JP7428468B2 - Antireflection film, antireflection film manufacturing method, optical member, and image display device - Google Patents

Description

The present invention relates to an antireflection film, a method for manufacturing an antireflection film, an optical member, and an image display device.

The outermost surface of image display devices such as liquid crystal displays (LCDs), plasma display panels (PDPs), and electroluminescent displays (ELDs) is equipped with a protective layer to prevent contrast degradation due to reflection of external light and image reflection. Glare films, anti-reflection films, etc. are used. There are many documents describing antireflection films, such as Patent Documents 1 to 3.

Japanese Patent Application Publication No. 2004-34002 Japanese Patent Application Publication No. 2003-315505 Japanese Patent Application Publication No. 2003-126768

From the viewpoint of good optical properties, the antireflection film needs to be resistant to scratches, that is, to have excellent scratch resistance. However, the surface of the antireflection film is easily damaged, and it is difficult to obtain excellent scratch resistance.

Therefore, an object of the present invention is to provide an antireflection film with excellent scratch resistance. Furthermore, the present invention aims to provide a method for manufacturing the antireflection film, an optical member using the antireflection film, and an image display device using the antireflection film.

In order to achieve the above object, the antireflection film of the present invention has the following features:
Including a light-transmissive base material (A), a hard coat layer (B), and an antireflection layer (C),
The hard coat layer (B) and the antireflection layer (C) are laminated in the above order on at least one surface of the light transmitting base material (A),
The elements constituting the antireflection layer (C) include at least carbon and fluorine,
The number of atoms of the antireflection layer (C) measured by X-ray photoelectric spectroscopy satisfies the following formulas (1) and (2) on the surface opposite to the hard coat layer (B), and When the depth is in the range of 15 to 30 nm, the following formula (3) is satisfied.

7≦[(n _F /n _total )×100]≦27 (1)
30≦[(n _c /n _total )×100]≦41 (2)
[( _nF / _ntotal )×100]≦0.5 (3)

In the above formulas (1) to (3), n _total is the total number of atoms of carbon, nitrogen, oxygen, silicon, and fluorine, n _F is the number of fluorine atoms, and n _c is the number of carbon atoms. be.

The method for producing an antireflection film of the present invention includes adding the antireflection layer (C) on the hard coat layer (B) in a laminate of the light-transmitting substrate (A) and the hard coat layer (B). including a step of forming an antireflection layer (C) to satisfy the above formulas (1) to (3),
The antireflection layer (C) forming step includes a coating step of applying an antireflection layer forming coating solution on the hard coat layer (B), and a coating step of coating the applied antireflection layer forming coating solution. A coating film forming step of drying to form a coating film,
The method for producing an antireflection film of the present invention is characterized in that the antireflection layer forming coating liquid contains a resin, a fluorine element-containing additive, and a diluting solvent.

The optical member of the present invention is an optical member containing the antireflection film of the present invention.

The image display device of the present invention is an image display device including the antireflection film of the present invention or the optical member of the present invention.

According to the present invention, an antireflection film with excellent scratch resistance can be provided. Further, according to the present invention, it is possible to provide a method for manufacturing the antireflection film, an optical member using the antireflection film, and an image display device using the antireflection film.

FIG. 1 is a cross-sectional view illustrating the structure of the antireflection film of the present invention. FIG. 2 is a cross-sectional view showing the structure of the antireflection layer in the antireflection film of FIG. 1.

Next, the present invention will be explained in more detail by giving examples. However, the present invention is not limited in any way by the following explanation.

In the antireflection film of the present invention, the hard coat layer (B) may be an antiglare hard coat layer, for example.

In the antireflection film of the present invention, for example, the antireflection layer (C) may include hollow particles and solid particles. The hollow particles and the solid particles may be, for example, silica particles.

In the method for producing an antireflection film of the present invention, for example, the antireflection layer (C) forming step may further include a curing step of curing the coating film.

In the method for producing an antireflection film of the present invention, for example, the diluting solvent may contain MIBK (methyl isobutyl ketone) and PMA (propylene glycol monomethyl ether acetate). Further, for example, the diluent solvent may further contain TBA (tertiary butyl alcohol).

In the method for producing an antireflection film of the present invention, for example, the antireflection film is an antireflection film containing the hollow particles and the solid particles, and the coating liquid for forming an antireflection layer further includes the hollow particles. particles and the solid particles described above.

The optical member of the present invention may be, for example, a polarizing plate.

[1. Anti-reflection film]
As mentioned above, the antireflection film of the present invention has the following features:
Including a light-transmissive base material (A), a hard coat layer (B), and an antireflection layer (C),
The hard coat layer (B) and the antireflection layer (C) are laminated in the above order on at least one surface of the light transmitting base material (A),
The elements constituting the antireflection layer (C) include carbon and fluorine,
The number of atoms of the antireflection layer (C) measured by X-ray photoelectric spectroscopy satisfies the following formulas (1) and (2) on the surface opposite to the hard coat layer (B), and When the depth is in the range of 15 to 30 nm, the following formula (3) is satisfied.

7≦[(n _F /n _total )×100]≦27 (1)
30≦[(n _c /n _total )×100]≦41 (2)
[( _nF / _ntotal )×100]≦0.5 (3)

In the above formulas (1) to (3), n _total is the total number of atoms of carbon, nitrogen, oxygen, silicon, and fluorine, n _F is the number of fluorine atoms, and n _c is the number of carbon atoms. be.

Note that X-ray photoelectron spectroscopy is also referred to as XPS (X-ray Photoelectron Spectroscopy) or ESCA (Electron Spectroscopy for Chemical Analysis).

The antireflection film of the present invention has excellent scratch resistance because the antireflection layer (C) satisfies all of the formulas (1) to (3).

As elements contained in the antireflection layer (C), carbon and fluorine are essential, but nitrogen, oxygen, and silicon are optional. That is, the antireflection layer (C) may or may not contain each of nitrogen, oxygen, and silicon as elements. Further, the antireflection layer (C) may or may not contain elements other than carbon, nitrogen, oxygen, silicon, and fluorine.

The formula (1) represents carbon and nitrogen on the surface of the antireflection layer (C) opposite to the hard coat layer (B) (hereinafter sometimes referred to as the "outmost surface" or simply "the surface"). , the total number of oxygen, silicon and fluorine atoms is 100%, meaning that the number of fluorine atoms is 7 to 27%. When the number of fluorine atoms on the outermost surface is less than 7%, the antireflection layer (C) has a decreased slipperiness and therefore abrasion resistance. When the number of fluorine atoms on the outermost surface exceeds 27%, the slipperiness of the antireflection layer (C) increases, but the strength decreases and the scratch resistance also decreases. The number of fluorine atoms on the outermost surface is, for example, 10% or more, 13% or more, 14% or more, 15% or more, or 16% or more, taking the total number of carbon, nitrogen, oxygen, silicon, and fluorine atoms as 100%. It may be 25% or less, 24% or less, 23% or less, 22% or less, or 21% or less.

The formula (2) means that the number of carbon atoms is 30 to 41%, with the total number of carbon, nitrogen, oxygen, silicon, and fluorine atoms on the outermost surface of the antireflection layer (C) being 100%. do. When the number of carbon atoms is less than 30%, the strength of the antireflection layer (C) decreases, and the scratch resistance also decreases. When the number of carbon atoms exceeds 41%, the antireflection layer (C) has a decreased slipperiness and therefore abrasion resistance. The number of carbon atoms on the outermost surface is, for example, 31% or more, 32% or more, 33% or more, 34% or more, or 35% or more, taking the total number of carbon, nitrogen, oxygen, silicon, and fluorine atoms as 100%. It may be 39% or less, 38% or less, 37% or less, or 36% or less.

