CN103777255A - Anti-dazzle film and manufacturing method therefor - Google Patents

Abstract

The present invention provides an anti-glare film which has an excellent balance between haze and sharpness, can improve anti-glare properties even if it is installed in a high-definition display device, can suppress glare to a high degree, and can also suppress blurring of characters. On the surface of the anti-glare layer of the anti-glare film of the present invention, elongated protrusions having a branched structure and a total length of 100 μm or more are formed on the surface of the anti-glare layer accompanying the phase separation of various resin components. One or more elongated protrusions are present per 1 mm ² on the surface of the antiglare layer. The elongated protrusions form a co-continuous phase structure, and the average diameter of the mesh of the co-continuous phase structure may be about 1 to 70 μm. The antiglare film of the present invention has a transmission image sharpness of 70 to 100%, a haze of 10 to 40%, and a total light transmittance of 70 to 100%. Measured by the image measuring instrument of the slit.

Description

Anti-glare film and manufacturing method thereof

technical field

The present invention relates to an antiglare film suitable for preventing glare on display surfaces of various display devices and reflection of external light sources and a method for producing the same.

Background technique

In order to prevent the reflection of the outside scene on the display surface of liquid crystal display devices, organic electroluminescent (EL) display devices, etc., usually by coating the mixture of particles and binder resin or curable resin on the base material and forming Anti-glare properties are exhibited by preventing regular reflections with fine unevenness. However, for a high-definition display device with a fine pixel size, image quality degradation such as glare on the screen, blurred characters, etc., may occur with the conventional size of surface irregularities. That is, in the case of a high-definition display device, the size of the existing surface unevenness is close to the pixel size of the high-definition display in order of magnitude, and the lens effect caused by the surface unevenness will cause glare. In addition, since the position of the center of gravity of the particles inside the coating and in the surface structure cannot be controlled, the transmitted scattered light has a Gaussian distribution centered on the straight forward transmitted light. Therefore, at the conventional particle size, the scattering near the straight-line transmitted light increases, and the outline of the pixel becomes blurred, resulting in blurred characters. Moreover, the intensity distribution of the transmitted scattered light depends on the size of the added particles. If the particle is smaller, the scattering of the straight-line transmitted light decreases and the glare is reduced. If the particle is larger, the scattering near the straight-line transmitted light increases, resulting in glare. .

In order to solve these problems, attempts have been made to control the uneven shape of the surface by reducing the size of the added particles or using particles with a narrow particle size distribution. However, in these methods, in order to prevent glare and blurred characters, it is necessary to control the position of the center of gravity of the particles. In addition, since the uneven shape of the surface becomes smaller, it is difficult to achieve sufficient anti-glare properties, and it is disadvantageous in terms of cost.

Japanese Unexamined Patent Publication No. 2001-215307 (Patent Document 1) discloses an antiglare layer in which transparent fine particles having an average particle diameter of 15 μm or less are contained in a film having a thickness twice or more the average particle diameter. In the obtained anti-glare layer, in the above-mentioned film, the above-mentioned transparent fine particles are unevenly present on the side in contact with the air and form a fine uneven structure on the surface. This document also discloses an optical member provided with the above-mentioned antiglare layer on at least one side of a polarizing plate or an elliptically polarizing plate.

However, in this anti-glare layer, the intensity distribution of transmitted and scattered light is controlled by the particle size, so that glare and blurring of characters on the display surface cannot be effectively prevented.

In Japanese Unexamined Patent Application Publication No. 2011-13238 (Patent Document 2), as an antiglare film having a surface unevenness capable of achieving antiglare properties and high contrast, a film in which an antiglare layer is laminated on a translucent substrate is disclosed. An anti-glare film, wherein the above-mentioned anti-glare layer has a co-continuum structure with a mesh size in the horizontal direction of 10-150 μm, and the above-mentioned anti-glare layer has at least a first phase and a second phase. In this document, an inorganic component is aggregated in the antiglare layer to form a cocontinuum structure during film formation. In addition, the "co-continuum structure" in this document is defined as a structure in which the inclination of the convex portion of the surface unevenness is smaller and gentler than that of the conventional anti-glare layer.

However, the cocontinuum structure of this document is produced by convection accompanying the aggregation of inorganic components, and since it is difficult to precisely control convection, the mesh size and mesh thickness (width) cannot be made uniform. Therefore, small-sized asperities that reduce glare and large-sized asperities that increase glare by orders of magnitude coexist, and it is essentially impossible to simultaneously achieve glare reduction and anti-glare properties. In addition, when the mesh size is small, although glare can be reduced, sufficient anti-glare properties cannot be exhibited. On the other hand, when the mesh size is large, the surface unevenness size is close to the pixel size in orders of magnitude, so glare cannot be reduced.

On the other hand, there is also known a method of forming concavo-convex shapes on the surface by spinodal decomposition of incompatible resin components, and Japanese Patent No. 4377578 (Patent Document 3) discloses a method comprising an antiglare layer An anti-glare film, the anti-glare layer has a concave-convex structure on the surface, transmits and scatters incident light isotropically, is composed of at least one polymer and at least one curable resin precursor, and has a phase-separated structure. This document describes that, in the method of evaporating the solvent from a solution in which at least one polymer and at least one curable resin precursor are uniformly dissolved to form a sheet, it is made to lose the solvent under appropriate conditions. When the above-mentioned precursor is decomposed stably and then solidified, a phase separation structure with regular interphase distance and a surface uneven structure corresponding to the phase structure can be formed; When used in a display device (such as a liquid crystal display device with a resolution of 150ppi), the glare and blurred characters on the display surface can be effectively eliminated. In particular, it is described in this document that a co-continuous structure is formed with the progress of phase separation, and when the phase separation progresses further, a droplet phase structure is formed; The droplet phase structure of (domain) is advantageous, and by forming island-like domains, unevenness can be formed on the surface of the anti-glare layer after drying. Moreover, it is described in this document that as the drying temperature for inducing phase separation caused by destabilizing decomposition, it can be selected from a temperature lower than the boiling point of the solvent (for example: a range of about 30 to 200° C.), preferably 40 to 200° C. 80°C, in the examples, drying at 60°C or 80°C.

Japanese Patent Application Laid-Open No. 2008-225195 (Patent Document 4) discloses an antiglare film formed from a cured product of ( A meth)acrylic resin, a (meth)acrylic resin having a polymerizable group having a weight average molecular weight of 1,000 to 100,000, and a multifunctional (meth)acrylate, wherein, on the surface of the antiglare film, Rope-like protrusions having an average width of 0.1 to 30 μm are dispersed in random directions, and the area ratio of the rope-like protrusions to the total surface is 50% or less. This document also states that it is advantageous to have a liquid droplet phase structure having at least island-like domains, and by forming island-like domains, unevenness can be formed on the surface of the anti-glare layer after drying. Moreover, it is also described in this document: in order to induce convection and phase separation, it is preferable to leave it at room temperature or room temperature for a certain period of time, and then place it at a temperature lower than the boiling point of the solvent (for example: 30-200 ° C, particularly preferably about 40-80 ° C). range) to dry, in an embodiment, after standing at room temperature for 10 seconds, dry in an explosion-proof oven at 60°C or 70°C with a wind speed of 3m/min.

But, with regard to the anti-glare film of patent document 3 and 4, in the resolution higher than 150ppi high-definition display device (for example: have the liquid crystal display device of 200ppi above resolution or organic EL display device etc.), cannot maintain Anti-glare while reducing glare. In particular, there is a tendency that the farther the distance between the display surface and the anti-glare layer is, the easier it is to generate glare. However, as for the protection or protective film of the display device (the film that is pasted on the display surface by the user after purchase), due to the Therefore, the distance between it and the display surface is relatively long, and it is difficult to suppress glare. Moreover, in high-definition display devices, organic EL panels are prone to glare due to the high luminous intensity of pixels, and it is difficult to achieve anti-glare properties and suppress blurring of characters at the same time. The anti-glare films of Patent Documents 3 and 4 cannot achieve both of the above characteristics. .

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2001-215307 (Claims)

Patent Document 2: Japanese Patent Laid-Open No. 2011-13238 (claims, paragraphs [0012][0035])

Patent Document 3: Japanese Patent No. 4377578 (Claim 1, Paragraphs [0058][0059][0071][0083], Examples)

Patent Document 4: Japanese Patent Laid-Open No. 2008-225195 (claims, paragraphs [0068][0069][0074][0075], examples)

Contents of the invention

The problem to be solved by the invention

Therefore, the object of the present invention is to provide an excellent balance of haze and sharpness, even if it is set in a high-definition display device (for example: a liquid crystal display device with a resolution of 200ppi or more, an organic EL display device, etc.) The anti-glare film and its production method are anti-glare film which can suppress glare highly, and can also suppress blurring of characters.

Another object of the present invention is to provide a device that can have both anti-glare and anti-glare properties, and can improve scratch resistance, even if it is placed away from the display surface of a high-definition display device such as an organic EL panel (or an organic EL display device). Harmful anti-glare film and manufacturing method thereof.

way of solving the problem

The inventors of the present invention first investigated the mechanism by which conventional antiglare films utilizing destabilizing decomposition of incompatible resin components cannot achieve both antiglare and antiglare properties in high-definition display devices. As shown in FIG. 1 , the existing concave-convex structure formed by phase separation is mainly a structure in which droplet-like structures are arranged relatively periodically. Phase separation is a phenomenon in which a resin mixture that is in a thermodynamically stable state by being uniformly dissolved in a coating solution becomes a thermodynamically unstable state as the solvent evaporates, causing destabilizing decomposition. It is characterized in that since the whole system reaches a thermodynamically unstable state at the same time, homogeneous phase separation occurs in the surface of the coating film, thus forming a relatively periodic and uniform surface unevenness. However, if the size of the surface irregularities is reduced to such an extent that glare can be suppressed relative to the pixel size corresponding to a resolution of 200 ppi or more, the anti-glare property will be reduced, and external light will be reflected on the display surface, deteriorating the image quality. On the other hand, if the inclination angle of the convex shape is increased in order to improve the anti-glare property, the haze increases and blurring of characters occurs.

It is generally believed that the glare is caused by the lens effect when the size of the concave-convex structure is close to the pixel size in the order of magnitude. Although it is only speculative, the following phenomenon is generally recognized as glare: when the uneven shape exists across pixels, the transmitted light of each pixel is refracted in different directions due to the uneven shape, and it should have reached the evaluator as RGB color mixing The color and brightness of the eyes changed randomly according to the pitch and inclination of the concavo-convex structure and were felt by the evaluators. When the uneven structure is sufficiently smaller than a pixel, even if there are unevenness across pixels, the proportion is small and the refraction is small, so it is less likely to feel glare. On the other hand, when the concave-convex structure is sufficiently larger than the pixel, if the slope of the concave-convex shape is large, the transmitted light will be refracted greatly to produce a lens effect, but the smaller the slope, the less the refraction of the transmitted light, and the less likely to feel glare. . It is easier to judge by taking the extreme case as an example. It can be predicted that if the inclination angle is infinitely close to zero, it will basically become a plane and the glare will be eliminated.

