TW201544833A - Method for producing laminate, laminate, polarizing plate, image display device, and method for improving readability of image display device - Google Patents

Abstract

Provided is a method for producing a laminate, having excellent production stability, and with which it is possible to obtain a display device with good anti-glare properties, while suppressing the occurrence of glare at an extremely high level, and having excellent contrast. Provided is a method for producing a laminate comprising an anti-glare layer having surface irregularities, on one surface of a light-transmitting substrate. The method has a step in which an anti-glare layer composition containing organic fine particles, inorganic fine particles, a binder resin and a solvent is applied to one surface of the light-transmitting substrate, and the applied film is dried and then cured, to form the anti-glare layer. The anti-glare layer composition is prepared by mixing and stirring the binder resin and organic fine particles into the solvent to prepare an intermediate composition, and subsequently mixing and dispersing the inorganic fine particles in the intermediate composition to form the anti-glare layer composition.

Description

Manufacturing method of laminated body, laminated body, polarizing plate, image display device, and visibility improving method of image display device

The present invention relates to a method for manufacturing a laminate, a laminate, a polarizing plate, an image display device, and a method for improving visibility of an image display device.

In the image display device such as a cathode ray tube display device (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), an electronic paper, a tablet PC, a touch panel, etc., usually at the outermost The surface is provided with an optical laminate for anti-reflection.

Such an optical layering system for antireflection suppresses the reflection of an image or reduces the reflectance by scattering or interference of light.

As one of the optical laminates for antireflection, an antiglare film having an antiglare layer having an uneven shape on the surface of a transparent substrate is known. The anti-glare film can scatter external light by the uneven shape of the surface to prevent a decrease in visibility due to reflection of external light or reflection of the image.

Further, since the optical laminate is usually provided on the outermost surface of the image display device, it is required to impart hard coat properties in order to prevent damage during operation.

As a conventional anti-glare film, for example, it is known to be coated on the surface of a light-transmitting substrate. A resin containing a filler such as silica is applied to form an antiglare layer (see, for example, Patent Documents 1 and 2).

The anti-glare film has a type in which an uneven shape is formed on the surface of the anti-glare layer by aggregation of particles such as cohesive ceria, and an organic filler is added to the resin to form a concavo-convex shape on the surface of the layer, or A type in which a film having irregularities on the surface of the layer is laminated to transfer the uneven shape or the like.

However, in the conventional anti-glare film, in order to improve the anti-glare property by the action of the surface shape of the anti-glare layer to obtain light diffusion and anti-glare effect, it is necessary to make the uneven shape coarser in any type. In many cases, if the unevenness becomes coarser and larger, the fog value (haze value) of the coating film rises and white blurring occurs, and the contrast of the display image is lowered.

Further, the anti-glare film of the conventional type also has a problem of causing the brilliance of the so-called glare on the surface of the film to reduce the visibility of the display screen. The glare is when the image display device is turned on, and when the transmitted light from the back reaches the screen, a small brightness unevenness appears on the surface of the screen. If the angle observed by the observer is changed, the brightness is uneven. The phenomenon of gradual change, especially when the entire surface is white or the entire surface is green.

In particular, in recent years, since a mobile terminal such as a 4K panel or a smart phone or a tablet has been increasingly refined, the glare cannot be sufficiently controlled by the conventional anti-glare film.

For such a problem, for example, a method of improving the glare of the antiglare layer by utilizing the internal haze is known (for example, refer to Patent Document 3 and Patent Document 4). However, in the method of utilizing the internal haze of the anti-glare layer, in order to cope with the ultra-high-definition panel in recent years, if the internal haze is increased to further suppress glare, the darkroom contrast and resolution of the displayed image are deteriorated. And other issues.