The formula (3) is based on fluorine atoms when the depth from the outermost surface of the antireflection layer (C) is in the range of 15 to 30 nm, and the total number of carbon, nitrogen, oxygen, silicon, and fluorine atoms is 100%. This means that the number is 0.5% or less. When the number of fluorine atoms exceeds 0.5%, the strength of the antireflection layer (C) decreases, and the scratch resistance also decreases. The number of fluorine atoms in the depth range of 15 to 30 nm from the outermost surface is, for example, 0.45% or less, 0.40%, assuming the total number of carbon, nitrogen, oxygen, silicon, and fluorine atoms as 100%. Below, it may be 0.35% or less, 0.30% or less, or 0.25% or less. The lower limit of the number of fluorine atoms is not particularly limited, but may be, for example, 0 or below the detection limit by X-ray photoelectric spectroscopy.

In the antireflection film of the present invention, the antireflection layer (C) is not particularly limited except that it satisfies the above formulas (1) to (3). The light-transmitting base material (A) and the hard coat layer (B) are also not particularly limited, and may be similar to or similar to the light-transmitting base material and hard coat layer used in general optical films, for example. You can. Further, the hard coat layer (B) may be, for example, a hard coat layer that does not have anti-glare properties, or may be an anti-glare hard coat layer. The hard coat layer that does not have anti-glare properties may have high transparency and low haze value, but is not limited thereto. Further, the anti-glare hard coat layer may have a high haze value, for example, but is not limited thereto.

An example of the structure of the antireflection film of the present invention is shown in the cross-sectional view of FIG. Further, the cross-sectional view of FIG. 2 shows the structure of the antireflection layer (C) in the antireflection film of FIG. 1. However, these are just examples, and the antireflection film of the present invention is not limited thereto.

As shown in FIG. 1, this antireflection film 10 has a hard coat layer (B) 12 and an antireflection layer (C) 13 laminated in the above order on one side of a light-transmitting substrate (A) 11. ing. The hard coat layer (B) 12 includes particles 12b in a resin layer 12a. On the surface of the hard coat layer (B) 12 opposite to the light-transmitting substrate (A) 11, irregularities are formed, and an antireflection layer (C) 13 is formed thereon. The antireflection layer (C) 13 satisfies the above formulas (1) and (2) at the surface (outermost surface) 13X opposite to the hard coat layer (B) 12, and has a depth of 15 to 30 nm from the surface 13X. , the above formula (3) is satisfied.

Further, as shown in FIG. 2, the antireflection layer (C) 13 includes hollow particles 13b and solid particles 13c in a resin layer 13a. As described above, the antireflection layer (C) 13 is not particularly limited as long as it satisfies the above formulas (1) to (3), but preferably includes hollow particles and solid particles. The details will be described later.

Hereinafter, each of the light-transmitting substrate (A), the hard coat layer (B), and the antireflection layer (C) will be further explained by giving examples. In addition, although the case where the said hard coat layer (B) is an anti-glare hard coat layer is mainly demonstrated below, as mentioned above, this invention is not limited to this.

The light-transmitting substrate (A) is not particularly limited, and examples thereof include transparent plastic film substrates and the like. The transparent plastic film substrate is not particularly limited, but preferably has excellent visible light transmittance (preferably 90% or more light transmittance) and excellent transparency (preferably haze value 1% or less). , for example, the transparent plastic film base material described in JP-A-2008-90263. As the transparent plastic film base material, one having optically low birefringence is suitably used. The antireflection film of the present invention can also be used, for example, as a protective film in a polarizing plate. In this case, the transparent plastic film base material may be triacetyl cellulose (TAC), polycarbonate, acrylic polymer, cyclic A film formed from polyolefin or the like having a norbornene structure is preferred. Furthermore, in the present invention, as described later, the transparent plastic film base material may be a polarizer itself. With such a configuration, a protective layer made of TAC or the like is not required and the structure of the polarizing plate can be simplified, thereby reducing the number of manufacturing steps of the polarizing plate or the image display device and improving production efficiency. Moreover, with such a configuration, the polarizing plate can be made thinner. In addition, when the said transparent plastic film base material is a polarizer, the said hard coat layer (B) and the said antireflection layer (C) will play a role as a protective layer. Further, with such a configuration, the antireflection film also functions as a cover plate when it is attached to the surface of the liquid crystal cell, for example.

In the present invention, the thickness of the light-transmitting substrate (A) is not particularly limited, but in consideration of workability such as strength and handleability, and thin layer property, the thickness is, for example, 10 to 500 μm, 20 to 300 μm. , or in the range of 30 to 200 μm. The refractive index of the light-transmitting substrate (A) is not particularly limited. The refractive index is, for example, in the range of 1.30 to 1.80 or 1.40 to 1.70.

In the antireflection film of the present invention, for example, the resin contained in the light-transmitting substrate (A) may include an acrylic resin.

In the antireflection film of the present invention, the light-transmitting substrate (A) may be an acrylic film, for example.

In the antireflection film of the present invention, for example, the antiglare hard coat layer (B) may contain a resin and a filler. The filler may include at least one of particles and a thixotropic agent.

In the antireflection film of the present invention, for example, the resin contained in the antiglare hard coat layer (B) may include an acrylate resin (also referred to as acrylic resin).

In the antireflection film of the present invention, for example, the resin contained in the antiglare hard coat layer (B) may contain a urethane acrylate resin.

In the antireflection film of the present invention, for example, the resin contained in the antiglare hard coat layer (B) may be a copolymer of a curable urethane acrylate resin and a polyfunctional acrylate.

In the antireflection film of the present invention, for example, the antiglare hard coat layer (B) is formed using an antiglare hard coat layer forming material containing a resin and a filler, and the antiglare hard coat layer (B) is formed using an antiglare hard coat layer forming material containing a resin and a filler. (B) may have an agglomerated part that forms a convex part on the surface of the anti-glare hard coat layer (B) by aggregating the filler. Further, in the agglomerated portion forming the convex portion, a plurality of the fillers may be present in a state in which they are gathered in one direction in the surface direction of the anti-glare hard coat layer (B). In the image display device of the present invention, the antireflection film of the present invention may be arranged such that, for example, one direction in which the plurality of fillers are gathered coincides with the long side direction of the black matrix pattern.

In the antireflection film of the present invention, the thixotropy imparting agent may be, for example, at least one selected from the group consisting of organic clay, oxidized polyolefin, and modified urea.

In the antireflection film of the present invention, for example, the thixotropy imparting agent is contained in a range of 0.2 to 5 parts by weight based on 100 parts by weight (mass) of the resin of the antiglare hard coat layer (B). You can.

In the antireflection film of the present invention, the particles are contained in an amount of, for example, 0.2 to 12 parts by weight or 0.5 to 12 parts by weight, based on 100 parts by weight of the resin of the antiglare hard coat layer (B). may be included.

In the method for producing an antireflection film of the present invention, the surface shape of the antireflection film is further adjusted by adjusting the number of parts by weight of the particles based on 100 parts by weight of the resin in the antiglare hard coat layer forming material. You may.

By having the agglomerated portion where particles are aggregated, for example, the uneven shape of the antireflection film becomes gentle, and the average distance between the unevenness Sm (mm) on the surface of the antiglare hard coat layer (B) increases. An antireflection film having such a surface shape can effectively prevent reflections of fluorescent lights and the like. However, the antireflection film of the present invention is not limited to this.

The anti-glare hard coat layer (B) is formed, for example, by applying a coating liquid containing the resin, the filler, and a solvent to at least one surface of the light-transmitting substrate (A), as described below. It is formed by forming a coating film, and then removing the solvent from the coating film. Examples of the resin include thermosetting resins and ionizing radiation-curable resins that are cured by ultraviolet light or light. As the resin, it is also possible to use commercially available thermosetting resins, ultraviolet curable resins, and the like.