Based on this, the present inventors found that the conventional anti-glare film tends to generate glare due to the liquid droplet phase structure, so the present inventors paid attention to the co-continuous phase structure (co-continuous structure or co-continuous phase separation structure). That is, for a phase-separated structure including a co-continuous phase structure, it is necessary to adjust the pixel size, and by adjusting the width of the convex portion forming the co-continuous phase structure to be sufficiently smaller than the width of the pixel, glare can be avoided in the width direction the elements of. On the other hand, in the direction of the length (continuous length) of the convex portion, there is theoretically no inclination except for the end portion, so glare does not easily occur. In particular, not only the co-continuous phase structure, but also the liquid droplet phase structure, when the length of the island-like domain is longer, the proportion of the end portion becomes smaller, so it is less likely to generate glare. In addition, although the dimension in the width direction is small, the co-continuous phase structure and the long island-like domains spread greatly in the film surface direction, so it is easy to ensure anti-glare properties. Moreover, the co-continuous phase structure has substantially few inclined portions, so there are few factors causing light scattering, and the haze is lower than that of a droplet-shaped surface uneven structure having the same size as the width direction, so it is not easy to Produces blurry characters.

Based on such knowledge, the present inventors conducted intensive studies to solve the above-mentioned problems. As a result, it was found that a branched structure with a total length of 100 μm or more is densely formed on the surface of the anti-glare layer accompanied by phase separation of various resin components. The elongated convex part can provide an excellent balance between haze and sharpness, and can improve the anti-glare property even if it is arranged in a high-definition display device (such as a liquid crystal display device with a resolution of 200ppi or more, an organic EL display device, etc.), Glare can be highly suppressed, and blurring of characters can also be suppressed, thereby completing the present invention.

That is, the anti-glare film of the present invention is an anti-glare film comprising an anti-glare layer having elongated protrusions on the surface, which are formed by phase separation of various resin components, wherein the elongated protrusions have branches structure and a total length of 100 μm or more, and there is one or more elongated protrusions per 1 mm ² of the surface of the anti-glare layer. The elongated protrusions form a co-continuous phase structure, and the average diameter of the mesh of the co-continuous phase structure may be 1-70 μm. On the surface of the anti-glare layer, the length ratio of the elongated protrusions having a branched structure to the other protrusions may be the former/the latter = about 100/0 to 50/50. The anti-glare film of the present invention can have a transmission image clarity of 70-100%, a haze of 10-40%, and a total light transmittance of 70-100%. The transmission image clarity is obtained by using a 0.5mm wide Measured by the image measuring instrument of the optical slit. The plurality of resin components may include a plurality of polymers and at least one curable resin precursor selected from the group consisting of styrene resins, (meth)acrylic resins, Alicyclic olefin resins, polyester resins, aliphatic organic acid cellulose esters and aromatic organic acid cellulose esters, the group of curable resin precursors includes: epoxy (meth)acrylate, urethane ester (meth)acrylate, polyester (meth)acrylate, silicone (meth)acrylate and polyfunctional monomers having at least two polymerizable unsaturated bonds, and the polymer At least two components of at least two components phase-separate by destabilizing decomposition from a liquid phase, and the curable resin precursor is cured. The curable resin precursor may include a low-viscosity curable resin precursor having a viscosity (25° C.) of 3000 mPa·s or less according to JIS Z8803. The antiglare film of the present invention may be an antiglare film capable of suppressing glare even if the antiglare layer is at a distance of 0.05 mm or more from the display surface when installed on a display device having a resolution of 200 ppi. The display device may be an organic EL display device. The antiglare film of the present invention may further include a transparent film, and the antiglare layer is formed on one side of the transparent film. In this antiglare film, an adhesive layer may be formed on the other side of the transparent film. The antiglare film of the present invention may also be a protective or protective film provided on the outermost surface of a display device (especially an organic EL display device).

The present invention also includes a method for producing the anti-glare film, which includes: applying a solution containing a plurality of resin components and drying to form a phase-separated structure by destabilizing decomposition accompanying solvent evaporation. In the drying step, heating may be performed at a temperature exceeding 80°C.

It should be noted that, in this specification, "(meth)acryloyl", "(meth)acrylate" and "(meth)acrylic acid" mean "acryloyl or methacryloyl", "acrylate or methacrylate" and "acrylic or methacrylic".

The effect of the invention

In the present invention, on the surface of the anti-glare layer, the elongated protrusions having a branched structure and a total length of 100 μm or more are densely formed on the surface of the anti-glare layer along with the phase separation of various resin components. Therefore, the balance between haze and sharpness Excellent, even if it is arranged in a high-definition display device (for example: a liquid crystal display device with a resolution of 200ppi or more, an organic EL display device, etc.), it can improve the anti-glare property, can highly suppress glare, and can also suppress blurring of characters. Furthermore, even if it is installed away from the display surface of a high-definition display device such as an organic EL panel, both anti-glare and anti-glare properties can be achieved, and scratch resistance can be improved. Therefore, even if it is used as a protective film of a high-definition display device such as an organic EL panel, it can have the above-mentioned characteristics.

Description of drawings

FIG. 1 is a laser reflection micrograph of the surface of the anti-glare layer of a conventional anti-glare film (anti-glare film obtained in Comparative Example 2) utilizing destabilizing decomposition of an incompatible resin component.

FIG. 2 is a laser reflection micrograph of the surface of the anti-glare layer of the anti-glare film obtained in Example 1. FIG.

3 is a laser reflection micrograph of the antiglare layer surface of the antiglare film obtained in Example 2.

Detailed ways

[Anti-glare layer]

The anti-glare film of the present invention includes an anti-glare layer having elongated (or elongated) protrusions formed with phase separation of various resin components on the surface of the anti-glare layer. The surface concave-convex structure can show anti-glare property. In particular, in the present invention, since the elongated protrusions have a branched structure and have a total length of 100 μm or more, and form a co-continuous phase structure in a dense state on the surface of the antiglare layer, the balance between haze and sharpness is excellent. , Even if it is arranged in a high-definition display device, it can suppress glare to a high degree without impairing the anti-glare property, and can also suppress blurring of characters.

(slender convex part)

The elongated protrusions are formed by phase separation of various resin components by a method described later, and the elongated (rope-like or linear) protrusions are formed in a substantially mesh shape on the surface of the anti-glare layer. Therefore, it can be observed that on the surface of the anti-glare layer, a mesh structure (like the mesh pattern of the skin of a muskmelon), that is, a variety of irregular rings (for example: continuous rings, or partially missing loop).

Specifically, the anti-glare layer only needs to have one or ^more elongated protrusions having a branched structure and a total length of 100 μm or more (preferably 200 μm or more, more preferably 500 μm or more) per 1 mm of the surface. . It should be noted that the above-mentioned elongated protrusions may also have a plurality, but in the case where the entire surface of the anti-glare layer has a co-continuous phase structure, the length of the above-mentioned elongated protrusions having a branched structure becomes infinitely long, The number of existence is 1 for any region to be measured. The "total length" of the elongated convex portion refers to the total length obtained by adding the lengths of branches branched on the continuous elongated convex portion.

The branched structure of the elongated protrusions may have at least one branch, but it is preferable that the branches of the elongated protrusions are reticulated to form a co-continuous phase structure (co-continuous structure or co-continuous phase-separated structure). In this specification, the "co-continuous phase structure" refers to a continuous structure (or network-like structure) in which droplet-shaped convex structures originating in the manufacturing process are connected during phase separation.

It should be noted that all the elongated protrusions do not need to have a co-continuous phase structure, and may include droplet-shaped protrusions (that is, elongated protrusions without branches, substantially circular protrusions, non-slender convex parts such as elliptical convex parts). In the present invention, by having such elongated protrusions, compared with island-shaped protrusions having a droplet phase structure (or sea-island structure), the ratio of the ends is reduced, and glare and blurring of characters can be suppressed. Furthermore, since the co-continuous phase structure formed with the phase separation of the resin component has a small inclination at the end, glare and blurring of characters can be suppressed.

On the surface of the above-mentioned antiglare layer, the length ratio of the elongated protrusions having a branched structure to other protrusions (droplet-shaped protrusions as origins) can be selected from, for example, the former/the latter=100/0 to 10/ The range of about 90 is, for example, 100/0 to 30/70 (for example, 99/1 to 30/70), preferably 100/0 to 50/50 (for example, 95/5 to 50/50), more preferably About 100/0 to 70/30 (particularly 100/0 to 90/10), particularly preferably approximately 100% (for example, the entire surface has a co-continuous phase structure). Preferably, the above-mentioned elongated convex portion accounts for a relatively high proportion of the convex portion, and generally, it is 50% or more (for example, , 50-90%). If the length ratio is small, the proportion of elongated protrusions having a branched structure is too small, and the proportion of the liquid droplet phase structure increases. Therefore, if the anti-glare property is improved, glare and blurred characters are likely to occur.

The co-continuous phase structure formed by the elongated protrusions is usually arranged in an irregular shape with meshes having the same diameter. The average diameter of each mesh of the co-continuous phase structure (in the case where each mesh of the co-continuous phase structure is an anisotropic shape such as an ellipse or a rectangle, is the average value of the major axis and the minor axis) can be, for example, 1 to 70 μm ( For example, 1 to 40 μm), preferably 2 to 50 μm (for example, 3 to 30 μm), more preferably about 5 to 20 μm (especially 10 to 20 μm). If the mesh diameter is too large, glare and blurred characters will easily occur; if it is too small, the anti-glare property will be reduced.

The shape of each elongated protrusion (the two-dimensional shape of the surface of the anti-glare layer) is usually a rope-like (linear or fibrous) part or all of which has a curved portion, and the average width of the elongated protrusion is 0.1 to 30 μm. As long as the pixel corresponding to the display device is selected from the above range and adjusted to a small width that can suppress glare, for example, it is 0.1 to 20 μm, preferably 0.1 to 15 μm, more preferably 0.1 to 10 μm (especially 0.1 to 5 μm) about. If the width is too large, glare and blurred characters are likely to occur, and if it is too small, the anti-glare property will be reduced. It should be noted that when the droplet-shaped protrusions are connected, the surface shape will change toward the direction of optimizing the surface tension. The width is not necessarily the same as the size of the originating droplet-shaped protrusion.

The average height of the elongated protrusions is, for example, 0.05 to 10 μm, preferably 0.07 to 5 μm, more preferably about 0.09 to 3 μm (particularly 0.1 to 2 μm). The inclination angle of the elongated convex portion is, for example, 10° or less, preferably 0.5° to 5°, more preferably about 1° to 3°. When the height of the convex part is high and the inclination is large, glare and blurred characters are likely to occur.