Further, for example, a method of controlling the surface shape of the antiglare layer to improve glare or contrast is known (for example, see Patent Document 5). However, in the method described in Patent Document 5, since a large amount Since the inorganic fine particles are added, the coating property of the composition for forming an antiglare layer is deteriorated, and the problem of coating defects such as spots or streaks is likely to occur.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. Hei 6-18706

Patent Document 2: Japanese Patent Laid-Open No. 10-20103

Patent Document 3: Japanese Patent Laid-Open No. 11-305010

Patent Document 4: Japanese Laid-Open Patent Publication No. 2002-267818

Patent Document 5: Japanese Patent No. 4510124

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a method for producing a laminated body which is excellent in manufacturing stability, has excellent anti-glare properties, can suppress generation of glare at an extremely high level, and can obtain a display image excellent in high contrast. A laminate, a polarizing plate using the laminate, an image display device, and a method for improving the visibility of the image display device.

The present invention relates to a method for producing a laminate, which is a method for producing a laminate having an antiglare layer having a concavo-convex shape on one surface of a light-transmitting substrate, and characterized in that it has the following steps: The composition for an anti-glare layer of the organic fine particles, the inorganic fine particles, the binder resin, and the solvent is applied onto one surface of the light-transmitting substrate, and the formed coating film is cured after drying to form the anti-glare layer; The antiglare layer composition is used in the above solvent The binder resin and the organic fine particles are mixed and stirred to prepare an intermediate composition, and then the inorganic fine particles are mixed and dispersed in the intermediate composition.

Moreover, the present invention is also a laminated body which has an antiglare layer having a concave-convex shape on a surface of one surface of a light-transmitting substrate, and is characterized in that the surface of the anti-glare layer is divided into 100 μm square. The measurement area is obtained, and the arithmetic mean roughness Sa of each measurement area is obtained. When the average value of the arithmetic mean roughness Sa is set to Ma, and the standard deviation of the arithmetic mean roughness Sa is Sq, the Ma and Sq are obtained. The ratio (Sq/Ma) is 0.15 or less.

In the laminate of the present invention, it is preferable that the antiglare layer contains a binder resin, organic fine particles, and inorganic fine particles.

Moreover, the present invention is also a laminated body which has an antiglare layer having a concavo-convex shape on one surface of a light-transmitting substrate, and is characterized in that the anti-glare layer contains a binder resin, organic fine particles, and In the inorganic fine particles, the inorganic fine particles are sparsely distributed around the organic fine particles, and are uniformly distributed in the antiglare layer other than the periphery of the organic fine particles.

In the laminate of the present invention, it is preferable that the inorganic fine particles are cerium oxide fine particles, and it is preferable that the aggregate of the cerium oxide fine particles has an average particle diameter of 100 nm to 1 μm.

Further, it is preferable that the binder resin has a polyfunctional acrylate monomer having no hydroxyl group in its molecule as a main material.

Further, it is preferable that the organic fine particles are selected from the group consisting of acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyethylene resins, epoxy resins, silicone resins, and polyvinylidene fluoride resins. The fine particles composed of at least one of the group consisting of the polyvinyl fluoride resin are preferably not subjected to surface hydrophilization treatment.

Moreover, the present invention is also a polarizing plate which is provided with a polarizing element, and is characterized in that the polarizing plate includes the laminated body on the surface of the polarizing element.

The present invention also provides an image display device comprising the above laminated body or the polarizing plate on an outermost surface.

Moreover, the present invention is also a method for improving the visibility of an image display device, which is characterized in that a laminate having an anti-glare layer having a concave-convex shape on a surface of one surface of a light-transmitting substrate is used, and is characterized in that: A composition for an antiglare layer containing organic fine particles, inorganic fine particles, a binder resin, and a solvent is applied onto one surface of the light-transmitting substrate, and the formed coating film is dried and then cured to form the laminate. The antiglare layer is prepared by mixing the binder resin and the organic fine particles in the solvent and stirring them to prepare an intermediate composition, and then mixing and dispersing the inorganic fine particles in the intermediate composition to prepare the antiglare. The layer is composed of a composition.

Hereinafter, the present invention will be described in detail.

