the high refractive index layer can be the same as the method for forming the anchor layer.
Moreover, when hardening the coating film of the curable resin composition for high refractive index layers, it is preferable to set it as inert gas atmosphere, for example, nitrogen gas atmosphere, in order to suppress the cure inhibition by oxygen.

  In addition, as described above, the anchor layer curable resin composition coating film is semi-cured in the anchor layer forming step, and the high refractive index layer curable resin composition coating film is also formed in the high refractive index layer forming step. Semi-cured, the coating film of the curable resin composition for the anchor layer, the coating film of the curable resin composition for the high refractive index layer, and the curable resin composition for the low refractive index layer in the low refractive index layer forming step described later The coating film of the product may be completely cured. In this case, the adhesion of the anchor layer, the high refractive index layer, and the low refractive index layer can be enhanced, and the scratch resistance and hardness can be further improved.

  In order to semi-cure the coating film of the curable resin composition for a high refractive index layer, the dose of ionizing radiation may be adjusted. The amount of ionizing radiation applied is such that when the curable resin composition for the low refractive index layer is applied onto the coating film of the curable resin composition for the high refractive index layer in a semi-cured state, the curability for the high refractive index layer is applied. The irradiation dose should be such that the coating film of the curable resin composition for the high refractive index layer can be semi-cured to such an extent that the coating film of the resin composition does not dissolve in the solvent contained in the curable resin composition for the low refractive index layer. That's fine. Specifically, it is preferable that the irradiation amount of ionizing radiation is about 1/10 to 1/4 of the complete curing irradiation amount of the coating film of the curable resin composition for a high refractive index layer. If the irradiation amount of ionizing radiation is too small, when the curable resin composition for a low refractive index layer is applied on the coating film of the curable resin composition for a high refractive index layer in a semi-cured state, the high refractive index layer The coating film of the curable resin composition is dissolved in the solvent contained in the curable resin composition for the low refractive index layer, the interface between the high refractive index layer and the low refractive index layer becomes unclear, and the antireflection function decreases. There is a risk. Moreover, when there is too much irradiation amount of ionizing radiation, there exists a possibility that the effect which improves the adhesiveness of a high refractive index layer and a low refractive index layer may not fully be acquired.

More specifically, the irradiation amount of ionizing radiation is appropriately adjusted according to the composition of the curable resin composition for the high refractive index layer, the thickness of the coating film, and the like. For example, the curable resin for the high refractive index layer If semi-curing the coating composition by ultraviolet radiation, the exposure amount of ultraviolet rays is preferably ² ~80mJ / cm 2 of about 20 mJ ^/ cm.

  In addition, since the other points of the high refractive index layer were described in detail in the above “A. Antireflection laminated body”, description thereof is omitted here.

3. Low Refractive Index Layer Forming Step The low refractive index layer forming step in the present invention is performed by applying a curable resin composition for a low refractive index layer on a high refractive index layer, curing by irradiation with ionizing radiation, and performing a heat treatment. This is a step of forming a low refractive index layer.

  The curable resin composition for a low refractive index layer contains, for example, a resin component, low refractive index fine particles, various additives, and a solvent. The solvent is not particularly limited as long as each component can be dissolved or dispersed. For example, JP 2013-142817 A, JP 2012-150226 A, JP 2011-170208 A, Examples thereof include those used for forming a low refractive index layer described in JP-A-2009-86360, JP-A-2008-9347, and the like.

The method for forming the low refractive index layer can be the same as the method for forming the anchor layer.
Moreover, when hardening the coating film of the curable resin composition for low refractive index layers, it is preferable to set it as inert gas atmosphere, for example, nitrogen gas atmosphere, in order to suppress the cure inhibition by oxygen. By performing so-called nitrogen purge, the scratch resistance of the low refractive index layer can be enhanced.

  Also, as described above, the anchor layer curable resin composition coating film is semi-cured in the anchor layer forming step, and the high refractive index layer curable resin composition coating film is formed in the high refractive index layer forming step. Is semi-cured, and the coating film of the curable resin composition for the anchor layer, the coating film of the curable resin composition for the high refractive index layer, and the curable resin composition for the low refractive index layer in the low refractive index layer forming step The coating film may be completely cured. In this case, the adhesion of the anchor layer, the high refractive index layer, and the low refractive index layer can be enhanced, and the scratch resistance and hardness can be further improved.

To completely cure the coating film of the curable resin composition for the anchor layer, the coating film of the curable resin composition for the high refractive index layer, and the coating film of the curable resin composition for the low refractive index layer, irradiation with ionizing radiation Adjust the amount. The irradiation amount of ionizing radiation is appropriately adjusted according to the composition of each curable resin composition, the thickness of the coating film, etc., for example, when the coating film of each curable resin composition is completely cured by ultraviolet irradiation, exposure of ultraviolet rays is preferably 160mJ ^/ cm ² ~400mJ ^/ cm 2 approximately.