On the surface of the anti-glare layer, the area ratio of all the protrusions relative to the entire surface is, for example, 10 to 99.9% (for example, 30 to 99.8%), preferably 50 to 99.5% (for example, 80 to 99%), more preferably 90-99% (especially 95-98%). If the area between the elongated protrusions is too small, the anti-glare property tends to decrease, and if it is too large, glare and blurred characters tend to occur.

In this specification, the size, shape (whether or not there are branches, etc.), and the area of the elongated protrusions can be measured or evaluated based on the two-dimensional shape observed on a micrograph. In addition, the average value is the average value of the values measured at arbitrary 10 or more places. In addition, the length ratio between the elongated convex portion and the other convex portion can be obtained by measuring each length in a region of 1 mm ² . In particular, for the elongated protrusions (or co-connected structures) in the present invention, since they will be connected by the droplet phase structure to form a continuous structure, when microscopic observation is carried out, the shape of each elongated protrusion It can be identified based on the ridge-like (ridgeline-like) portion where the vertices of the convex parts are connected. In addition, in this specification, the length of the elongated convex portion can be measured as the length of the above-mentioned ridge portion, and the mesh diameter of the co-continuous phase structure can be obtained based on the above-mentioned ridge portion. Specifically, it is measured by the method described in the Examples described later. In addition, the inclination angle of an elongated convex part can be measured with the surface roughness meter based on JIS standard (for example, "SURFCOM" manufactured by Toyo Seiki Co., Ltd.).

(resin component)

The antiglare layer contains a plurality of resin components capable of phase separation, and the phase separation structure of the antiglare layer is formed by destabilizing decomposition from a liquid phase (wet destabilizing decomposition). As the resin component, as long as it contains a resin component capable of phase separation, it is preferable to contain a polymer component and a curable resin precursor from the viewpoint that the aforementioned elongated protrusions can be formed and scratch resistance can be improved. .

(polymer composition)

As a polymer component, a thermoplastic resin is generally used. Examples of thermoplastic resins include styrene-based resins, (meth)acrylic resins, organic acid vinyl ester-based resins, vinyl ether-based resins, halogen-containing resins, olefin-based resins (including alicyclic olefin-based resins), Polycarbonate resins, polyester resins, polyamide resins, thermoplastic polyurethane resins, polysulfone resins (polyethersulfone, polysulfone, etc.), polyphenylene ether resins (polymerization of 2,6-xylenol substances, etc.), cellulose derivatives (cellulose esters, cellulose carbamates, cellulose ethers, etc.), silicone resins (polydimethylsiloxane, polymethylphenylsiloxane, etc.) , rubber or elastomer (polybutadiene, polyisoprene and other diene rubber, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylic rubber, polyurethane rubber, silicone rubber, etc. )wait. These thermoplastic resins can be used individually or in combination of 2 or more types.

Styrenic resins include homopolymers or copolymers of styrene monomers (polystyrene, styrene-α-methylstyrene copolymers, styrene-vinyltoluene copolymers, etc.), styrene monomers Copolymers with other polymerizable monomers [(meth)acrylic monomers, maleic anhydride, maleimide monomers, dienes, etc.]. Examples of styrene-based copolymers include: styrene-acrylonitrile copolymer (AS resin), copolymers of styrene and (meth)acrylic monomers [styrene-methyl methacrylate copolymer , styrene-methyl methacrylate-(meth)acrylate copolymer, styrene-methyl methacrylate-(meth)acrylic acid copolymer, etc.], styrene-maleic anhydride copolymer, etc. Preferred styrenic resins include polystyrene, copolymers of styrene and (meth)acrylic monomers [styrene-methyl methacrylate copolymers, etc., with styrene and methyl methacrylate as main components Copolymer], AS resin, styrene-butadiene copolymer, etc.

As the (meth)acrylic resin, a homopolymer or a copolymer of a (meth)acrylic monomer, a copolymer of a (meth)acrylic monomer and a copolymerizable monomer, or the like can be used. Among the (meth)acrylic monomers, for example, (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth) (Meth)acrylic acid C _{1- 10} Alkyl esters; aryl (meth)acrylates such as phenyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; Glycidyl (meth)acrylate; N,N-dialkylaminoalkyl (meth)acrylate; (meth)acrylonitrile; tricyclodecane and other (meth)acrylates with alicyclic hydrocarbon groups wait. Among the copolymerizable monomers, the above-mentioned styrene-based monomers, vinyl ester-based monomers, maleic anhydride, maleic acid, fumaric acid, and the like can be illustrated. These monomers can be used individually or in combination of 2 or more types.

Examples of (meth)acrylic resins include poly(meth)acrylates such as polymethyl methacrylate, methyl methacrylate-(meth)acrylic acid copolymers, methyl methacrylate- (meth)acrylate copolymer, methyl methacrylate-acrylate-(meth)acrylic acid copolymer, (meth)acrylate-styrene copolymer (MS resin, etc.), etc. As preferred (meth)acrylic resins, poly(meth)acrylates such as poly(meth)acrylate C _1-6 alkyl esters, especially methyl methacrylate as the main component (50 ~100% by weight, preferably about 70 to 100% by weight) of methyl methacrylate resin.

Examples of organic acid vinyl ester resins include: homopolymers or copolymers of vinyl ester monomers (polyvinyl acetate, polyvinyl propionate, etc.), vinyl ester monomers and copolymerizable monomers Copolymers formed (ethylene-vinyl acetate copolymers, vinyl acetate-vinyl chloride copolymers, vinyl acetate-(meth)acrylate copolymers, etc.) or derivatives thereof. Derivatives of vinyl ester resins include polyvinyl alcohol, ethylene-vinyl alcohol copolymers, polyvinyl acetal resins, and the like.

Examples of vinyl ether resins include homopolymers or copolymers of vinyl C _1-10 alkyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and vinyl tert-butyl ether; Copolymers of C _1-10 alkyl ethers and comonomers (vinyl alkyl ether-maleic anhydride copolymers, etc.).

Examples of halogen-containing resins include: polyvinyl chloride, polyvinylidene fluoride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-(meth)acrylate copolymer, vinylidene chloride-(meth)acrylate copolymer things etc.

Among the olefin resins, for example, homopolymers of olefins such as polyethylene and polypropylene, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene-(meth)acrylic acid copolymers, ethylene - Copolymers such as (meth)acrylate copolymers. Examples of alicyclic olefin resins include homopolymers or copolymers of cyclic olefins (norbornene, dicyclopentadiene, etc.) polymers, etc.), copolymers of the above-mentioned cyclic olefins and copolymerizable monomers (ethylene-norbornene copolymers, propylene-norbornene copolymers, etc.), and the like. Alicyclic olefin-based resins are available as, for example, a product named "ARTON" or a product named "ZEONEX".

The polycarbonate-based resins include aromatic polycarbonates based on bisphenols (bisphenol A, etc.), aliphatic polycarbonates such as diethylene glycol diallyl carbonate, and the like.

Examples of polyester-based resins include aromatic polyesters using aromatic dicarboxylic acids such as terephthalic acid [polyethylene terephthalate, polybutylene terephthalate, etc.] Homopolyesters such as C _2-4 alkylene dicarboxylate or C _2-4 alkylene naphthalate, containing C _2-4 alkylene arylate units (C _2-4 alkylene terephthalate Alkyl ester and/or C _2-4 alkylene naphthalate unit) as the main component (for example, 50% by weight or more) of the copolyester, etc.]. As a copolyester, it includes: in the structural unit of polyarylate C _2-4 alkylene ester, a part of C _2-4 alkylene glycol is replaced by polyoxygen C _2-4 alkylene glycol, C _{6- 10} alkylene glycols, cycloaliphatic diols (cyclohexanedimethanol, hydrogenated bisphenol A, etc.), diols with aromatic rings (9,9-bis(4-(2- Hydroxyethoxy) phenyl) fluorene, bisphenol A, bisphenol A-alkylene oxide adduct, etc.) and other copolyesters; a part of the aromatic dicarboxylic acid is replaced by phthalic acid, isophthalic acid, etc. Copolyesters substituted with asymmetric aromatic dicarboxylic acids such as diacids, and aliphatic _C6-12 dicarboxylic acids such as adipic acid. Polyester-based resins also include polyarylate-based resins, aliphatic polyesters using aliphatic dicarboxylic acids such as adipic acid, and homopolymers or copolymers of lactones such as ε-caprolactone. Preferred polyester-based resins are usually amorphous like amorphous copolyesters (for example, C _2-4 alkylene arylate-based copolyesters, etc.).

Examples of polyamide resins include aliphatic polyamides such as nylon 46, nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, and nylon 12; acid, adipic acid, etc.) and diamines (such as hexamethylenediamine, m-xylylenediamine), etc. The polyamide-based resin may be a homopolymer or a copolymer of a lactam such as ε-caprolactam, or may be a copolyamide instead of a homopolyamide.

Among cellulose derivatives, as cellulose esters, for example, aliphatic organic acid esters (cellulose acetates such as cellulose diacetate and cellulose triacetate; cellulose propionate, cellulose butyrate, C _1-6 organic acid esters such as cellulose acetate propionate, cellulose acetate butyrate, etc.), aromatic organic acid esters (C _7-12 aromatic carboxylates such as cellulose phthalate, cellulose benzoate, etc.) esters), inorganic acid esters (for example, cellulose phosphate, cellulose sulfate, etc.), and mixed acid esters such as acetic acid-cellulose nitrate. In cellulose derivatives, also include: cellulose carbamates (for example, cellulose phenyl carbamate, etc.), cellulose ethers (for example, cyanoethyl cellulose; hydroxyethyl cellulose, hydroxy Hydroxyl C _2-4 alkyl cellulose such as propyl cellulose; C _1-6 alkyl cellulose such as methyl cellulose and ethyl cellulose; carboxymethyl cellulose or its salt, benzyl cellulose, acetyl cellulose Alkyl cellulose, etc.).

Examples of preferable thermoplastic resins include styrene-based resins, (meth)acrylic resins, vinyl acetate-based resins, vinyl ether-based resins, halogen-containing resins, alicyclic olefin-based resins, polycarbonate resins, Ester resins, polyester resins, polyamide resins, cellulose derivatives, silicone resins, rubber or elastomers, etc. As the resin, generally, an amorphous resin soluble in an organic solvent (especially a general-purpose solvent capable of dissolving various polymers and curable compounds) can be used. Resins with high formability, film-forming properties, transparency, and weather resistance are particularly preferred, such as styrene-based resins, (meth)acrylic resins, alicyclic olefin-based resins, polyester-based resins, cellulose derivatives ( cellulose esters, etc.), etc.