The present inventors have conducted an effort to study a laminate including an antiglare layer having a concavo-convex shape on a light-transmitting substrate, and as a result, it has been found that a composition for an antiglare layer prepared by a specific method is used. The antiglare layer of the laminate has a more uniform and uniform shape than the antiglare layer of the conventional laminate, and the laminate having such an antiglare layer has excellent antiglare properties and can be extremely high. The level suppresses the generation of glare, and an excellent display image with high contrast can be obtained, thereby completing the present invention.

In addition, the inventors of the present invention conducted an effort to find that the ratio (Sq/Ma) of the average value Ma of the arithmetic mean roughness Sa of the uneven shape to the standard deviation Sq of the arithmetic mean roughness Sa is within a specific range. The anti-glare layer which is highly controlled is formed so that the uneven shape is extremely uniform and uniform, and the laminated body of the present invention is completed.

Further, the inventors of the present invention have made an effort to study, and have found that an antiglare layer having a concavo-convex shape controlled in a more uniform and uniform manner than a concavo-convex shape on the surface of a conventional antiglare layer can be used. The layered body of the present invention of another aspect is obtained by controlling the organic fine particles and the inorganic fine particles contained in the inside to be in a specific state.

The present invention relates to a method for producing a laminate having an antiglare layer having an uneven shape on its surface on one surface of a light-transmitting substrate.

The light-transmitting substrate preferably has smoothness and heat resistance and is excellent in mechanical strength. Specific examples of the material for forming the light-transmitting substrate include polyester (polyethylene terephthalate, polyethylene naphthalate), cellulose triacetate, and cellulose diacetic acid. Ester, cellulose acetate butyrate, polyamine, polyimide, polyether oxime, polyfluorene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polymethyl A thermoplastic resin such as methyl acrylate, polycarbonate, or polyurethane. Preferably, polyester (polyethylene terephthalate, polyethylene naphthalate) or cellulose triacetate is exemplified.

The light-transmitting substrate preferably uses the thermoplastic resin in the form of a flexible film-like body. However, depending on the aspect of use of the curable property, a plate of the thermoplastic resin may be used, or a glass plate may be used. Such as the plate body.

In addition, examples of the light-transmitting substrate include an amorphous olefin polymer (COP, Cyclo-Olefin-Polymer) film having an alicyclic structure. A substrate such as a decene-based polymer, a monocyclic cyclic olefin polymer, a cyclic conjugated diene polymer, or a vinyl alicyclic hydrocarbon polymer can be used, and examples thereof include: Zeonex or Zeonor (northene-based resin) manufactured by Swion, SUMILITE FS-1700 manufactured by SUMITOMO BAKELITE, Arton (modified decene-based resin) manufactured by JSR, and Mitsui Chemicals Apel (cyclic olefin copolymer) manufactured by the company, Topas (cyclic olefin copolymer) manufactured by Ticona Co., Ltd., OPTOREZ OZ-1000 series (alicyclic acrylic resin) manufactured by Hitachi Chemical Co., Ltd., and the like.

Further, as a substituting substrate of triacetyl cellulose, an FV series (low birefringence, low photoelastic modulus film) manufactured by Asahi Kasei Chemicals Co., Ltd. is also preferable.

The thickness of the light-transmitting substrate is preferably 5 to 300 μm, more preferably 20 μm, and the upper limit is 200 μm in the case of the film-like body. In the case where the light-transmitting substrate is a plate-like body, it may be a thickness exceeding the thickness.

In the case where the above-mentioned hard coat layer or the like is formed thereon, in order to improve the adhesion, in addition to physical or chemical treatment such as corona discharge treatment or oxidation treatment, a anchoring agent or a primer may be previously prepared. Coating of the coating.

In addition, in the case where triacetyl cellulose which is mainly used for a light-transmitting substrate of an LCD is used as a material and is used for the purpose of thinning a display, it is preferable as the thickness of the light-transmitting substrate. It is 20~65μm.

The antiglare layer is formed on one surface of the light-transmitting substrate and has a concavo-convex shape on the surface.