As the thermosetting resin or the ultraviolet curable resin, for example, a curable compound having at least one of an acrylate group and a methacrylate group that is cured by heat, light (such as ultraviolet rays), or electron beam, etc. can be used, for example, Silicone resins, polyester resins, polyether resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, oligomers or prepolymers such as acrylates and methacrylates of polyfunctional compounds such as polyhydric alcohols, etc. can give. These may be used alone or in combination of two or more.

For example, a reactive diluent having at least one of an acrylate group and a methacrylate group can also be used in the resin. The reactive diluent can be, for example, the reactive diluent described in JP-A No. 2008-88309, and includes, for example, monofunctional acrylate, monofunctional methacrylate, polyfunctional acrylate, polyfunctional methacrylate, and the like. As the reactive diluent, trifunctional or higher functional acrylates or trifunctional or higher functional methacrylates are preferred. This is because the hardness of the anti-glare hard coat layer (B) can be made excellent. Examples of the reactive diluent include butanediol glycerol ether diacrylate, isocyanuric acid acrylate, isocyanuric acid methacrylate, and the like. These may be used alone or in combination of two or more.

The particles for forming the anti-glare hard coat layer (B) impart anti-glare properties by making the surface of the anti-glare hard coat layer (B) uneven and provide anti-glare properties. Its main function is to control the haze value of the coating layer (B). The haze value of the antiglare hard coat layer (B) can be designed by controlling the refractive index difference between the particles and the resin. Examples of the particles include inorganic particles and organic particles. The inorganic particles are not particularly limited, and include, for example, silicon oxide particles, titanium oxide particles, aluminum oxide particles, zinc oxide particles, tin oxide particles, calcium carbonate particles, barium sulfate particles, talc particles, kaolin particles, calcium sulfate particles, etc. can be given. The organic particles are not particularly limited, and include, for example, polymethyl methacrylate resin powder (PMMA particles), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin. Examples include resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, polyfluoroethylene resin powder, and the like. One type of these inorganic particles and organic particles may be used alone, or two or more types may be used in combination.

The particle size (D) (weight average particle size) of the particles is not particularly limited, but is, for example, within the range of 2.5 to 10 μm. By setting the weight average particle diameter of the particles within the above range, it is possible to obtain, for example, an antireflection film that has better antiglare properties and can prevent white blurring. The weight average particle diameter of the particles is more preferably within the range of 3 to 7 μm. Note that the weight average particle diameter of the particles can be measured, for example, by the Coulter counting method. For example, using a particle size distribution measuring device (trade name: Coulter Multisizer, manufactured by Beckman Coulter) that uses the pore electrical resistance method, an electrolyte solution corresponding to the volume of the particles when the particles pass through the pores is measured. By measuring electrical resistance, the number and volume of the particles are measured, and the weight average particle diameter is calculated.

The shape of the particles is not particularly limited, and may be, for example, approximately spherical in the form of beads, or irregularly shaped such as powder, but is preferably approximately spherical, and more preferably has an aspect ratio. The particles are approximately spherical particles with a ratio of 1.5 or less, and most preferably spherical particles.

The proportion of the particles in the anti-glare hard coat layer (B) is, for example, 0.2 to 12 parts by weight, 0.5 to 12 parts by weight, or 1 to 7 parts by weight based on 100 parts by weight of the resin. range. By setting it as the said range, the said aggregation part can be formed suitably, and, for example, it can be made into the antireflection film which is more excellent in anti-glare property, and can prevent white blurring.

In the antiglare hard coat layer (B), the filler may be particles and a thixotropy imparting agent. The thixotropy-imparting agent may be contained alone, or the particles may further contain the thixotropy-imparting agent in addition to the particles. By including the thixotropy agent, the aggregation state of the particles can be easily controlled. Examples of the thixotropy-imparting agent include organic clay, oxidized polyolefin, and modified urea.

It is preferable that the organic clay is a layered clay that has been subjected to an organic treatment in order to improve its affinity with the resin. The organic clay may be prepared in-house or a commercially available product may be used. Examples of the commercially available products include Lucentite SAN, Lucentite STN, Lucentite SEN, Lucentite SPN, Somasif ME-100, Somasif MAE, Somasif MTE, Somasif MEE, Somasif MPE (trade names, all manufactured by Co-op Chemical Co., Ltd.) ); Esben, Esben C, Esben E, Esben W, Esben P, Esben WX, Esben N-400, Esben NX, Esben NX80, Esben NO12S, Esben NEZ, Esben NO12, Esben NE, Esben NZ, Esben NZ70, Olga Knight, Organite D, Organite T (trade names, all manufactured by Hojun Co., Ltd.); Kunipia F, Kunipia G, Kunipia G4 (trade names, all manufactured by Kunimine Industries Co., Ltd.); Thixogel VZ, Clayton HT, Clayton 40 (Product names, all manufactured by Rockwood Additives).

The oxidized polyolefin may be prepared in-house or a commercially available product may be used. Examples of the commercially available products include Disparon 4200-20 (trade name, manufactured by Kusumoto Kasei Co., Ltd.), Fluonon SA300 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

The modified urea is a reaction product of an isocyanate monomer or its adduct and an organic amine. The modified urea may be prepared in-house or a commercially available product may be used. Examples of the commercially available products include BYK410 (manufactured by Big Chemie).

The thixotropy imparting agent may be used alone or in combination of two or more.

The proportion of the thixotropy imparting agent in the anti-glare hard coat layer (B) is preferably in the range of 0.2 to 5 parts by weight, more preferably 0.4 to 4 parts by weight, based on 100 parts by weight of the resin. is within the range of

The thickness (d) of the antiglare hard coat layer (B) is not particularly limited, but is preferably within the range of 3 to 12 μm. By setting the thickness (d) of the anti-glare hard coat layer (B) within the above range, it is possible to prevent, for example, the occurrence of curling in the anti-reflection film, thereby reducing the problem of reduced productivity such as poor conveyance. can be avoided. Further, when the thickness (d) is within the above range, the weight average particle diameter (D) of the particles is preferably within the range of 2.5 to 10 μm, as described above. Since the thickness (d) of the anti-glare hard coat layer (B) and the weight average particle diameter (D) of the particles are in the above-mentioned combination, an anti-reflection film with excellent anti-glare properties can be obtained. can. The thickness (d) of the antiglare hard coat layer (B) is more preferably in the range of 3 to 8 μm.

The relationship between the thickness (d) of the anti-glare hard coat layer (B) and the weight average particle diameter (D) of the particles is preferably within the range of 0.3≦D/d≦0.9. . By having such a relationship, it is possible to obtain an antireflection film that has better antiglare properties, can prevent white blurring, and has no defects in appearance.

In the antireflection film of the present invention, for example, as described above, the antiglare hard coat layer (B) has a convex shape on the surface of the antiglare hard coat layer (B) due to the aggregation of the filler. The filler has an agglomerated part forming a convex part, and in the agglomerated part forming the convex part, a plurality of the fillers are gathered in one direction in the surface direction of the anti-glare hard coat layer (B). May exist. As a result, the convex portion has a gentle shape with anisotropy. The antireflection film can prevent reflections of fluorescent lamps and the like by having the convex portion having such a shape. However, the antireflection film of the present invention is not limited to this.

The surface shape of the anti-glare hard coat layer (B) can be arbitrarily designed by controlling the aggregation state of the filler contained in the anti-glare hard coat layer forming material. The aggregation state of the filler can be controlled by, for example, the material of the filler (for example, the chemical modification state of the particle surface, the affinity for solvents and resins, etc.), the type and combination of resin (binder) or solvent, and the like. Furthermore, the thixotropy-imparting agent allows precise control of the agglomeration state of the particles. As a result, in the present invention, it is possible to control (adjust) the surface shape of the antireflection film over a wide range. For example, the aggregation state of the filler can be made as described above, and the convex shape can be adjusted. The portion can have a gentle shape. Furthermore, as described above, by adjusting the number of parts by weight of the particles based on 100 parts by weight of the resin in the anti-glare hard coat layer forming material, the surface shape of the anti-reflection film can be controlled over a wider range ( adjustment) is also possible.