As the polymer component, a polymer having a functional group participating in a curing reaction (or a functional group capable of reacting with a curable compound) can also be used. The above-mentioned polymer may have a functional group on the main chain, or may have a functional group on the side chain. The above-mentioned functional groups may be introduced into the main chain by copolymerization, cocondensation, etc., but are usually introduced into side chains. Examples of such functional groups include condensable groups, reactive groups (for example, hydroxyl groups, acid anhydride groups, carboxyl groups, amino groups, imino groups, epoxy groups, glycidyl groups, isocyanate groups, etc.), polymerizable groups (For example, C _2-6 alkenyl groups such as vinyl, propenyl, isopropenyl, butenyl, allyl, etc., C _2-6 alkynyl groups such as ethynyl, propynyl, butynyl, vinylidene etc. C _2-6 alkenylene group, or a group having these polymerizable groups ((meth)acryloyl group, etc.), etc.). Among these functional groups, polymerizable groups are preferable.

As a method for introducing a polymerizable group into a side chain, for example, a method of reacting a thermoplastic resin having a functional group such as a reactive group or a condensable group with a polymerizable compound having a reactive group that reacts with the functional group method.

Examples of thermoplastic resins having functional groups include thermoplastic resins having carboxyl groups or their anhydride groups (for example, (meth)acrylic resins, polyester resins, polyamide resins, etc.), thermoplastic resins having hydroxyl groups (for example, (meth)acrylic resins, polyurethane resins, cellulose derivatives, polyamide resins, etc.), thermoplastic resins having amino groups (e.g., polyamide resins, etc.), thermoplastic resins having epoxy groups (e.g., Epoxy-based (meth)acrylic resins, polyester resins, etc.) and the like. In addition, resins obtained by introducing the above-mentioned functional groups into thermoplastic resins such as styrene-based resins, olefin-based resins, and alicyclic olefin-based resins by copolymerization or graft polymerization may also be used.

As the polymerizable compound, in the case of a thermoplastic resin having a carboxyl group or an acid anhydride group thereof, a polymerizable compound having an epoxy group, a hydroxyl group, an amino group, an isocyanate group, or the like can be used. In the case of the thermoplastic resin which has a hydroxyl group, the polymeric compound etc. which have a carboxyl group, its acid anhydride group, or isocyanate group etc. are mentioned. In the case of a thermoplastic resin having an amino group, a polymerizable compound having a carboxyl group or an acid anhydride group thereof, an epoxy group, an isocyanate group, or the like is exemplified. In the case of the thermoplastic resin which has an epoxy group, the polymeric compound etc. which have a carboxyl group, its acid anhydride group, or an amino group etc. are mentioned.

Among the above-mentioned polymerizable compounds, examples of polymerizable compounds having an epoxy group include epoxy cyclohexenyl (meth)acrylate and other epoxy ring C _5-8 alkenyl (methyl) Acrylates, glycidyl (meth)acrylate, allyl glycidyl ether, etc. As the compound having a hydroxyl group, for example, hydroxy C _1-4 alkyl (meth)acrylate such as hydroxypropyl (meth)acrylate, C _2-6 alkylene such as ethylene glycol mono(meth)acrylate, etc. Alkyl glycol (meth)acrylate, etc. As a polymerizable compound having an amino group, for example, C _1-4 alkyl (meth)acrylate amino groups such as amino ethyl acrylate, C _3-6 alkenyl amines such as allylamine, Aminostyrenes such as 4-aminostyrene and diaminostyrene, etc. As a polymeric compound which has an isocyanate group, (poly)urethane (meth)acrylate, vinyl isocyanate, etc. can be illustrated, for example. As a polymeric compound which has a carboxyl group or its acid anhydride group, unsaturated carboxylic acid, such as (meth)acrylic acid and maleic anhydride, or its anhydride etc. can be illustrated, for example.

As a representative example, a combination of a thermoplastic resin having a carboxyl group or an acid anhydride group thereof and an epoxy group-containing compound, especially a (meth)acrylic resin ((meth)acrylic acid-(meth)acrylate copolymer substances, etc.) and a combination of epoxy-containing (meth)acrylates (epoxycycloalkenyl (meth)acrylate, glycidyl (meth)acrylate, etc.). Specifically, a polymer obtained by introducing a polymerizable unsaturated group into some carboxyl groups of a (meth)acrylic resin, for example, a (meth)acrylic acid-(meth)acrylate copolymer can be used. A (meth)acrylic polymer in which a part of the carboxyl group reacts with the epoxy group of 3,4-epoxycyclohexenyl methacrylate to introduce a photopolymerizable unsaturated group into the side chain, etc.

The amount of functional groups involved in the curing reaction (especially polymerizable groups) introduced into the thermoplastic resin is 0.001 to 10 moles, preferably 0.01 to 5 moles, more preferably about 0.02 to 3 moles per 1 kg of thermoplastic resin.

These polymers can be used in appropriate combination. That is, the polymer may be composed of multiple polymers. Many polymers can also undergo phase separation by liquid-phase destabilizing decomposition. In addition, multiple polymers may also be incompatible with each other. In the case of combining a plurality of polymers, the combination of the first resin and the second resin is not particularly limited, and a plurality of polymers that are incompatible with each other near the processing temperature, for example, two polymers that are incompatible with each other and Use in proper combination. For example, when the first resin is a styrenic resin (polystyrene, styrene-acrylonitrile copolymer, etc.), the second resin may be a cellulose derivative (for example, cellulose esters such as cellulose acetate propionate, etc.) class), (meth)acrylic resins (polymethyl methacrylate, etc.), alicyclic olefin resins (polymers with norbornene as a monomer, etc.), polycarbonate resins, polyester resins ( The above-mentioned C _2-4 alkylene arylate copolyester, etc.) and the like. In addition, for example, when the first polymer is a cellulose derivative (for example, cellulose esters such as cellulose acetate propionate), the second polymer may be a styrenic resin (polystyrene, styrene-propylene Nitrile copolymers, etc.), (meth)acrylic resins, alicyclic olefin resins (polymers containing norbornene as a monomer, etc.), polycarbonate resins, polyester resins (the above-mentioned polyarylic acid C _{2 -4} alkylene ester copolyester, etc.), etc. In the combination of various resins, at least cellulose esters ( _such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, etc.) can be used. esters).

It should be noted that the phase-separated structure generated by destabilizing decomposition is finally cured by active light rays (ultraviolet rays, electron beams, etc.), heat, etc., to form a cured resin. Thereby, scratch resistance can be imparted to the antiglare layer, and durability can be improved.

From the viewpoint of scratch resistance after curing, it is preferable that among the plurality of polymers, at least one polymer, for example, one polymer among mutually incompatible polymers (in which the first resin and the second In the case of a combination of resins, in particular, two types of polymers) are polymers having a functional group capable of reacting with a curable resin precursor in a side chain.

The ratio (weight ratio) of the first polymer to the second polymer is selected from, for example: the former/the latter=1/99 to 99/1, preferably 5/95 to 95/5, more preferably 10/90 to 90/10 The range of left and right is usually about 20/80 to 80/20, especially about 30/70 to 70/30.

It should be noted that, as the polymer for forming the phase-separated structure, in addition to the above-mentioned two incompatible polymers, the above-mentioned thermoplastic resin or other polymers may also be included.

The glass transition temperature of the polymer is selected from the range of, for example, -100°C to 250°C, preferably -50°C to 230°C, more preferably about 0 to 200°C (for example, about 50 to 180°C). In addition, from the viewpoint of surface hardness, it is advantageous that the glass transition temperature is 50° C. or higher (for example, about 70 to 200° C.), preferably 100° C. or higher (for example, about 100 to 170° C.). The weight average molecular weight of a polymer is selected from the range of 1,000,000 or less, Preferably it is about 1,000-500,000, for example.

(curable resin precursor)

As a curable resin precursor, a compound having a functional group that reacts with heat, active energy rays (ultraviolet rays, electron beams, etc.), that is, can be cured or crosslinked by heat, active energy rays, etc. In particular curing or crosslinking resins) of various curable compounds. As the resin precursor, for example, thermosetting compounds or resins [low molecular weight compounds having epoxy groups, polymerizable groups, isocyanate groups, alkoxysilyl groups, silanol groups, etc. (for example, epoxy-based resins, unsaturated polyester resins, urethane resins, silicone resins, etc.], photocurable compounds that can be cured by active light (ultraviolet rays, etc.) (photocurable monomers, oligomers, etc. curable compound, etc.), etc., and the photocurable compound may be an EB (electron beam) curable compound or the like. In addition, photocurable compounds such as photocurable monomers, oligomers, or photocurable resins optionally having a low molecular weight are also simply referred to as “photocurable resins”.

Photocurable compounds include, for example, monomers and oligomers (or resins, especially low-molecular-weight resins). As monomers, for example, monofunctional monomers [(meth)acrylic acid such as (meth)acrylate monomers, vinyl monomers such as vinylpyrrolidone, isobornyl (meth)acrylate, adamantyl (meth)acrylate and other (meth)acrylic acid with bridged hydrocarbon groups], at least two Polyfunctional monomers with polymerizable unsaturated bonds [ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate base) acrylate, hexanediol di(meth)acrylate and other alkylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate , polyoxytetramethylene glycol di(meth)acrylate, etc. (poly)oxyalkylene glycol di(meth)acrylate; tricyclodecane dimethanol di(meth)acrylate, adamantane Di(meth)acrylates and other di(meth)acrylates with bridged hydrocarbon groups; trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol Polyfunctional monomers having about 3 to 6 polymerizable unsaturated bonds, such as tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate].

Examples of oligomers or resins include (meth)acrylates of bisphenol A-alkylene oxide adducts, epoxy (meth)acrylates (bisphenol A epoxy (meth)acrylates, Novolak type epoxy (meth)acrylate, etc.), polyester (meth)acrylate (e.g., aliphatic polyester type (meth)acrylate, aromatic polyester type (meth)acrylate, etc.) , (poly)urethane (meth)acrylate (polyester urethane (meth)acrylate, polyether urethane (meth)acrylate, etc.), silicone (meth)acrylate ) acrylate, etc. These photocurable compounds can be used individually or in combination of 2 or more types.

Preferable curable resin precursors are photocurable compounds that can be cured in a short time, for example: ultraviolet curable compounds (monomers, oligomers, or optionally low molecular weight resins, etc.), EB curable compounds. In particular, a useful resin precursor is an ultraviolet curable resin. In addition, in order to improve durability such as scratch resistance, the photocurable compound (photocurable resin) is preferably a compound having 2 or more (preferably 2 to 15, more preferably about 4 to 10) polymerizable unsaturated bonds in the molecule. Specifically, epoxy (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, silicone (meth)acrylate, having at least two polymerizable non- A polyfunctional monomer with a saturated bond.

The molecular weight of the curable resin precursor is 5,000 or less, preferably 2,000 or less, and more preferably about 1,000 or less in consideration of the compatibility with the polymer.