The method for producing a laminate of the present invention comprises the step of forming such an antiglare layer. In this step, a coating film formed by applying a composition for an antiglare layer containing organic fine particles, inorganic fine particles, a binder resin, and a solvent onto one surface of the light-transmitting substrate is dried and then cured. The above anti-glare layer is formed.

In the method for producing a laminate according to the present invention, since the composition for forming an antiglare layer contains organic fine particles and inorganic fine particles, it is formed on the surface of the formed antiglare layer. The concavo-convex shape is formed more uniformly and uniformly than the concavo-convex shape formed on the surface of the anti-glare layer by a single microparticle (for example, organic microparticles or the like) or agglomerates of a single particle (for example, an aggregate of cerium oxide microparticles). The shape. It is presumed that the inorganic fine particles and the organic fine particles are distributed in the antiglare layer in a specific state in the laminate produced by the method for producing a laminate according to the present invention.

Further, it is preferable that the organic fine particles and the inorganic fine particles have a spherical shape in a single particle state. When the single particles of the organic fine particles and the inorganic fine particles are in the form of such a spherical shape, when the laminated body to be produced is applied to an image display device, a display image with high contrast can be obtained.

In addition, the above-mentioned "spherical shape" includes, for example, a true spherical shape, an elliptical spherical shape, and the like, and does not include the meaning of a so-called amorphous shape.

The organic fine particles are mainly fine particles which form a surface uneven shape of the antiglare layer, and are fine particles which are easy to control the refractive index or the particle diameter. By containing such organic fine particles, it is easy to control the size of the uneven shape formed on the antiglare layer or the refractive index of the antiglare layer, thereby controlling the antiglare property and suppressing the occurrence of glare and white blur.

The organic fine particles are preferably selected from the group consisting of acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyethylene resins, epoxy resins, polyoxyxylene resins, polyvinylidene fluoride resins, and polyvinyl fluoride resins. Microparticles composed of at least one of the constituent groups. Among them, styrene-acrylic acid copolymer fine particles can be suitably used.

The above organic fine particles are preferably not subjected to surface hydrophilization treatment. When the organic fine particles are hydrophilized on the surface, the affinity with the inorganic fine particles is too high, and it is difficult to cause the inorganic fine particles to be sparsely distributed around the organic fine particles. Furthermore, regarding the above "Sparse distribution" is described in detail below.

In addition, the hydrophilization treatment is not particularly limited, and a known method can be used. For example, a method of copolymerizing a monomer having a functional group such as a carboxylic acid group or a hydroxyl group on the surface of the organic fine particles can be mentioned.

The content of the organic fine particles is preferably from 1 to 50% by mass based on the solid content of the composition for an antiglare layer. If it is less than 1% by mass, the antiglare performance of the laminated body to be produced may be insufficient. When it exceeds 50% by mass, there is a problem that white blurring occurs, and the following situation occurs: When the manufactured laminate is used in an image display device, the contrast of the displayed image is poor. A more preferred lower limit is 5% by mass, and a more preferred upper limit is 20% by mass.

Further, the organic fine particles are preferably fine particles having a relatively uniform particle diameter.

Here, the above-mentioned "fine particles having a relatively uniform particle diameter" means that the average particle diameter of the fine particles obtained by weight average is MV, the cumulative 25% diameter is d25, and the cumulative 75% diameter is d75. (d75-d25)/MV is less than 0.25.

In addition, the cumulative 25% diameter means a particle diameter when the particles having a small particle diameter in the particle size distribution are counted to be 25% by mass, and the cumulative 75% diameter is similarly counted to be 75. Particle size in mass %.

The average particle diameter, the cumulative 25% diameter, and the cumulative 75% diameter of the fine particles obtained by the weight average can be measured as the weight average diameter by the Coulter counter method.

When the composition for forming an antiglare layer contains such organic fine particles, it is easy to form a uniform and uniform uneven shape on the surface of the antiglare layer.