In addition, in the antireflection film of the present invention, the convex portions may have a gentle shape to prevent the occurrence of protrusions on the surface of the anti-glare hard coat layer (B) that would cause defects in appearance. However, it is not limited to this. Further, in the antireflection film of the present invention, some of the particles may be present, for example, at positions directly or indirectly overlapping the antiglare hard coat layer (B) in the thickness direction.

The antireflection film of the present invention may have a haze value within the range of 0 to 10%, for example. The haze value is the haze value (cloudiness) of the entire antireflection film according to JIS K 7136 (2000 edition). The haze value is more preferably in the range of 0 to 5%, and even more preferably in the range of 0 to 3%. In order to keep the haze value within the above range, it is preferable to select the particles and the resin so that the difference in refractive index between the particles and the resin is in the range of 0.001 to 0.02. When the haze value is within the above range, a clear image can be obtained and the contrast in a dark place can be improved.

As described above, the antireflection layer (C) is not particularly limited except that it satisfies the above formulas (1) to (3). As shown in the above formulas (1) to (3), the antireflection layer (C) necessarily contains carbon and fluorine as elements. Further, as shown by the above formulas (1) and (3), fluorine exists at a certain ratio on the outermost surface of the antireflection layer (C), and fluorine does not exist within a range of 15 to 30 nm from the outermost surface. , very few. In order to satisfy these conditions, the antireflection layer (C) may be manufactured by adding a fluorine element-containing additive to the resin, for example. Further, the antireflection layer (C) may contain solid particles and hollow particles in the resin, for example, as described above. The material for forming the antireflection layer (C) and the method for forming the antireflection layer (C) will be described in detail later.

For example, when an antireflection film is attached to an image display device, one of the factors that reduces the visibility of images is the reflection of light at the interface between air and the antiglare hard coat layer (B). The antireflection layer (C) in the antireflection film of the present invention reduces surface reflection. The anti-glare hard coat layer (B) and the anti-reflection layer (C) may be formed only on one side of the light-transmitting substrate (A), but they may also be formed on both sides. good. Moreover, the antiglare hard coat layer (B) and the antireflection layer (C) may each have a multilayer structure in which two or more layers are laminated.

In the present invention, the antireflection layer (C) may be an optical thin film whose thickness and refractive index are strictly controlled, or a laminate of two or more optical thin films. The antireflection layer (C) exhibits an antireflection function by canceling out the reversed phases of incident light and reflected light using light interference effects. The wavelength range of visible light that exhibits the antireflection function is, for example, 380 to 780 nm, and the wavelength range with particularly high visibility is 450 to 650 nm, and the reflectance at the center wavelength of 550 nm is minimized. The antireflection layer (C) may be designed as follows.

In addition, for example, in order to prevent the adhesion of contaminants and to improve the ease of removing the adhered contaminants, a contamination prevention layer formed from a fluorine group-containing silane compound or a fluorine group-containing organic compound may be added to the above. It may be laminated on the antireflection layer (C).

[2. Manufacturing method of anti-reflection film]
The method for producing the antireflection film of the present invention is not particularly limited and may be produced by any method, but it is preferably produced by the method for producing the antireflection film of the present invention.

The method for manufacturing the antireflection film can be performed, for example, as follows.

First, a laminate of the light-transmitting substrate (A) and the hard coat layer (B) is prepared. The method for producing the laminate is not particularly limited, but for example, the coating liquid for forming the anti-glare hard coat layer (B) is coated on the light-transmitting substrate (A), and further, You may manufacture by drying the said coating liquid. Further, for example, the material forming the anti-glare hard coat layer (B) may be further hardened. The curing can be performed, for example, after the drying, but is not limited thereto. The curing can be performed by heating, light irradiation, etc., for example. The light is not particularly limited, and may be, for example, ultraviolet light. The light source for the light irradiation is also not particularly limited, and may be, for example, a high-pressure mercury lamp.

The coating liquid may be, for example, an anti-glare hard coat layer forming material (coating liquid) containing the resin, the particles, the thixotropy imparting agent, and a solvent.

The coating liquid preferably exhibits thixotropic properties, and preferably has a Ti value defined by the following formula in the range of 1.3 to 3.5, more preferably 1.4 to 3. 2, more preferably 1.5 to 3.

Ti value = β1/β2

In the above formula, β1 is the viscosity measured at a shear rate of 20 (1/s) using Rheostress RS6000 manufactured by HAAKE, and β2 is the viscosity measured at a shear rate of 200 (1/s) using Rheostress RS6000 manufactured by HAAKE. This is the viscosity measured under the following conditions.

If the Ti value is 1.3 or more, problems such as appearance defects and deterioration of anti-glare properties and white blurring properties are unlikely to occur. Further, if the Ti value is 3.5 or less, problems such as the particles not agglomerating and becoming dispersed are less likely to occur.

Further, the coating liquid may or may not contain a thixotropy-imparting agent, but it is preferable to include a thixotropy-imparting agent because it tends to exhibit thixotropy. Further, as described above, when the coating liquid contains the thixotropy imparting agent, an effect of preventing sedimentation of the particles (thixotropic effect) can be obtained. Furthermore, by shear aggregation of the thixotropy imparting agent itself, it is also possible to freely control the surface shape of the antireflection film over a wider range.

The solvent is not particularly limited, and various solvents can be used, and one type may be used alone or two or more types may be used in combination. Depending on the composition of the resin, the types and contents of the particles and the thixotropy-imparting agent, there is an optimal solvent type and solvent ratio in order to obtain the antireflection film of the present invention. Examples of the solvent include, but are not limited to, alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and 2-methoxyethanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone; methyl acetate, ethyl acetate. , esters such as butyl acetate; ethers such as diisopropyl ether and propylene glycol monomethyl ether; glycols such as ethylene glycol and propylene glycol; cellosolves such as ethyl cellosolve and butyl cellosolve; aliphatic hydrocarbons such as hexane, heptane, and octane. Aromatic hydrocarbons such as benzene, toluene, xylene, etc. Further, for example, the solvent may include a hydrocarbon solvent and a ketone solvent. The hydrocarbon solvent may be, for example, an aromatic hydrocarbon. The aromatic hydrocarbon may be, for example, at least one selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and benzene. The ketone solvent may be, for example, cyclopentanone and at least one selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, isophorone, and acetophenone. The solvent may be, for example, a mixture of the hydrocarbon solvent and the ketone solvent at a mass ratio of 90:10 to 10:90. The mass ratio of the hydrocarbon solvent to the ketone solvent may be, for example, 80:20 to 20:80, 70:30 to 30:70, or 40:60 to 60:40.

In addition, by appropriately selecting the solvent, the antiglare hard coat layer forming material (coating liquid) can exhibit good thixotropy when it contains a thixotropy imparting agent. For example, when using organoclay, toluene and xylene can be preferably used alone or in combination; for example, when using oxidized polyolefin, methyl ethyl ketone, ethyl acetate, propylene glycol monomethyl ether can be preferably used alone. For example, when using modified urea, butyl acetate and methyl isobutyl ketone can be suitably used alone or in combination.

Various leveling agents can be added to the anti-glare hard coat layer forming material. As the leveling agent, for example, a fluorine-based or silicone-based leveling agent can be used for the purpose of preventing uneven coating (uniform coating surface). In the present invention, when antifouling properties are required on the surface of the anti-glare hard coat layer (B), or when the layer containing the anti-reflection layer (low refractive index layer) or interlayer filler is An appropriate leveling agent can be selected depending on the case where the leveling agent is formed on the coating layer (B). In the present invention, for example, by including the thixotropy imparting agent, the coating liquid can exhibit thixotropy, so that coating unevenness is less likely to occur. In this case, for example, there is an advantage that the options for the leveling agent can be expanded.