The viscosity of the curable resin precursor (viscosity at 25° C. based on JIS Z8803) can be selected from the range of about 100 to 10000 mPa·s (especially 500 to 8000 mPa·s). It is particularly preferable that the curable resin precursor contains at least a low-viscosity curable resin precursor having a viscosity of 3000 mPa·s or less from the viewpoint of easiness of forming the elongated protrusions. The viscosity of the low-viscosity curable resin precursor (viscosity at 25° C. based on JIS Z8803) is, for example, 100 to 3000 mPa·s, preferably 300 to 2800 mPa·s, more preferably 500 to 2500 mPa·s (especially 1000 to 2300 mPa·s) s) or so. If the viscosity of the low-viscosity curable resin precursor is too high, it will be difficult to form the above-mentioned elongated protrusions. The mechanism by which the low-viscosity curable resin precursor makes it easy to form the elongated protrusions is not clear, but it is presumed that this is because the low-viscosity curable resin precursor improves the melt fluidity of the coating liquid in the drying process, In particular, the degree of freedom of the above-mentioned thermoplastic resin in which phase separation occurs increases, thereby promoting destabilizing decomposition, thereby promoting transition from a liquid droplet phase structure to a co-continuous phase structure.

The proportion of the low-viscosity curable resin precursor can be selected from the range of about 1 to 50% by weight, for example, 3 to 40% by weight, preferably 5 to 35% by weight, more preferably 10 to 30% by weight, relative to the total resin components. % by weight (especially 15 to 25% by weight). If the proportion of the low-viscosity curable resin precursor is too high, the formation of initial unevenness due to the phase separation of destabilization decomposition is suppressed, and the chances of the protrusions being connected due to melting are reduced, so it is difficult to form elongated protrusions; if When the ratio of the low-viscosity curable resin precursor is too small, the melt fluidity of the coating liquid decreases, making it difficult to form elongated protrusions.

The curable resin precursor may contain a curing agent depending on its type. For example, a thermosetting resin may contain curing agents such as amines and polycarboxylic acids, and a photocurable resin may contain a photopolymerization initiator. As the photopolymerization initiator, can illustrate: common components, for example: acetophenones or propiophenones, benzils, benzoyls, benzophenones, thioxanthones, acylphosphine oxides ( Ashilhosfin Okisid) and the like. The content of curing agents such as photocuring agents is 0.1 to 20 parts by weight relative to 100 parts by weight of the curable resin precursor, preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight (especially 1 to 5 parts by weight) About 3 to 8 parts by weight may be sufficient.

Furthermore, a curable resin precursor may contain a hardening accelerator. For example, photocurable resins may contain photocuring accelerators such as tertiary amines (dialkylaminobenzoate, etc.), phosphine photopolymerization accelerators, and the like.

Of the at least one polymer and the at least one curable resin precursor, at least two components may be used in a combination that phase-separates from each other around the processing temperature. Examples of combinations in which phase separation occurs include: (a) a combination in which a plurality of polymers are incompatible with each other and phase separation occurs; (b) a combination in which a polymer and a curable resin precursor are incompatible and phase separation occurs; Separate combinations, (c) a combination in which multiple curable resin precursors are incompatible with each other and undergo phase separation, and the like. Among these combinations, (a) combinations of multiple types of polymers, (b) combinations of polymers and curable resin precursors are generally preferred, and (a) combinations of multiple types of polymers are particularly preferred. When the compatibility between the two phase-separated components is high, the phase-separated components cannot be effectively phase-separated during the drying process for evaporating the solvent, and the function as an anti-glare layer decreases.

It should be noted that thermoplastic resins and curable resin precursors (or cured resins) are generally incompatible with each other. In the case where the polymer and the curable resin precursor are incompatible and phase-separated, a plurality of polymers may be used as the polymer. When a plurality of polymers are used, at least one polymer may be incompatible with the resin precursor (or cured resin), and other polymers may be compatible with the resin precursor.

In addition, it is also possible to combine two types of thermoplastic resins and curable compounds (in particular, monomers or oligomers having a plurality of curable functional groups) that are incompatible with each other. Moreover, from the viewpoint of scratch resistance after curing, one polymer (especially two polymers) of the above-mentioned incompatible thermoplastic resins may have a functional group that participates in the curing reaction (before participating in the above-mentioned curable resin) Body of cured functional groups) thermoplastic resin.

In the case where phase separation occurs when a polymer is composed of mutually incompatible multiple polymers, the curable resin precursor and the incompatible multiple polymers may be used in a combination that is compatible with each other near the processing temperature. at least one polymer. That is, for example, when a plurality of mutually incompatible polymers are composed of a first resin and a second resin, it is sufficient that the curable resin precursor is compatible with at least one of the first resin or the second resin, Compatibility with both polymer components may also be preferred. In the case of compatibility with two polymer components, phase separation is at least two phases, the at least two phases being a mixture mainly composed of the first resin and curable resin precursor, and a mixture mainly composed of the second resin and curable resin precursor. The resin precursor is a mixture of the main ingredients.

When the compatibility of the selected polymers is high, phase separation between the polymers cannot effectively occur during the drying process for evaporating the solvent, and the function as an anti-glare layer decreases. The phase separation property of various polymers can be judged as follows: a homogeneous solution is prepared using a solvent that is a good solvent for both components, and in the process of slowly evaporating the solvent, it is visually confirmed whether the remaining solid component becomes cloudy or not. This can be easily determined.

Furthermore, generally, the cured or crosslinked resins produced by curing the polymer and resin precursors differ in refractive index from each other. In addition, the refractive indices of the plurality of polymers (the first resin and the second resin) are also different from each other. The difference between the refractive index of the polymer and the cured or crosslinked resin, or the difference between the refractive indices of the multiple polymers (first resin and second resin) may be, for example, 0.001 to 0.2, preferably about 0.05 to 0.15.

The ratio (weight ratio) of the polymer to the curable resin precursor is not particularly limited. For example, it can be selected from the range of the former/the latter = 5/95 to 95/5, and is preferably 5/5 from the viewpoint of surface hardness. About 95 to 60/40, more preferably 10/90 to 50/50, particularly preferably about 10/90 to 40/60.

[Anti-glare film]

The anti-glare film of the present invention consists of at least an anti-glare layer. The thickness of the anti-glare layer may be formed by, for example, the anti-glare layer alone, but usually further includes a transparent film, and the anti-glare layer may be formed on one side of the transparent film.

In the antiglare layer, conventional additives such as organic or inorganic particles, stabilizers (antioxidants, ultraviolet absorbers, etc.), surfactants, water-soluble polymers, etc. , fillers, cross-linking agents, coupling agents, colorants, flame retardants, lubricants, waxes, preservatives, viscosity modifiers, tackifiers, leveling agents, defoamers, etc.

The thickness of the anti-glare layer can be, for example, 0.3-20 μm, preferably about 1-15 μm (for example, 1-10 μm), usually about 2-10 μm (especially 3-7 μm). It should be noted that, when the anti-glare film is composed of the anti-glare layer alone, the thickness of the anti-glare layer can be selected from a range of, for example, 1 to 100 μm, preferably about 3 to 50 μm.

(Transparent film)

As a transparent film (transparent support body or base material sheet), glass, ceramics, and a resin sheet can be illustrated. As the resin constituting the transparent film, the same resin as that of the above-mentioned anti-glare layer can be used. As a preferred transparent film, can enumerate: transparent polymer film, for example: by cellulose derivative [cellulose acetate such as triacetate cellulose (TAC), diacetate cellulose etc.], polyester resin [ Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyarylate resins, etc.], polysulfone resins [polysulfone, polyethersulfone (PES), etc.] , polyether ketone resins [polyether ketone (PEK), polyether ether ketone (PEEK), etc.], polycarbonate resins (PC), polyolefin resins (polyethylene, polypropylene, etc.), cyclic polyolefins resins [ARTON, ZEONEX, etc.], halogen-containing resins (polyvinylidene chloride, etc.), (meth)acrylic resins, styrenic resins (polystyrene, etc.), vinyl acetate or vinyl alcohol resins (polyethylene Alcohol, etc.) etc. formed film.

The transparent film may be uniaxially or biaxially stretched, but is preferably optically isotropic. Preferred transparent films are low birefringence supported films. Examples of optically isotropic transparent films include unstretched films, for example, polyesters (PET, PBT, etc.), cellulose esters, particularly cellulose acetates (cellulose diacetate, A film formed of cellulose acetate such as cellulose triacetate, cellulose acetate such as cellulose acetate propionate, cellulose acetate butyrate ( _C3-4 organic acid ester) and the like.

The thickness of the transparent film of the two-dimensional structure can be selected from the range of, for example, 5 to 2000 μm, preferably 15 to 1000 μm, more preferably about 20 to 500 μm.

(other optical layers)

The antiglare film of the present invention not only has high antiglare properties but also has high light scattering properties. In particular, it is possible to increase the scattering intensity in a specific angle range while isotropically transmitting and scattering the transmitted light. Furthermore, the vividness of the transmitted image is also high. Therefore, the antiglare film of the present invention can also be formed in combination with other optical layers (for example, polarizers, retardation plates, light guide plates, antireflection plates, low refractive index layers, etc., which are arranged in the optical path) Optical components. That is, the above-mentioned anti-glare film may be provided or laminated on at least one optical path surface of the optical element. For example, an antiglare film may be laminated on at least one surface of the retardation plate, or an antiglare film may be provided or laminated on the outgoing surface of the light guide plate.

In particular, the anti-glare film in which the anti-glare layer is provided with scratch resistance can function as a protective film. Therefore, the antiglare film of the present invention is preferably used as a laminate (optical member) using an antiglare film instead of at least one of the two protective films of the polarizer, that is, an antiglare film is laminated on at least one side of the polarizer. A laminated body (optical member) made of a film. When used as a protective film on both surfaces of a polarizing plate, high scratch resistance can be imparted to optical elements (polarizing plate, etc.) while preventing glare on the display surface.

In addition, these optical layers may be used instead of the said transparent film, and an optical layer may be laminated|stacked further besides a transparent film.

(adhesive layer)

In the antiglare film of the present invention, an adhesive layer may be formed on at least a part of the other surface of the transparent film. The anti-glare film in which the adhesive layer is formed on the other side of the transparent film of the anti-glare layer can also be used as a protective film for various touch panel display devices including smartphones and tablet PCs.

The adhesive layer is formed of a conventional transparent adhesive. As the binder, for example, rubber-based adhesives, acrylic-based adhesives, olefin-based adhesives (modified olefin-based adhesives, etc.), silicone-based adhesives, and the like can be illustrated.

Examples of rubber-based binders include combinations of rubber components (natural rubber, synthetic rubber, thermoplastic elastomer, etc.) and tackifiers (terpene resins, rosin-based resins, petroleum resins, modified olefin-based resins, etc.) wait.