Further, the size of the organic fine particles is based on the thickness of the antiglare layer formed, and the like. With appropriate determination, for example, it is preferred that the average particle diameter is from 0.3 to 6.0 μm. If it is less than 0.3 μm, the dispersibility of the organic fine particles cannot be controlled. When the thickness exceeds 6.0 μm, the uneven shape of the surface of the anti-glare layer may increase, and the problem of surface glare may occur. A more preferred lower limit is 2.0 μm, and a more preferred upper limit is 4.0 μm.

Further, it is preferable that the average particle diameter of the organic fine particles is 20 to 90% with respect to the thickness of the formed antiglare layer. When it exceeds 90%, the influence of the film thickness variation on the uneven shape is enhanced, and the antiglare layer is formed into a speckle shape. If it is less than 20%, it may not be sufficient to form a sufficient uneven shape on the surface of the antiglare layer, and the antiglare performance may be insufficient.

Further, when the average particle diameter of the organic fine particles is measured by the organic fine particles alone, the average particle diameter can be measured as a weight average diameter by the Coulter counter method. On the other hand, the average particle diameter of the organic fine particles in the antiglare layer was determined as a value obtained by averaging the maximum diameter of 10 particles in the transmission optical microscope observation of the antiglare layer. Or, when the method is not suitable, in the observation by an electron microscope (preferably TEM, STEM, etc., the same below) of the cross section near the center of the particle, 30 are selected as any of the same species and are substantially the same. Diffusion particles observed in the form of the particle size (the number of selected particles is not clearly defined as the cross section of the particles), and the maximum particle size of the cross section is measured, and the average value is calculated as the average value. The value. Since it is judged based on the image, it can also be calculated using the image analysis software.

The inorganic fine particles mainly have a function of stably forming the organic fine particles in the antiglare layer in a state in which a uniform uneven shape can be formed, and are preferably uniformly dispersed in the composition for an antiglare layer.

As such inorganic fine particles, for example, cerium oxide fine particles are preferable. Following the above The inorganic fine particles are described as cerium oxide fine particles.

By uniformly dispersing the above-mentioned ceria fine particles in the composition for an antiglare layer, it is uniformly dispersed in the formed antiglare layer, and a uniform and uniform uneven shape can be formed on the surface.

The term "homogeneously distributed in the anti-glare layer" means that the thickness direction of the anti-glare layer is not observed under the condition of a magnification of 10,000 times by an electron microscope (preferably a TEM or a STEM type). When 10 sections of the organic fine particles were observed, the area ratio of the cerium oxide microparticles in the observation area of 5 μm square was measured in each cross section, and when the average value was M and the standard deviation was S, For S/M≦0.1.

Further, the distribution of such cerium oxide microparticles can be easily determined by observation of a cross-sectional electron microscope in the thickness direction of the antiglare layer. For example, FIG. 2 is a cross-sectional STEM photograph of the laminate of Example 1, and FIG. 3 is another STEM photograph of the laminate of Example 1. In FIGS. 2 and 3, the dark strip region near the center is the above. In the cross section of the anti-glare layer, in the cross section of the anti-glare layer, blackening is observed, and the plaque-like portion is an agglomerate of the above-mentioned cerium oxide microparticles, and it is possible to clearly confirm that the condensed particles of the cerium oxide microparticles are uniformly dispersed. In the above anti-glare layer. Further, the area ratio of the aggregate of the above-mentioned ceria microparticles can be calculated, for example, using an image analysis software.

In the present invention, the above-mentioned cerium oxide fine particles are preferably surface-treated. By subjecting the above-mentioned cerium oxide microparticles to surface treatment, the composition of the anti-glare layer of the cerium oxide microparticles and the distribution in the formed anti-glare layer can be appropriately controlled, and can be sparsely distributed to the organic microparticles. The surrounding effects are controlled to a moderate range. Further, it is also possible to improve the chemical resistance and saponification resistance of the cerium oxide microparticles themselves.