The blending amount of the leveling agent is, for example, 5 parts by weight or less, preferably in the range of 0.01 to 5 parts by weight, based on 100 parts by weight of the resin.

The anti-glare hard coat layer forming material may contain pigments, fillers, dispersants, plasticizers, ultraviolet absorbers, surfactants, antifouling agents, and antioxidants, as necessary, to the extent that performance is not impaired. etc. may be added. These additives may be used alone or in combination of two or more.

For the material for forming the anti-glare hard coat layer, a conventionally known photopolymerization initiator as described in JP-A-2008-88309, for example, can be used.

Examples of the method for forming a coating film by coating the coating liquid on the light-transmitting substrate (A) include fountain coating, die coating, spin coating, spray coating, and gravure coating. Coating methods such as , roll coating, bar coating, etc. can be used.

Next, as described above, the coating film is dried and cured to form an antiglare hard coat layer (B). The drying may be, for example, natural drying, air drying by blowing wind, heat drying, or a combination of these methods.

The drying temperature of the coating liquid for forming the antiglare hard coat layer (B) may be, for example, in the range of 30 to 200°C. The drying temperature may be, for example, 40°C or higher, 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, 90°C or higher, or 100°C or higher, 190°C or lower, 180°C or lower, or 170°C or lower. It may be below 160°C, below 150°C, below 140°C, below 135°C, below 130°C, below 120°C, or below 110°C. The drying time is not particularly limited, but may be, for example, 30 seconds or more, 40 seconds or more, 50 seconds or more, or 60 seconds or more, and 150 seconds or less, 130 seconds or less, 110 seconds or less, or 90 seconds or less. You can.

The means for curing the coating film is not particularly limited, but ultraviolet curing is preferred. The irradiation amount of the energy ray source is preferably 50 to 500 mJ/cm ² as a cumulative exposure amount at an ultraviolet wavelength of 365 nm. When the irradiation amount is 50 mJ/cm ² or more, curing is likely to proceed sufficiently, and the hardness of the formed anti-glare hard coat layer (B) is likely to be high. Moreover, if it is 500 mJ/cm ² or less, coloring of the anti-glare hard coat layer (B) to be formed can be prevented.

In the manner described above, a laminate of the light-transmitting substrate (A) and the hard coat layer (B) can be manufactured. Next, an antireflection layer (C) forming step is performed to form the antireflection layer (C) on the hard coat layer (B) in the laminate.

First, an antireflection layer forming coating liquid for forming the antireflection layer (C) is prepared. The coating liquid for forming an antireflection layer may contain, for example, a resin, a fluorine element-containing additive, hollow particles, solid particles, a diluent solvent, etc., and can be produced, for example, by mixing these.

Examples of the resin include thermosetting resins and ionizing radiation-curable resins that are cured by ultraviolet light or light. As the resin, it is also possible to use commercially available thermosetting resins, ultraviolet curable resins, and the like.

As the thermosetting resin or the ultraviolet curable resin, for example, a curable compound having at least one of an acrylate group and a methacrylate group that is cured by heat, light (such as ultraviolet rays), or electron beam, etc. can be used, for example, Silicone resins, polyester resins, polyether resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, oligomers or prepolymers such as acrylates and methacrylates of polyfunctional compounds such as polyhydric alcohols, etc. can give. These may be used alone or in combination of two or more.

For example, a reactive diluent having at least one of an acrylate group and a methacrylate group can also be used in the resin. The reactive diluent can be, for example, the reactive diluent described in JP-A No. 2008-88309, and includes, for example, monofunctional acrylate, monofunctional methacrylate, polyfunctional acrylate, polyfunctional methacrylate, and the like. As the reactive diluent, trifunctional or higher functional acrylates or trifunctional or higher functional methacrylates are preferred. This is because the hardness of the anti-glare hard coat layer (B) can be made excellent. Examples of the reactive diluent include butanediol glycerol ether diacrylate, isocyanuric acid acrylate, isocyanuric acid methacrylate, and the like. These may be used alone or in combination of two or more. The weight average molecular weight of the resin before curing may be, for example, 100 or more, 300 or more, 500 or more, 1,000 or more, or 2,000 or more, and 100,000 or less, 70,000 or less, 50 or more. ,000 or less, 30,000 or less, or 10,000 or less. If the weight average molecular weight before curing is high, the hardness decreases, but cracking tends to be less likely to occur when bent. On the other hand, if the weight average molecular weight before curing is low, the intermolecular crosslink density tends to improve and the hardness tends to increase.

For example, a curing agent may be added to cure the curable resin. The curing agent is not particularly limited, and for example, known polymerization initiators (eg, thermal polymerization initiators, photopolymerization initiators, etc.) can be used as appropriate. The amount of the curing agent added is not particularly limited, but for example, 0.5 parts by weight or more, 1.0 parts by weight or more, 1.5 parts by weight, based on 100 parts by weight of the resin in the coating liquid for forming an antireflection layer. It may be at least 15 parts by weight, at least 13 parts by weight, at most 10 parts by weight, at most 7 parts by weight, or at most 5 parts by weight. There may be.

The fluorine element-containing additive is not particularly limited, but may be, for example, an organic compound or an inorganic compound containing fluorine in its molecule. The organic compound is not particularly limited, and examples thereof include fluorine-containing antifouling coating agents, fluorine-containing acrylic compounds, fluorine- and silicon-containing acrylic compounds, and the like. Specific examples of the organic compound include "KY-1203" (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., "Megafac" (trade name) manufactured by 100DIC Corporation, and the like. The inorganic compound is also not particularly limited. The amount of the fluorine element-containing additive added is not particularly limited, but for example, the weight of the fluorine element in the solid content is, for example, relative to the weight of the entire solid content in the coating liquid for forming an antireflection layer. It may be 0.05% by weight or more, 0.1% by weight or more, 0.15% by weight or more, 0.20% by weight or more, or 0.25% by weight or more, and 20% by weight or less, 15% by weight or less , 10% by weight or less, 5% by weight or less, or 3% by weight or less. Further, for example, the weight of the fluorine element-containing additive is 0.05% by weight or more, 0.1% by weight or more, 0. .15% by weight or more, 0.20% by weight or more, or 0.25% by weight or more, and 20% by weight or less, 15% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight. It may be the following. From the viewpoint of satisfying the above formulas (1) and (3), it is preferable that the amount of the fluorine element-containing additive added is neither too large nor too small.

The hollow particles are not particularly limited, and may be, for example, silica particles, acrylic particles, acrylic-styrene copolymer particles, or the like. Examples of the silica particles include products such as "Surulia 5320" and "Surulia 4320" manufactured by JGC Catalysts & Chemicals Co., Ltd. The weight average particle diameter of the hollow particles is not particularly limited, but may be, for example, 30 nm or more, 40 nm or more, 50 nm or more, 60 nm or more, or 70 nm or more, 150 nm or less, 140 nm or less, 130 nm or less, 120 nm or less, Or it may be 110 nm or less. The shape of the hollow particles is not particularly limited, and may be, for example, approximately spherical in the shape of a bead, or irregularly shaped such as powder, but is preferably approximately spherical, and more preferably, The particles are approximately spherical particles with an aspect ratio of 1.5 or less, and most preferably spherical particles. By adding the hollow particles, it is possible to achieve, for example, a low refractive index and good antireflection properties of the antireflection layer (C). The amount of the hollow particles added is not particularly limited, but for example, 30 parts by weight or more, 50 parts by weight or more, 70 parts by weight or more, 90 parts by weight based on 100 parts by weight of the resin in the coating liquid for forming an antireflection layer. parts or more, or 100 parts by weight or more, and 300 parts by weight or less, 270 parts by weight or less, 250 parts by weight or less, 200 parts by weight or less, or 180 parts by weight or less. From the viewpoint of lowering the refractive index of the antireflection layer (C), it is preferable that the amount of the hollow particles added is not too small, and from the viewpoint of ensuring the mechanical properties of the antireflection layer (C), the addition of the hollow particles It is preferable that the amount is not too large.