As an acrylic adhesive, for example, an adhesive composed of an acrylic copolymer mainly composed of C _2-10 alkyl acrylates such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate can be used. agent. Examples of copolymerizable monomers for acrylic copolymers include: (meth)acrylic monomers [e.g. (meth)acrylic acid, methyl (meth)acrylate, hydroxyethyl (meth)acrylate , hydroxypropyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, acrylamide, N-methylolacrylamide, etc.], polymerizable nitrile compounds [such as , (meth)acrylonitrile, etc.], unsaturated dicarboxylic acids or their derivatives (for example, maleic anhydride, itaconic acid, etc.), vinyl esters (for example, vinyl acetate, vinyl propionate, etc.), Aromatic vinyls (for example, styrene, etc.) and the like.

Examples of olefin-based binders include ethylene-(meth)acrylic acid copolymers, ethylene-2-hydroxyethyl(meth)acrylate copolymers, and ethylene-glycidyl(meth)acrylate copolymers. , ethylene-vinyl acetate-(meth)acrylic acid copolymer, ethylene-(meth)acrylate-maleic acid (anhydride) copolymer, partially saponified ethylene-vinyl acetate copolymer, etc.

As a silicone-based binder, for example, a silicone rubber component [made of monofunctional R ₃ SiO _1/2 (wherein, R represents an alkyl group such as a methyl group, an aryl group such as a phenyl group, etc.; the same below) can be used. ) and four-functional SiO ₂ formed MQ resin, etc.] and silicone resin components (difunctional R ₂ SiO alone, or an oily combination of difunctional R ₂ SiO and monofunctional R ₃ SiO _1/2 Or gum (gum)-like components, etc.) are dissolved in organic solvents, such as binders. The above-mentioned silicone rubber component may also be cross-linked.

Among these adhesives, silicone-based adhesives are preferable in terms of optical properties, reworkability, and the like.

The thickness of the adhesive layer is, for example, 1 to 150 μm, preferably 10 to 100 μm, more preferably about 20 to 70 μm (especially 25 to 50 μm).

The adhesive layer may be formed on the entire surface of the other surface, or may be formed on a part of the other surface (for example, the peripheral portion). Further, in the case of being formed on the peripheral edge, in order to improve the workability for bonding, a frame-shaped member may be formed on the peripheral edge of the anti-glare film (for example, a plastic sheet is laminated on the peripheral edge), and the frame-shaped member may be form an adhesive layer.

(Characteristics of anti-glare film)

The antiglare film of the present invention has a large number of fine uneven structures corresponding to the phase separation structure formed on the surface of the antiglare layer. Therefore, it is possible to suppress the reflection of the outside scene due to the surface reflection, and it is possible to improve the anti-glare property. In addition, evaluation of the anti-glare property can be performed by visually observing the reflection of fluorescent lamps, and by using a gloss meter according to JIS K7105. The 60° gloss of the anti-glare film (anti-glare layer) of the present invention may be 30 or more, for example, 30-80, preferably 40-70, more preferably about 50-60 (especially 52-55). If the gloss is too small, glare or blurred characters are likely to occur.

In addition, the evaluation of glare and blurred characters can be evaluated by using a high-definition liquid crystal display device with a resolution of about 200ppi. More simply, it can be evaluated by visual inspection using a high-definition smartphone with a resolution of about 300ppi. When the antiglare film of the present invention is disposed on a display device having a resolution of 200 ppi, glare can be suppressed even if the antiglare layer is separated from the display surface by 0.05 mm or more (especially about 0.1 to 0.4 mm).

In addition, for the anti-glare film of the present invention, as the optical characteristics of ensuring anti-glare properties, reducing glare, and avoiding blurred characters at an optimal level, transmission image clarity, haze, and total light rays are preferred. The transmittance is adjusted in a specific range.

In the case of using an optical slit with a width of 0.5 mm, the clarity of the transmitted image of the anti-glare film can be selected from the range of about 70 to 100%, preferably 75 to 100% (for example, 75 to 95%), and more preferably Around 80-100% (especially 80-90%). If the sharpness of the transmitted image is too small, the blurring of the transmitted light will increase, and when it is used in a high-definition display device, the outline of the pixel will be blurred, so that blurring of characters will easily occur.

The transmission image sharpness is a scale for quantifying blurring and distortion (distortion) of light transmitted through a film. The clarity of the transmitted image is measured after passing through an optical slit for moving the transmitted light from the film, and calculated from the amount of light in the bright and dark parts of the optical slit. That is, when the film blurs the transmitted light, the image of the slit formed on the optical slit becomes coarse, so the light quantity of the transmitted part is 100% or less. On the other hand, in the non-transmitted part, Light leakage is therefore 0% or more. The value C of the sharpness of the transmitted image is defined by the following formula, where M is the maximum value of the transmitted light in the transparent part of the optical slit, and m is the minimum value m of the transmitted light in the opaque part.

C(%)=[(M-m)/(M+m)]×100

That is, the closer the value of C is to 100%, the smaller the image blur caused by the anti-glare film [Reference: Suga, Mitamura, Coating Technology, July 1985 Issue].

As a measuring device for measuring the sharpness of the above-mentioned transmission image, an image measuring instrument ICM-IDP manufactured by Suga Test Instruments Co., Ltd. can be used. As the optical slit, an optical slit having a width of 0.125 to 2 mm can be used.

The haze of the antiglare film of the present invention is, for example, 10 to 40%, preferably 12 to 35%, more preferably about 15 to 30% (especially 20 to 30%). If the haze is too high, glare and characters will be blurred easily, and if the haze is too small, the anti-glare property will be reduced.

The total light transmittance of the antiglare film of the present invention is, for example, 70 to 100%, preferably 80 to 100%, more preferably 85 to 100% (for example, 85 to 95%), particularly preferably 90 to 100% ( For example, about 90-99%).

The haze and the total light transmittance can be measured in accordance with JIS K7105 using an NDH-5000W haze meter manufactured by Nippon Denshoku Kogyo Co., Ltd.

The pencil hardness (750g load) of the anti-glare film (anti-glare layer) of the present invention may be, for example, H or higher (especially 2H or higher) according to JIS K5400, or may be, for example, H to 4H, preferably about 2H to 3H.

(Manufacturing method of anti-glare film)

The anti-glare film of the present invention is obtained by a production method including a drying step of applying a solution containing various resin components on a support (especially a transparent film) and utilizing Destabilization decomposes to form a phase-separated structure. When containing a curable resin precursor, the antiglare film of this invention is obtained through the hardening process of hardening the said curable resin precursor further.

Specifically, in the drying process, a resin composition (particularly a liquid composition such as a homogeneous solution or a mixed solution) composed of various resin components (particularly polymers and curable resin precursors) and a solvent is used, and the In the process of evaporating or removing the solvent by drying etc. in the liquid phase (or homogeneous solution or its coating) of the resin composition, phase separation is caused by destabilizing decomposition accompanied by concentration concentration, and the interphase distance (pitch or mesh diameter) Can form a more regular phase separation structure. The co-continuous phase structure can be produced by setting drying conditions or formulations that can improve the melt fluidity of the resin composition after solvent evaporation.

More specifically, the above-mentioned wet destabilization decomposition can generally be carried out by coating a mixed liquid or a resin composition (homogeneous solution) comprising at least one polymer, at least one curable resin precursor, and a solvent on a support, and This is done by evaporating the solvent from the coating. In the case of using a releasable support as the above-mentioned support, by peeling the anti-glare layer from the support, an anti-glare film composed of the anti-glare layer alone can be obtained, and by using a non-releasable support (preferably a transparent support) As the support body, an anti-glare film having a laminated structure composed of a support body and an anti-glare layer can be obtained. In addition, by raising the evaporation temperature of the solvent or using a low-viscosity component as part of the resin, a co-continuous phase structure in which phase-separated structures are connected can be produced. The reason why the concave-convex structure becomes a co-continuous phase structure is generally presumed to be because the resin component does not lose fluidity even after the solvent evaporates, and the concave-convex structure is melted by heat and they are connected.

In the present invention, when destabilizing decomposition occurs, a co-continuous phase structure is formed with the progress of phase separation. When the phase separation further proceeds and becomes coarser, the continuous phase becomes discontinuous due to the existence of its own surface tension, and becomes a droplet phase. Structure (sea-island structure of independent phases such as spherical, spherical, disc-shaped or ellipsoid-shaped). Therefore, depending on the degree of phase separation, an intermediate structure between the co-continuous phase structure and the droplet phase structure (the phase structure during the transition from the above-mentioned co-continuous phase to the droplet phase) may also be formed. In the present invention, the phase separation structure of the anti-glare layer can be a sea-island structure (a liquid droplet phase structure, or a phase independent or isolated phase structure), a co-continuous phase structure (or a network structure), or a co-continuous phase structure (or mesh structure) in the initial stage of drying. It may be an intermediate structure in which a co-continuous phase structure and a liquid droplet phase structure are mixed. With these phase separation structures, fine unevenness can be formed on the surface of the antiglare layer after the solvent is dried. In addition, in the drying process, by increasing the drying temperature to such an extent that the fluidity of the resin composition can be ensured even after the solvent is dried, and/or including a low-viscosity component as the resin component, the fine unevenness on the surface can be melted and connected, even if it is originally A co-continuous structure can also be mutated into a concave-convex structure with further increased continuity.

烷、四氢呋喃等)、脂肪族烃类(己烷等)、脂环族烃类(环己烷等)、芳香族烃类(甲苯、二甲苯等)、卤代烃类(二氯甲烷、二氯乙烷等)、酯类(乙酸甲酯、乙酸乙酯、乙酸丁酯等)、水、醇类(乙醇、异丙醇、丁醇、环己醇等)、溶纤剂类(甲基溶纤剂、乙基溶纤剂等)、乙酸溶纤剂类、亚砜类(二甲亚砜等)、酰胺类(二甲基甲酰胺、二甲基乙酰胺等)等。另外，溶剂也可以为混合溶剂。In the wet destabilization decomposition, the solvent can be selected according to the types and solubility of the above-mentioned polymers and curable resin precursors, as long as the solid components (multiple polymers and curable resin precursors, reaction initiators, etc.) can be dissolved uniformly at least , other additives) solvent. As such solvents, for example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (di

alkane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (methylene chloride, di ethyl chloride, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), acetic acid cellosolves, sulfoxides (dimethyl sulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.), etc. In addition, the solvent may be a mixed solvent.

As a preferred form of the above-mentioned resin composition (mixed solution), a composition comprising the above-mentioned thermoplastic resin, a photocurable compound, a photopolymerization initiator, and a solvent capable of dissolving the above-mentioned thermoplastic resin and photocurable compound can be used. In a preferred aspect, a composition containing the above-mentioned plural kinds of mutually incompatible polymers, a photocurable compound, a photopolymerization initiator, and a solvent can also be used.