  Further, after irradiation with ionizing radiation, heat treatment is performed in order to increase the scratch resistance and hardness. The heating temperature is not particularly limited as long as it is a temperature at which the anchor layer, the high refractive index layer and the low refractive index layer do not yellow, and a desired scratch resistance can be obtained. It adjusts suitably according to the composition of the curable resin composition, the curable resin composition for the high refractive index layer, the curable resin composition for the low refractive index layer, the thickness of the coating film, and the like. Specifically, the heating temperature is preferably in the range of 200 ° C to 300 ° C. If the heating temperature is too low, sufficient scratch resistance may not be obtained. If the heating temperature is too high, yellowing may occur.

  Here, “yellowing” can be evaluated by transmittance within a wavelength range of 400 nm to 500 nm. Specifically, when the transmittance within a wavelength range of 400 nm to 500 nm is less than 98%, yellow When the changed transmittance within the wavelength range of 400 nm to 500 nm is 98% or more, it is evaluated that the material is not yellowed.

  In addition, since the other points of the low refractive index layer were described in detail in the above-mentioned “A. Antireflection laminated body”, description here is omitted.

4). Intermediate refractive index layer forming step In the present invention, the intermediate refractive index layer is formed by applying a curable resin composition for the intermediate refractive index layer on the anchor layer before the high refractive index layer forming step, and curing it by irradiation with ionizing radiation. The medium refractive index is formed, or the medium refractive index layer is formed by applying a curable resin composition for the medium refractive index layer on the high refractive index layer after the high refractive index layer forming step, and curing by applying ionizing radiation. A layer forming step may be performed.

The curable resin composition for the medium refractive index layer can be the same as the above curable resin composition for the high refractive index layer.
The method for forming the medium refractive index layer can be the same as the method for forming the high refractive index layer.

  Also, as described above, the anchor layer curable resin composition coating film is semi-cured in the anchor layer forming step, and the high refractive index layer curable resin composition coating film is formed in the high refractive index layer forming step. And semi-curing the coating film of the curable resin composition for the medium refractive index layer in the intermediate refractive index layer forming step, and then coating the curable resin composition for the anchor layer in the low refractive index layer forming step. The coating film of the curable resin composition for the high refractive index layer, the coating film of the curable resin composition for the middle refractive index layer, and the coating film of the curable resin composition for the low refractive index layer may be completely cured. In this case, the adhesion of the anchor layer, the high refractive index layer, the medium refractive index layer, and the low refractive index layer can be improved, and the scratch resistance and hardness can be further improved.

  What is necessary is just to adjust the irradiation amount of ionizing radiation in order to semi-harden the coating film of the curable resin composition for middle refractive index layers. In addition, about the irradiation amount of ionizing radiation, since it can be made the same as that of the said high refractive index layer, description here is abbreviate | omitted.

  In addition, since the other points of the medium refractive index layer were described in detail in the above “A. Antireflection laminated body”, description thereof is omitted here.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

[Example 1]
(Composition of curable resin composition A for anchor layer)
The following materials were stirred and mixed at room temperature to obtain an anchor layer curable resin composition A.
Anchor layer material Z7503 (n = 1.51, manufactured by JSR): 99% by mass
-Antioxidant Irganox 1010 (manufactured by BASF): 1% by mass
Z7503 made by JSR is an ultraviolet curable resin composition containing silica particles having an average particle diameter of 10 nm to 20 nm.

(Formation of antireflection layer)
As a transparent base material, a 0.7 mm thick tempered glass substrate (Asahi Glass Co., Ltd. Dragonrail) is used, and spin coating is performed on one surface with the curable resin composition A for anchor layer to a thickness of 3.0 μm. An anchor layer was formed by irradiating an exposure amount of 80 mJ using a high-pressure mercury lamp with an exposure illuminance of 80 mW in a nitrogen atmosphere. Next, a high refractive index layer having a thickness of 150 nm was formed on the anchor layer using KZ6661 (n = 1.60, manufactured by JSR) in the same process as the formation of the anchor layer. Subsequently, TU2205 (n = 1.35, manufactured by JSR Corporation) was spin-coated to a film thickness of 100 nm, irradiated with an exposure amount of 320 mJ using a high-pressure mercury lamp with an exposure illuminance of 80 mW in a nitrogen atmosphere, and at 280 ° C. Heat treatment was performed for 30 minutes to form a low refractive index layer, and an antireflection laminate was obtained.

[Comparative Example 1]
(Formation of antireflection layer)
As a transparent substrate, a tempered glass substrate having a thickness of 0.7 mm (Asahi Glass Co., Ltd. Dragonrail) is used, and Z7503 (n = 1.51, manufactured by JSR) is formed on one surface so that the film thickness becomes 3.0 μm. An anchor layer was formed by spin coating and irradiating an exposure dose of 320 mJ using a high-pressure mercury lamp with an exposure illuminance of 80 mW in a nitrogen atmosphere. Next, a high refractive index layer having a thickness of 150 nm was formed on the anchor layer using KZ6661 (n = 1.60, manufactured by JSR) in the same process as the formation of the anchor layer. Subsequently, TU2205 (n = 1.35, manufactured by JSR) was spin-coated so as to have a film thickness of 100 nm, and irradiated with an exposure amount of 320 mJ using a high-pressure mercury lamp with an exposure illuminance of 320 mW in a nitrogen atmosphere at 150 ° C. Heat treatment was performed for 30 minutes to form a low refractive index layer, and an antireflection laminate was obtained.