The solid particles are not particularly limited, and may be, for example, silica particles, zirconium oxide particles, titanium-containing particles (eg, titanium oxide particles), or the like. Examples of the silica particles include products such as "MEK-2140Z-AC", "MIBK-ST", and "IPA-ST" manufactured by Nissan Chemical Industries, Ltd. The weight average particle diameter of the solid particles is not particularly limited, but may be, for example, 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, or 25 nm or more, and 3300 nm or less, 250 nm or less, 200 nm or less, or 150 nm or less. , or 100 nm or less. The shape of the solid particles is not particularly limited, and may be, for example, approximately spherical in the form of beads, or irregularly shaped such as powder, but approximately spherical is preferred, and more preferably , approximately spherical particles with an aspect ratio of 1.5 or less, and most preferably spherical particles. By adding the solid particles, for example, the fluorine element-containing additive tends to be unevenly distributed on the surface of the coated coating liquid for forming an antireflection layer, and the antireflection layer (C) has the formula It becomes easier to satisfy (1) and (3). A low refractive index, good antireflection properties, etc. of the antireflection layer (C) can be achieved. The amount of the solid particles added is not particularly limited, but is, for example, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, based on 100 parts by weight of the resin in the coating liquid for forming an antireflection layer. It may be at least 25 parts by weight, or at most 150 parts by weight, at most 120 parts by weight, at most 100 parts by weight, or at most 80 parts by weight. From the viewpoint of ensuring mechanical properties and adjusting the refractive index, it is preferable that the amount of the solid particles added is not too small, and from the viewpoint of preventing clouding of the coating film due to scattering, the amount of the solid particles added is not too large. It is preferable.

The diluting solvent is not particularly limited, and various solvents can be used, and one type may be used alone or two or more types may be used in combination. Examples of the diluting solvent include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, TBA (tertiary butyl alcohol), and 2-methoxyethanol; acetone, methyl ethyl ketone, MIBK (methyl isobutyl ketone), and cyclopentanone. Ketones; Esters such as methyl acetate, ethyl acetate, butyl acetate, and PMA (propylene glycol monomethyl ether acetate); Ethers such as diisopropyl ether and propylene glycol monomethyl ether; Glycols such as ethylene glycol and propylene glycol; Ethyl cellosolve, Examples include cellosolves such as butyl cellosolve; aliphatic hydrocarbons such as hexane, heptane, and octane; and aromatic hydrocarbons such as benzene, toluene, and xylene. For example, the polarity of the diluting solvent may be adjusted by mixing a plurality of solvents at an arbitrary ratio.

The diluent solvent may be, for example, a mixed solvent containing MIBK (methyl isobutyl ketone) and PMA (propylene glycol monomethyl ether acetate). The mixing ratio in this case is not particularly limited, but when the weight of MIBK is 100% by weight, the weight of PMA is, for example, 20% by weight or more, 50% by weight or more, 100% by weight or more, 150% by weight or more, or It may be 200% by weight or more, 400% by weight or less, 350% by weight or less, 300% by weight or less, or 250% by weight or less.

The diluent solvent may be, for example, a mixed solvent containing TBA (tertiary butyl alcohol) in addition to MIBK and PMA. The mixing ratio in this case is not particularly limited, but when the weight of MIBK is 100% by weight, the weight of PMA is, for example, 10% by weight or more, 30% by weight or more, 50% by weight or more, 80% by weight or more, or It may be 100% by weight or more, 200% by weight or less, 180% by weight or less, 150% by weight or less, 130% by weight or less, or 110% by weight or less. Furthermore, when the weight of MIBK is 100% by weight, the weight of TBA may be, for example, 10% by weight or more, 30% by weight or more, 50% by weight or more, 80% by weight or more, or 100% by weight or more. , 200% by weight or less, 180% by weight or less, 150% by weight or less, 130% by weight or less, or 110% by weight or less.

The amount of the diluting solvent added is also not particularly limited, but for example, the solid content relative to the weight of the entire coating solution for forming an antireflection layer is, for example, 0.1% by weight or more, 0.3% by weight or more, or 0.3% by weight or more. It may be 5% by weight or more, 1.0% by weight or more, or 1.5% by weight or more, and 20% by weight or less, 15% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight. % or less. From the viewpoint of ensuring coating properties (wetting, leveling), it is preferable that the solid content is not too high, and from the viewpoint of preventing appearance defects caused by drying such as air drying unevenness and whitening, the solid content is preferably not too low.

Next, the antireflection layer forming coating liquid is applied onto the antiglare hard coat layer (B) (the coating step). The coating method is not particularly limited, and for example, known coating methods such as fountain coating, die coating, spin coating, spray coating, gravure coating, roll coating, and bar coating may be used as appropriate. can. The coating amount of the coating liquid for forming an antireflection layer is not particularly limited, but the thickness of the antireflection layer (C) to be formed is, for example, 0.1 μm or more, 0.3 μm or more, 0.5 μm or more, It may be 1.0 μm or more, or 2.0 μm or more, or it may be 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less.

Next, the applied coating solution for forming an antireflection layer is dried to form a coating film (the coating film forming step). The drying temperature is not particularly limited, and may be, for example, in the range of 30 to 200°C. The drying temperature may be, for example, 40°C or higher, 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, 90°C or higher, or 100°C or higher, 190°C or lower, 180°C or lower, or 170°C or lower. It may be below 160°C, below 150°C, below 140°C, below 135°C, below 130°C, below 120°C, or below 110°C. The drying time is not particularly limited, but may be, for example, 30 seconds or more, 40 seconds or more, 50 seconds or more, or 60 seconds or more, and 150 seconds or less, 130 seconds or less, 110 seconds or less, or 90 seconds or less. You can.

Furthermore, the coating film may be cured (curing step). The curing can be performed by heating, light irradiation, etc., for example. The light is not particularly limited, and may be, for example, ultraviolet light. The light source for the light irradiation is also not particularly limited, and may be, for example, a high-pressure mercury lamp. The irradiation amount of the energy ray source in the ultraviolet curing is preferably 50 to 500 mJ/cm ² as a cumulative exposure amount at an ultraviolet wavelength of 365 nm. When the irradiation amount is 50 mJ/cm ² or more, curing is likely to proceed sufficiently, and the hardness of the antireflection layer (C) to be formed is likely to be high. Moreover, if it is 500 mJ/cm ² or less, coloring of the antireflection layer (C) to be formed can be prevented.

As described above, the anti-reflection layer of the present invention has the hard coat layer (B) and the anti-reflection layer (C) laminated in the above order on at least one surface of the light-transmitting substrate (A). Film can be manufactured. Note that, as described above, the antireflection film of the present invention may include layers other than the light-transmissive base material (A), the hard coat layer (B), and the antireflection layer (C). .

Moreover, in the manufacturing process of the antireflection film of the present invention, it is preferable to perform a surface treatment on at least one of the light-transmitting substrate (A) and the anti-glare hard coat layer (B). If the surface of the light-transmitting substrate (A) is surface-treated, the adhesion with the anti-glare hard coat layer (B) or the polarizer or polarizing plate is further improved. Moreover, if the surface of the antiglare hard coat layer (B) is subjected to a surface treatment, the adhesion with the antireflection layer (C) is further improved.

[3. Optical members and image display devices]
The optical member of the present invention is not particularly limited, but may be, for example, a polarizing plate. The polarizing plate is also not particularly limited, but may include, for example, the antireflection film and polarizer of the present invention, and may further include other components. Each component of the polarizing plate may be bonded together using, for example, an adhesive or a pressure-sensitive adhesive.