The concentration of the solute (polymer and curable resin precursor, reaction initiator, other additives) in the mixed solution can be selected within the range that phase separation occurs and the range that does not impair the casting and coating properties, for example, 1 to 80% by weight, preferably 5 to 60% by weight, more preferably 15 to 40% by weight (especially 20 to 40% by weight).

As the casting or coating method, conventional methods such as spray coating, roll coating, air knife coating, blade coating, bar coating, reverse roll coating, wire-wound bar coating, comma coating (comma coating) can be mentioned. coater), dip-extrusion roll coating, die coating, gravure coating, micro gravure coating, screen coating method, dipping method, spray method, spin coating method, etc. Among these methods, a wire bar coating method, a gravure coating method, and the like are commonly used.

Phase separation by destabilizing decomposition can be induced by evaporating the solvent after casting or coating the above mixed solution. In terms of evaporation of the solvent, heat drying is preferable from the viewpoint of easiness of forming elongated protrusions on the surface of the anti-glare layer. The drying temperature can be selected from the range of, for example, 30 to 200° C. (for example, 40 to 150° C.). From the viewpoint of easy formation of a co-continuous phase structure, the solvent can be evaporated by drying at a temperature exceeding 80° C. For example, the temperature is about 82 to 120°C, preferably 85 to 110°C, more preferably about 88 to 105°C (especially 90 to 100°C). The drying time is, for example, 1 to 60 minutes, preferably 1.2 to 50 minutes, more preferably about 1.5 to 30 minutes (particularly 1.8 to 10 minutes). If the drying temperature is too low or the drying time is too short, the amount of heat applied to the resin component becomes insufficient, the melt fluidity of the resin component decreases, and it becomes difficult to form elongated protrusions. On the other hand, if the drying temperature is too high or the drying time is too long, the temporarily formed elongated protrusions will be reduced in height due to further flow, but the structure will be maintained. Therefore, drying temperature and drying time can be used as a method of adjusting the anti-glare property and sliding property by changing the height.

In the present invention, by drying at such a relatively high temperature for an appropriate time, heat sufficient to melt and flow the resin component can be applied. Therefore, the above-mentioned elongated protrusions and co-continuous phase structure can be easily formed by destabilizing decomposition accompanying solvent evaporation, and regularity or periodicity can be imparted to the average distance between domains of the phase separation structure.

In the curing step, the phase-separated structure formed by destabilizing decomposition can be immobilized immediately by curing the precursor. Depending on the type of curable resin precursor, the curing of the precursor can be performed by heating, light irradiation, etc., or a combination of these methods. The heating temperature can be selected from an appropriate range as long as it has the above-mentioned phase separation structure, for example, about 50 to 150° C., or can be selected from the same temperature range as in the above-mentioned phase separation step.

Irradiation can be selected according to the type of photocurable components and the like, and usually ultraviolet rays, electron beams, and the like can be used. A commonly used exposure source is usually an ultraviolet irradiation device. In addition, light irradiation can be performed in an inert atmosphere as needed.

As the light source, for example, in the case of ultraviolet rays, Deep UV lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, halogen lamps, laser light sources (light sources such as helium-cadmium lasers and excimer lasers) and the like can be used. The amount of irradiation light (irradiation energy) varies depending on the thickness of the coating film, and may be, for example, 50 to 10000 mJ/cm ² , preferably 70 to 7000 mJ/cm ² , more preferably about 100 to 5000 mJ/cm ² .

In the case of further forming an adhesive layer, it can be applied to the other surface of the transparent film by using a conventional method, for example, the above-mentioned casting or coating method.

[display device]

The antiglare film of the present invention has hard coat properties and high antiglare properties. In addition, it is possible to increase light scattering intensity in a specific angle range while isotropically transmitting and scattering transmitted light. Furthermore, the clarity of the transmitted image is excellent, and characters on the display surface are less blurred. Therefore, the antiglare film of the present invention can be used in various display devices, such as display devices such as liquid crystal display (LCD) devices, organic EL display (OLED) devices, plasma displays, and display devices with touch panels. In particular, the anti-glare film of the present invention can be used as a member that does not deteriorate image quality due to glare or blurred characters even in high-definition display devices of 200 ppi or more (especially 300 ppi or more). Therefore, the antiglare film of the present invention can be preferably used in devices that are often used as high-definition display devices among these display devices, such as: liquid crystal display devices (including liquid crystal display devices that can be used as display devices with touch panels), organic EL Display devices (including organic EL devices that can be used as display devices with touch panels).

The liquid crystal display device may be a reflective liquid crystal display device that illuminates a display unit including a liquid crystal unit with external light, or may be a transmissive liquid crystal display device that includes a backlight unit for illuminating the display unit. In the reflective liquid crystal display device described above, incident light from the outside can be introduced through the display unit, and the transmitted light transmitted through the display unit can be reflected by the reflective member to illuminate the display unit. In the reflective liquid crystal display device, the anti-glare film and optical members (particularly, a laminate of a polarizing plate and an anti-glare film) may be provided in the optical path ahead of the reflective member. For example, the antiglare film of the present invention may be provided or laminated between the reflective member and the display unit, on the front surface of the display unit, or the like.

In a transmissive liquid crystal display device, the backlight unit may also include a light guide plate for entering light from a light source (a tubular light source such as a cold cathode tube, a point light source such as a light-emitting diode, etc.) from one side and emitting it from a front emitting surface. (For example, a light guide plate with a wedge-shaped cross section). In addition, a prism sheet may be provided on the front side of the light guide plate as needed. It should be noted that, generally, a reflection member for reflecting light from the light source to the exit surface side is provided on the back surface of the light guide plate. In such a transmissive liquid crystal display device, generally, the above-mentioned anti-glare film and optical member may be provided in the optical path in front of the light source. For example, the above-mentioned anti-glare film and optical member may be provided or laminated between the light guide plate and the display unit, on the front surface of the display unit, or the like.

The antiglare film of the present invention is particularly effective for organic EL display devices. The organic EL is composed of a light-emitting diode (LED) whose light-emitting layer is made of an organic compound, and emits light using excitons generated by recombination of electrons and holes injected into the organic compound. The light-emitting material used in the light-emitting layer may be a high-molecular material or a low-molecular material. In addition, organic EL forms a light-emitting element on each pixel, and the light-emitting element is usually on a substrate such as a cathode/electron injection layer/electron transport layer/light-emitting layer/hole transport layer/hole injection layer/anode/glass plate or transparent plastic plate Formed on.

In addition, organic EL has a heterojunction, and electrons and holes are respectively sealed in other layers. The aforementioned heterojunction may also be a double heterojunction.

等。电极间各层的厚度为数nm至数百nm，整体具有1μm以下左右的厚度即可。As electrodes, metal oxides such as ITO are generally used as anodes, and metals such as Al, Mg, Ag, and Li alloys are used as cathodes. As materials for each layer, organic substances such as diamine, anthracene, and metal complexes are generally used. In detail, the hole transport layer can be composed of Formation of oxadiazole/triazole etc. The hole blocking layer can be formed of a phenanthrene derivative or the like. The doping material can be DCM2[4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl-4H-pyran], coumarin 6,

wait. The thickness of each layer between the electrodes is several nm to several hundreds nm, and the overall thickness may be about 1 μm or less.

As a driving method, it is possible to adopt an active matrix driving method in which active elements such as TFTs (thin film transistors) are arranged in each pixel for driving, or to sequentially drive each intersection point by passing current to orthogonal strip-shaped electrodes sequentially. Any one of the passive matrix driving methods for pixels.

The reason why the anti-glare film of the present invention can be used in organic EL is presumably because organic EL has high pixel luminous intensity and the pixel itself emits light that does not pass through color filters such as liquid crystals. That is, it is presumed that since organic EL light has no directivity and tends to glare, when the conventional anti-glare film is used to suppress the glare of organic EL, the anti-glare property decreases.

In addition, for a liquid crystal display device or an organic EL display device (especially an organic EL display device) in which the pixel arrangement is a Pentile arrangement (an arrangement in which one pixel is formed by two colors of GR or GB and alternately filled), the anti-aging method of the present invention The glare film can also suppress glare, so it can be preferably used.

Moreover, the antiglare film of the present invention can suppress glare even if the antiglare layer is far away from the display surface, so it can also be preferably used as an aftermarket protection or protective film (especially an organic film) for preventing damage to a display device. protective film for EL display devices). In particular, since the anti-glare film of the present invention can suppress glare even when the anti-glare layer is spaced apart from the display surface, it is particularly suitable for use with a distance from the display surface (distance between the display surface and the anti-glare layer). A protective film (a film having a large distance from the display surface because it is provided on the outermost surface and the adhesive layer is spaced apart) used in an aspect of 0.05 mm or more (especially about 0.1 to 0.4 mm) is particularly useful.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples. The anti-glare films obtained in Examples and Comparative Examples were evaluated by the following items.

[Size and area of elongated convex portion]

Based on the reflective laser micrograph of the film surface, the presence or absence of elongated protrusions per 1 mm ² was observed, and the average diameter of the meshes of the co-continuous phase structure was obtained as an average value at any 10 locations. In addition, in a region of 1 mm ² , the length ratio of the elongated protrusions having a branched structure to other protrusions was measured.

The convex portion area was measured using a non-contact surface/layer cross-sectional shape measurement system ["VertScan" manufactured by Ryoka Systems Co., Ltd.]. In this system, the surface shape can be measured three-dimensionally by light interference, and the area of the convex part can be obtained by image processing.

[viscosity]

The viscosity at 25° C. was measured in accordance with JIS Z8803 using a B-type viscometer (“BL-type” manufactured by Tokyo Keiki Co., Ltd.).

[Haze and total light transmittance]

Measurement was carried out in accordance with JIS K7136 using a haze meter (manufactured by Nippon Denshoku Co., Ltd., trade name "NDH-5000W").

[transmitted image (image) sharpness]

Using an image measuring instrument (manufactured by Suga Test Instruments Co., Ltd., trade name "ICM-1T"), based on JIS K7105, the film was placed so that the film forming direction of the film was parallel to the slit direction of the optical slit, and the optical measurement was carried out. Determination of image sharpness of films. In the optical slit of the image measuring instrument, the image sharpness in the optical slit with a width of 0.5 mm was measured.

[60° Gloss]

Evaluation was performed using a gloss meter ("1G-320" manufactured by Horiba Seisakusho Co., Ltd.) in accordance with JIS K7105.

[Pencil hardness]

Pencil hardness was measured with a load of 750 g in accordance with JIS K5400.

[Anti-glare]

As for the judgment of the anti-glare property, a naked fluorescent lamp without a louver was irradiated on the anti-glare film, and the degree of glare of the specularly reflected light was visually evaluated according to the following criteria.

◎: No glare

○: slightly dazzling

X: It feels dazzling.

[glare]

For the judgment of glare on the display surface, the obtained anti-glare film was installed on a smartphone ("GALAXY NEXUS" manufactured by Samsung Electronics Co., Ltd.) having an organic EL display with a resolution of 315ppi, and it was visually judged according to the following criteria commented.