[Comparative Example 2]
An antireflection laminate was obtained in the same manner as in Comparative Example 1 except that the heat treatment temperature of the low refractive index layer was changed to 230 ° C.

[Comparative Example 3]
An antireflection laminate was obtained in the same manner as in Comparative Example 1, except that the exposure illuminance of the anchor layer and the high refractive index layer was 80 mJ, and the heat treatment temperature of the low refractive index layer was 230 ° C.

[Evaluation]
(Abrasion resistance)
Regarding the antireflection laminates obtained in Example 1 and Comparative Examples 1 to 3, the surface of the laminate was visually checked for the presence or absence of damage after 10 rounds of # 1000 steel wool were reciprocated under the conditions of each load. The maximum load at which there was no damage was shown as steel wool resistance in Table 1.

In Comparative Example 1 and Comparative Example 2, the anchor layer and the high refractive index layer are sufficiently cured, and after the low refractive index layer is cured, the heat treatment temperature condition is changed, so that the antireflection laminates have scratch resistance. evaluated.
As shown in Table 1, the steel wool resistance of Comparative Example 1 and Comparative Example 2 showed no scratches at a load of 500 g and a load of 800 g, and both showed scratch resistance such as no scratches at a load of 1000 g or less. It was found that the higher the treatment temperature, the better the scratch resistance.
On the other hand, in Comparative Example 3, the anchor layer and the high refractive index layer were not sufficiently cured, and the low refractive index layer was laminated in a semi-cured state, sufficiently cured, and then subjected to heat treatment. . As with Comparative Example 2, the heat treatment temperature was set higher than that of Comparative Example 1. As a result, the antireflection laminate of Comparative Example 3 had a steel wool resistance of 1200 g with no flaws and excellent scratch resistance. Indicated.
In Example 1, as in Comparative Example 3, the anchor layer and the high refractive index layer were only semi-cured and the low refractive index layer was sufficiently cured, and then heat treatment was performed at a high temperature. When the heat treatment temperature was set to a temperature higher than that of Comparative Example 3 (280 ° C.), the steel wool resistance was no scratch at a load of 1700 g, and the scratch resistance was further improved.
Therefore, the anchor layer and the high refractive index layer are not completely cured, but semi-cured, and after laminating the low refractive index layer, it is found that the scratch resistance is improved by sufficiently curing, and It was found that the scratch resistance can be further improved by performing the heat treatment after curing of each layer at a high temperature.
In addition, by adding an antioxidant to the anchor layer, even when heat treatment is performed at a high temperature, it is possible to suppress deterioration in optical characteristics such as reflectance of the antireflection laminate and quality deterioration such as yellowing. I also found that I can do it.

DESCRIPTION OF SYMBOLS 1 ... Antireflection laminated body 2 ... Transparent base material 3 ... Anchor layer 4 ... High refractive index layer 5 ... Low refractive index layer

Claims (4)

A transparent substrate;
An anchor layer formed on the transparent substrate and containing an antioxidant;
A high refractive index layer formed on the anchor layer;
A low refractive index layer formed on the high refractive index layer and having a refractive index lower than that of the high refractive index layer, and the anchor layer, the high refractive index layer, and the low refractive index layer are ionizing radiation curable resins. An antireflective laminate comprising:   The antireflection laminate according to claim 1, wherein the steel wool resistance determined by the steel wool resistance test is a flaw free at a load of 1000 g. An anchor layer forming step in which an anchor layer is formed by applying an curable resin composition for an anchor layer containing an antioxidant on a transparent substrate, and curing by irradiation with ionizing radiation;
A high refractive index layer forming step of applying a curable resin composition for a high refractive index layer on the anchor layer and curing the composition by irradiation with ionizing radiation; and
A low refractive index layer having a refractive index lower than that of the high refractive index layer is applied on the high refractive index layer by applying a curable resin composition for a low refractive index layer, cured by irradiation with ionizing radiation, and subjected to heat treatment. A method for producing an antireflection laminate, comprising: a step of forming a low refractive index layer.   In the anchor layer forming step, the coating film of the curable resin composition for the anchor layer is semi-cured, and in the high refractive index layer forming step, the coating film of the curable resin composition for the high refractive index layer is semi-cured, In the low refractive index layer forming step, the anchor layer curable resin composition coating film, the high refractive index layer curable resin composition coating film, and the low refractive index layer curable resin composition coating film The method for producing an antireflection laminate according to claim 3, wherein: is cured.