The image display device of the present invention is not particularly limited, and may be any image display device, including, for example, a liquid crystal display device, an organic EL display device, and the like.

The image display device of the present invention is, for example, an image display device having the antireflection film of the present invention on the viewing side surface, and the image display device may have a black matrix pattern.

The antireflection film of the present invention can be bonded, for example, to an optical member used in an LCD via a pressure-sensitive adhesive or an adhesive on the light-transmitting substrate (A) side. In addition, in this bonding, the surface of the light-transmitting substrate (A) may be subjected to various surface treatments as described above. As described above, according to the method for producing an antireflection film of the present invention, the surface shape of the antireflection film can be freely controlled over a wide range. Therefore, the optical properties that can be obtained by laminating the antireflection film with other optical members using adhesives, pressure-sensitive adhesives, etc. range over a wide range depending on the surface shape of the antireflection film.

Examples of the optical member include a polarizer or a polarizing plate. A polarizing plate generally has a structure in which a transparent protective film is provided on one or both sides of a polarizer. When providing transparent protective films on both sides of the polarizer, the front and back transparent protective films may be made of the same material or may be made of different materials. Polarizing plates are typically placed on both sides of the liquid crystal cell. Moreover, the polarizing plates are arranged so that the absorption axes of the two polarizing plates are substantially orthogonal to each other.

The configuration of the polarizing plate laminated with the antireflection film is not particularly limited, but for example, a transparent protective film, the polarizer, and the transparent protective film may be laminated in this order on the antireflection film. However, the polarizer and the transparent protective film may be laminated in this order on the antireflection film.

The image display device of the present invention has the same configuration as a conventional image display device except that the antireflection film is arranged in a specific direction. For example, in the case of an LCD, it can be manufactured by appropriately assembling each component such as a liquid crystal cell, optical members such as a polarizing plate, and, if necessary, a lighting system (such as a backlight), and incorporating a drive circuit.

The image display device of the present invention may be used for any appropriate purpose. Applications include, for example, computer monitors, notebook computers, office equipment such as copy machines, mobile phones, watches, digital cameras, personal digital assistants (PDAs), portable devices such as portable game consoles, video cameras, televisions, microwave ovens, etc. household electrical equipment, rear view monitors, car navigation system monitors, in-vehicle equipment such as car audio, exhibition equipment such as information monitors for commercial stores, security equipment such as surveillance monitors, nursing care monitors, medical monitors, etc. Nursing care/medical equipment, etc.

Next, examples of the present invention will be described together with comparative examples. However, the present invention is not limited to the following examples and comparative examples. In addition, various characteristics in the following Examples and Comparative Examples were evaluated or measured by the following methods.

[Example 1]
An antireflection film was manufactured as follows.

[Preparation of coating solution for forming anti-glare hard coat layer]
As a resin contained in the anti-glare hard coat layer forming material, 80 parts by weight of ultraviolet curable urethane acrylate resin (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., trade name "UV1700B", solid content 100%) and pentaerythol trichloride. 20 parts by weight of a polyfunctional acrylate containing acrylate as a main component (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat #300", solid content 100% by weight) was prepared. Per 100 parts by weight of resin solid content of the resin, crosslinked polymethyl methacrylate particles (manufactured by Sekisui Plastics Co., Ltd., trade name "Techpolymer", weight average particle diameter: 5 μm, refractive index: 1.51) are used as the particles. 2 parts by weight of synthetic smectite (manufactured by Co-op Chemical Co., Ltd., trade name "Lucentite SAN"), which is an organic clay as the thixotropy imparting agent, 0.4 parts by weight of a photopolymerization initiator (manufactured by BASF, trade name "Lucentite SAN"). 3 parts by weight of "Irgacure 907") and 0.05 parts by weight of a leveling agent (manufactured by DIC Corporation, trade name "PC4100", solid content 10% by weight) were mixed. The organic clay was diluted with toluene to have a solid content of 6% by weight. This mixture was diluted with a toluene/cyclopentanone (CPN) mixed solvent (weight ratio 80/20) so that the solid content concentration was 40% by weight, and an anti-glare hardener was diluted using an ultrasonic disperser. A coating layer forming material (coating liquid) was prepared.

[Formation of anti-glare hard coat layer (B)]
As the light-transmitting substrate (A), a transparent plastic film substrate (acrylic film, manufactured by Nitto Denko Corporation, trade name "HX-40UC", thickness: 40 μm, refractive index: 1.52) was prepared. The anti-glare hard coat layer forming material (coating liquid) was applied to one side of the transparent plastic film substrate using a wire bar to form a coating film (coating step). The coating film was then dried by heating at 95° C. for 1 minute (drying step). Thereafter, the coating film was cured by irradiating ultraviolet rays with a cumulative light intensity of 300 mJ/cm ² using a high-pressure mercury lamp to form an anti-glare hard coat layer (B) having a thickness of 6.5 μm. In this way, a laminate of the light-transmitting substrate (A) and the anti-glare hard coat layer (B) was obtained.

[Preparation of coating solution for forming antireflection layer]
100 parts by weight of polyfunctional acrylate whose main component is pentaerythritol triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., product name "Viscoat #300", solid content 100% by weight), hollow nano silica particles (JGC Catalysts & Chemicals Co., Ltd.) 100 parts by weight, solid nano silica particles (manufactured by Nissan Chemical Industries, Ltd., trade name "MEK-2140Z-AC", solid content 20% by weight, weight average particle diameter 75 nm), solid content 30% (wt%, weight average particle diameter 10 nm), 12 parts by weight of a fluorine element-containing additive (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KY-1203", solid content 20 wt%), and a photopolymerization initiator (manufactured by BASF) , trade name "OMNIRAD907", solid content 100% by weight) were mixed. To the mixture, a mixed solvent of TBA (tertiary butyl alcohol), MIBK (methyl isobutyl ketone) and PMA (propylene glycol monomethyl ether acetate) mixed in a weight ratio of 60:25:15 was added as a diluting solvent to dissolve the entire solid. The coating solution for forming an antireflection layer was prepared by stirring the mixture so that the amount thereof was 4% by weight.

[Formation of antireflection layer (C)]
The coating solution for forming an antireflection layer was applied to the hard coat surface (the surface opposite to the light transmitting substrate (A)) of the antiglare hard coat layer (B) using a wire bar (coating). construction process). The applied coating solution was heated at 80° C. for 1 minute and dried to form a coating film (drying step). The dried coating film was cured by irradiating ultraviolet rays with a cumulative light intensity of 300 mJ/cm ² using a high-pressure mercury lamp (curing step). Thereby, the coating film was cured, and an antireflection layer (C) having a thickness of 0.1 μm was formed (antireflection layer (C) forming step). In the manner described above, the antireflection film of this example was manufactured.

[Example 2]
In the preparation of the coating solution for forming an antireflection layer, the amount of the fluorine element-containing additive was changed to 10 parts by weight, and the diluting solvent was changed to a mixed solvent mixed at a weight ratio of PMA: MIBK = 75:25. An antireflection film was produced in the same manner as in Example 1, except that the diluting solvent was used to make the total solid content 2% by weight.

[Example 3]
An antireflection film was produced in the same manner as in Example 2, except that in preparing the coating solution for forming an antireflection layer, the amount of the fluorine element-containing additive was changed to 5 parts by weight.

[Comparative example 1]
An antireflection film was produced in the same manner as in Example 2, except that the amount of Viscoat #300 was changed to 80 parts by weight in preparing the coating solution for forming an antireflection layer.

[Comparative example 2]
An antireflection film was produced in the same manner as in Example 1, except that solid silica particles were not blended in the preparation of the coating solution for forming an antireflection layer.