◎: No glare felt

○: Slightly felt glare

×: Glare is felt.

[character blurred]

In terms of judging blurred characters on the display surface, the anti-glare film provided on a smartphone having an organic EL display with a resolution of 315ppi ("GALAXY-NEXUS" manufactured by Samsung Electronics Co., Ltd.) passed the following criteria Evaluation was performed visually.

◎: Characters are not blurred

○: Characters are slightly blurred

X: Characters are felt to be blurred.

Example 1

An acrylic resin having a polymerizable unsaturated group in the side chain [made by adding 3,4-epoxycyclohexenyl methacrylate to a part of the carboxyl group of (meth)acrylic acid-(meth)acrylate copolymer The compound; "CYCLOMER P (ACA) 320M" manufactured by Daicel Co., Ltd., solid content: 49.6% by weight] 5.65 parts by weight, cellulose acetate propionate (degree of acetylation = 2.5%, degree of propionylation = 46%, poly Styrene-equivalent number average molecular weight: 75,000; "CAP-482-20" manufactured by Eastman Co., Ltd.) 1.2 parts by weight, polyfunctional acrylic UV-curable compound ("DPHA" manufactured by Daicel-Cytec Co., Ltd., viscosity: 5250 mPa·s) 4 Parts by weight, 2.77 parts by weight of an acrylic UV curable compound ("PET1A" manufactured by Daicel-Cytec, viscosity 1100mPa·s), and 0.53 parts by weight of a photoinitiator ("IRGACURE907" manufactured by BASF Corporation) were dissolved in methyl ethyl ketone (MEK ) in a mixed solvent of 25 parts by weight and 12.15 parts by weight of 1-butanol. This solution was cast onto a 100 μm thick PET film (“A4300” manufactured by Toyobo Co., Ltd.) using a wire-wound squeegee #24, and left in an oven at 95°C for 2 minutes to evaporate the solvent to form a thickness of 100 μm. Coating of about 7 μm. Then, the coating was irradiated with ultraviolet light from a high-pressure mercury lamp (manufactured by Eyegraphics) for about 10 seconds to perform UV curing.

As a result of observation with a reflection laser microscope, as shown in FIG. 2 , a co-continuous phase-separated structure was formed on the entire surface of the coating. That is, one continuous mesh-shaped elongated protrusion is formed every 1 mm ² , and the proportion of elongated protrusions having a branched structure is approximately 100% in all the protrusions. In this surface structure, the average diameter of the meshes of the co-continuous phase structure was about 5 μm, and protrusions were formed on more than half of the entire surface (about 98%).

In addition, when the obtained sheet was pasted on the display of a high-definition organic EL smartphone, no glare from the display was felt. In addition, the indoor fluorescent lights were not reflected, the anti-glare property was excellent, and the characters did not feel blurred.

Example 2

5.65 parts by weight of acrylic resin [CYCLOMERP (ACA) 320M] having a polymerizable unsaturated group in the side chain, 1.2 parts by weight of cellulose acetate propionate (CAP-482-20), a polyfunctional acrylic UV-curable compound (DPHA ) 6 parts by weight, 0.77 parts by weight of an acrylic UV-curable compound containing siloxane ("EB1360" manufactured by Daicel-Cytec Co., Ltd., viscosity: 2100mPa·s), and 0.53 parts by weight of a photoinitiator (IRGACUR907) were dissolved in In a mixed solvent of 25 parts by weight of MEK and 12.15 parts by weight of 1-butanol. After casting this solution on a PET film (A4300) with a thickness of 100 μm using a wire-wound paint bar #24, it was placed in an oven at 90°C for 2 minutes to evaporate the solvent and form a coating with a thickness of about 7 μm . Then, the coating was irradiated with ultraviolet light from a high-pressure mercury lamp (manufactured by Eyegraphics) for about 10 seconds to perform UV curing.

As a result of observation with a reflection laser microscope, as shown in FIG. 3 , a co-continuous phase separation structure having a droplet phase separation structure (droplet phase structure) was formed on a part of the surface of the coating. That is, one continuous mesh-like elongated convex portion is formed every 1 mm ² , and the length ratio of the elongated convex portion having a branched structure to other convex portions is about 80/20. In this surface structure, the average diameter of the meshes of the co-continuous phase structure was about 4 μm, and protrusions were formed on more than half of the entire surface (about 89%).

In addition, when the obtained sheet was pasted on a high-definition organic EL smartphone, no glare from the display was felt. In addition, indoor fluorescent lights are not reflected, and the anti-glare property is also excellent.

Comparative example 1

A UV-cured coating was produced in exactly the same manner as in Example 1 except that the drying temperature was set to 70°C. Observation by a transmission optical microscope revealed that the coating had a droplet-like phase-separated structure.

In addition, when the obtained sheet was pasted on a high-definition organic EL smartphone, the indoor fluorescent light was not reflected, the anti-glare property was excellent, and the characters were not blurred, but the glare of the display was felt.

Comparative example 2

5.65 parts by weight of acrylic resin [CYCLOMERP (ACA) 320M] having a polymerizable unsaturated group in the side chain, 1.2 parts by weight of cellulose acetate propionate (CAP-482-20), and a multifunctional acrylic UV-curable compound ( 6.77 parts by weight of DPHA) and 0.53 parts by weight of photoinitiator (IRGACUR907) were dissolved in a mixed solvent of 25 parts by weight of MEK and 12.15 parts by weight of 1-butanol. This solution was cast on a PET film (A4300) with a thickness of 100 μm using a wire-wound paint bar #24, and then left in an oven at 90° C. for 2 minutes to evaporate the solvent to form a coating with a thickness of about 7 μm. Then, the coating was irradiated with ultraviolet light from a high-pressure mercury lamp (manufactured by Eyegraphics) for about 10 seconds to perform UV curing.

Observation with a reflection laser microscope revealed that the coating had a droplet-like phase-separated structure as shown in FIG. 1 .

In addition, when the obtained sheet was pasted on a high-definition organic EL smartphone, the indoor fluorescent light was not reflected, and the anti-glare property was excellent, and the glare of the display was not felt, but the blurring of characters was remarkable.

Table 1 shows the evaluation results of the antiglare films obtained in Examples and Comparative Examples.

[Table 1]

Example 1 Example 2 Comparative example 1 Comparative example 2 structure co-continuous co-continuous droplet droplet Total light transmittance (%) 91 91 91 89 Haze (%) 18 28 twenty one 42 Transmission image sharpness (%) 75 85 63 80 60° Gloss 51 54 48 41 pencil hardness 2H 2H 2H 2H Anti-glare ◎ ○ ◎ ◎ glare ○ ◎ x ◎ blurred characters ◎ ◎ ◎ x

As can be seen from the results in Table 1, the anti-glare film of the example is excellent in anti-glare and can suppress glare and blurred characters, while the anti-glare film of the comparative example produces glare or blurred characters.

Industrial Applicability

The antiglare film of the present invention can be used as an antiglare film for various display devices including, for example, liquid crystal display (LCD) devices, cathode ray tube display devices, organic or inorganic electroluminescence (EL) displays, Field Emission Displays (FED), Surface Conduction Electron Emission Displays (SED), Rear Projection TV Displays, Plasma Displays, Display Devices with Touch Panels, etc.

Among them, the anti-glare film of the present invention is useful for various displays including PC monitors and televisions. For high-definition display devices, anti-glare and anti-glare properties can be simultaneously realized, and blurring of characters can be suppressed, so it is used as a display for car navigation. , smartphones, tablet personal computers (PCs) and other displays and anti-glare films with touch panel display devices are particularly useful.

In particular, a film containing a curable resin precursor in the anti-glare layer has excellent scratch resistance, and in a display device (for example, 300PPi or more) with extremely high precision, it can maintain the scratch resistance even if it is spaced from the display. Therefore, it is particularly useful as a protective film (protective film) for after-sales of liquid crystal display devices and organic EL display devices (especially organic EL display devices) because of the above-mentioned optical properties.

Claims (13)

1. An anti-glare film comprising an anti-glare layer having elongated protrusions on the surface, the elongated protrusions being formed by phase separation of a plurality of resin components, Wherein, the elongated convex part has a branch structure and the total length is more than 100 μm, In addition, one or more elongated protrusions exist per 1 mm ² of the surface of the antiglare layer. 2 . The antiglare film according to claim 1 , wherein the elongated protrusions form a co-continuous phase structure, and the average diameter of the meshes of the co-continuous phase structure is 1 to 70 μm. 3. The antiglare film according to claim 1 or 2, wherein the length ratio of the elongated protrusions having a branched structure to the other protrusions is the former/the latter=100/0 to 50/50. 4. The antiglare film according to any one of claims 1 to 3, which has a transmission image clarity of 70 to 100%, a haze of 10 to 40%, and a total light transmittance of 70 to 100%. The above-mentioned clarity of the transmitted image was measured with a visibility measuring instrument using an optical slit with a width of 0.5 mm. 5. The antiglare film according to any one of claims 1 to 4, wherein the multiple resin components comprise multiple polymers and at least one curable resin precursor selected from the group consisting of multiple The polymer is selected from styrene resins, (meth)acrylic resins, alicyclic olefin resins, polyester resins, aliphatic organic acid cellulose esters and aromatic organic acid cellulose esters, and the curable resin The group of precursors includes: epoxy (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates, silicone (meth)acrylates and at least two polymerizable Polyfunctional monomers with unsaturated bonds, and, at least two components of the polymer phase separate by destabilizing decomposition from the liquid phase, Also, the curable resin precursor is cured. 6 . The antiglare film according to claim 5 , wherein the curable resin precursor includes a low-viscosity curable resin precursor having a viscosity at 25° C. based on JIS Z8803 of 3000 mPa·s or less. 7. The antiglare film according to any one of claims 1 to 6, wherein when provided on a display device having a resolution of 200 ppi, glare can be suppressed even if the antiglare layer is at a distance of 0.05 mm or more from the display surface. 8. The antiglare film according to claim 7, wherein the display device is an organic EL display device. 9. The antiglare film according to any one of claims 1 to 8, further comprising a transparent film, and an antiglare layer is formed on one surface of the transparent film. 10 . The antiglare film according to claim 1 , wherein an adhesive layer is formed on at least a part of the other surface of the transparent film. 11 . 11. The antiglare film according to any one of claims 1 to 10, which is a protective or protective film provided on the outermost surface of a display device. 12. A method for producing an antiglare film, which is a method for producing the antiglare film according to claim 1, the method comprising the following drying process: a solution containing multiple resin components is coated on a support, and the The destabilizing decomposition accompanying solvent evaporation forms a phase-separated structure. 13. The manufacturing method according to claim 12, wherein heating is performed at a temperature exceeding 80° C. in the drying step.

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