[Comparative example 3]
In the preparation of the coating solution for forming an antireflection layer, the amount of the fluorine element-containing additive was changed to 10 parts by weight, and TBA was changed to PGM (propylene glycol monomethyl ether) among the solvents used as the dilution solvent. An antireflection film was manufactured in the same manner as in Example 1 except for the following.

[Comparative example 4]
An antireflection film was produced in the same manner as in Example 2, except that in preparing the coating solution for forming an antireflection layer, the amount of the fluorine element-containing additive was changed to 3 parts by weight.

(XPS measurement)
C (carbon) atoms and F (fluorine) in the antireflection layer (C) in the antireflection films of Examples and Comparative Examples at a depth of 0 to 30 nm from the surface opposite to the hard coat layer (B). ) The atomic ratio of atoms was measured by XPS (X-ray photoelectron spectroscopy). The measurement conditions were as shown below. The atomic ratio is defined as C (carbon) atoms, where the total number of atoms of C (carbon), N (nitrogen), O (oxygen), Si (silicon) and F (fluorine) at the measured depth is taken as 100%. and the ratio (%) of F (fluorine) atoms.

XPS measurement conditions:
Equipment: Quantera SXM manufactured by ULVAC-PHI
X-ray source; monochrome Al Ka.
Xray Setting; 100μmφ[15kV, 25W]
Photoelectron extraction angle; 45 degrees binding energy correction relative to the sample surface; peak derived from CC bond corrected to 285.0eV (top surface)
Neutralization conditions: Combined use of electron neutralization gun and Ar ion gun (neutralization mode)
Acceleration voltage and current of C ₆₀ ion gun: 10kV, 5nA
Raster size of C ₆₀ ion gun: 2.5mm x 2.5mm
Sputtering speed of C ₆₀ ion gun: 2nm/min (SiO ₂ equivalent value)

(Scratch resistance)
The scratch resistance (SW resistance) of the antireflection layer (C) in the antireflection films of Examples and Comparative Examples was evaluated using the following test contents.
(1) A 150 mm x 50 mm sample was cut out from the center of the antireflection film and placed on a glass plate with the side on which the antireflection layer was not formed facing down.
(2) After uniformly attaching steel wool #0000 to the smooth cross section of a cylinder with a diameter of 10 mm, and reciprocating the sample surface (antireflection layer surface) 1000 times at a speed of about 100 mm per second with a load of 1.0 kg, The condition of the sample surface was visually observed and judged using the following index.

4: No visible scratches 3: Five or fewer visible scratches 2: Five or more visible scratches, but there are many areas without scratches 1: There are scratches on almost the entire sample surface

The ratio (%) of C (carbon) atoms and F (fluorine) atoms determined by the XPS measurement and the scratch resistance evaluation results in the antireflection films of Examples and Comparative Examples are summarized in Table 1 below. .

As shown in Table 1 above, in the antireflection films of Examples 1 to 3, the ratio (%) of C (carbon) atoms and F (fluorine) atoms satisfied all of the above formulas (1) to (3). . Furthermore, the antireflection films of Examples 1 to 3 all had good scratch resistance evaluations of "4".

In the anti-reflection film of Comparative Example 1, 0.7% of F (fluorine) atoms were observed at a depth of 15 nm, and the above formula (3) was not satisfied, and the scratch resistance was evaluated as "3" and some scratches were observed. It was done.

In the antireflection film of Comparative Example 2, the ratio (%) of C (carbon) atoms at a depth of 0 nm (on the surface of the antireflection layer (C)) exceeds 41%, and does not satisfy the above formula (2). Fluorine (F) atoms were observed at a wavelength of 15 to 30 nm, which did not satisfy the above formula (3), and the scratch resistance was evaluated as "3", with some scratches observed.

In the antireflection film of Comparative Example 3, the ratio (%) of C (carbon) atoms at a depth of 0 nm (on the surface of the antireflection layer (C)) exceeds 41%, and does not satisfy the above formula (2). Fluorine (F) atoms were observed at a wavelength of 15 to 30 nm, which did not satisfy the above formula (3), and the scratch resistance was evaluated as "2", indicating that a rather large number of scratches were observed.

The antireflection film of Comparative Example 4 satisfied the above formulas (2) and (3), but the ratio of F (fluorine) atoms at a depth of 0 nm (surface of the antireflection layer (C)) was less than 7%. The above formula (1) was not satisfied, the scratch resistance was evaluated as "1", and many scratches were observed.

As described above, according to the present invention, an antireflection film with excellent scratch resistance can be provided. Further, according to the present invention, it is possible to provide a method for manufacturing the antireflection film, an optical member using the antireflection film, and an image display device using the antireflection film. The antireflection film of the present invention can be suitably used, for example, in optical members such as polarizing plates, liquid crystal panels, and image display devices such as LCDs (liquid crystal displays) and OLEDs (organic EL displays), and its uses are not limited. Therefore, it is applicable to a wide range of fields. The present invention is applicable to a wide range of uses and fields, including, for example, various uses where visibility is important.

10 Antireflection film 11 Light transmitting base material (A)
12 Hard coat layer (B)
12a Resin layer 12b Particles 13 Antireflection layer (C)
13a Resin layer 13b Hollow particles 13c Solid particles

Claims (12)

Including a light-transmissive base material (A), a hard coat layer (B), and an antireflection layer (C),
The hard coat layer (B) and the antireflection layer (C) are laminated in the above order on at least one surface of the light transmitting base material (A),
The elements constituting the antireflection layer (C) include at least carbon and fluorine,
The number of atoms of the antireflection layer (C) measured by X-ray photoelectric spectroscopy satisfies the following formulas (1) and (2) on the surface opposite to the hard coat layer (B), and An antireflection film that satisfies the following formula (3) in a depth range of 15 to 30 nm.

7≦[(n _F /n _total )×100]≦27 (1)
30≦[(n _c /n _total )×100]≦41 (2)
[( _nF / _ntotal )×100]≦0.5 (3)

In the above formulas (1) to (3), n _total is the total number of atoms of carbon, nitrogen, oxygen, silicon, and fluorine, n _F is the number of fluorine atoms, and n _c is the number of carbon atoms. be. The antireflection film according to claim 1, wherein the hard coat layer (B) is an anti-glare hard coat layer. The antireflection film according to claim 1 or 2, wherein the antireflection layer (C) contains hollow particles and solid particles. The antireflection film according to claim 3, wherein the hollow particles and the solid particles are silica particles. The antireflection layer (C) is formed on the hard coat layer (B) in the laminate of the light-transmissive base material (A) and the hard coat layer (B) according to the formulas (1) to (3). Including the step of forming an antireflection layer (C) to meet the requirements,
The antireflection layer (C) forming step includes a coating step of applying an antireflection layer forming coating solution on the hard coat layer (B), and a coating step of coating the applied antireflection layer forming coating solution. A coating film forming step of drying to form a coating film,
The method for producing an antireflection film according to any one of claims 1 to 4, wherein the coating liquid for forming an antireflection layer contains a resin, a fluorine element-containing additive, and a diluent solvent. . The manufacturing method according to claim 5, wherein the antireflection layer (C) forming step further includes a curing step of curing the coating film. The manufacturing method according to claim 5 or 6, wherein the diluent solvent contains MIBK (methyl isobutyl ketone) and PMA (propylene glycol monomethyl ether acetate). The manufacturing method according to claim 7, wherein the diluent solvent further contains TBA (tertiary butyl alcohol). The antireflection film is the antireflection film according to claim 3 or 4,
The manufacturing method according to any one of claims 5 to 8, wherein the antireflection layer forming coating liquid further contains the hollow particles and the solid particles. An optical member comprising the antireflection film according to any one of claims 1 to 4. The optical member according to claim 10, which is a polarizing plate. An image display device comprising the antireflection film according to claim 1 or the optical member according to claim 10 or 11.

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