As the surface treatment, it is preferred that the surface of the microparticles be hydrophobic. Hydration treatment. As such a hydrophobization treatment, for example, a method of treating the above-mentioned ceria microparticles by a decane compound having an alkyl group such as a methyl group or an octyl group can be mentioned.

Here, in general, a hydroxyl group (stanol group) is present on the surface of the above-mentioned ceria microparticles, and by performing the surface treatment described above, the hydroxyl group on the surface of the ceria microparticles is reduced, and the ceria microparticles can be prevented from being excessively aggregated. The effect of preventing uneven dispersion of cerium oxide microparticles.

Further, the above-mentioned ceria fine particles are preferably composed of amorphous ceria. When the above-mentioned cerium oxide microparticles are composed of crystalline cerium oxide, the Lewis acidity of the cerium oxide microparticles is enhanced due to lattice defects contained in the crystal structure, and there is an uncontrollable excessive control of the cerium oxide microparticles. The situation of cohesion.

As such a cerium oxide microparticle, since the aggregate of the above-described particle diameter is easily formed by aggregation of the cerium oxide fine particles, for example, cerium oxide can be suitably used. Here, the above-mentioned so-called cerium oxide is an amorphous cerium oxide having a particle diameter of 200 nm or less which is produced by a dry method, and can be reacted in a gas phase by a volatile compound containing cerium. And get. Specifically, for example, a ruthenium compound, for example, a catalyst obtained by hydrolyzing SiCl ₄ in a flame of oxygen and hydrogen, or the like can be mentioned. Specifically, for example, AEROSIL R805 (manufactured by Nippon Aerosil Co., Ltd.) or the like can be mentioned.

The content of the above-mentioned ceria fine particles is not particularly limited, but is preferably 1.0 to 10.0% by mass in the antiglare layer. When it is less than 1.0% by mass, the organic fine particles may not be formed in such a manner that a uniform uneven shape may be formed. When the amount is more than 10.0% by mass, the viscosity of the composition for an antiglare layer is excessively increased to coat the suitability. The difference is worse. A more preferred lower limit is 3.0% by mass, and a more preferred upper limit is 8.0% by mass.

The above-mentioned cerium oxide fine particles preferably have an average primary particle diameter of 1 to 100 nm. If it is less than 1 nm, a preferable agglomerate may not be formed. When it exceeds 100 nm, light may be diffused by the cerium oxide microparticles, and the contrast of the dark room of the image display apparatus using the laminated body produced may be inferior. A more preferred lower limit is 5 nm, and a more preferred upper limit is 50 nm.

In addition, the average primary particle diameter of the above-mentioned cerium oxide microparticles is a value measured by using an image processing software based on a cross-sectional electron microscope (preferably a TEM, STEM, etc., and a magnification of 50,000 times or more).

Further, in the present invention, in the case where the cerium oxide microparticles form an aggregate, the cerium oxide microparticles are formed in a prismatic shape in a cross-sectional electron microscope of the antiglare layer.

By forming the aggregates which are connected in a pearl necklace shape in the above-mentioned anti-glare layer, it is possible to effectively exhibit the function of stably forming the organic fine particles in a state in which a uniform uneven shape can be formed.

In addition, the structure in which the cerium oxide microparticles are connected in a pearl necklace shape is, for example, a structure in which the cerium oxide microparticles are continuously connected in a straight line (linear structure), and the linear structure is entangled with each other. The structure has an arbitrary structure such as a branched structure in which one or two or more of the plurality of ceria particles are continuously formed in the linear structure.

Moreover, it is preferable that the aggregate of the above-mentioned ceria fine particles has an average particle diameter of 100 nm to 1 μm. If it is less than 100 nm, the above effect may not be exhibited. If it exceeds 1 μm, light may be diffused by the aggregate of the cerium oxide microparticles, and the contrast of the dark room of the image display device using the laminated body produced is poor. situation. A more preferred lower limit of the average particle diameter of the above agglomerates is 200 nm, and a more preferred upper limit is 800 nm.

Further, the average particle diameter of the agglomerates of the cerium oxide microparticles is selected from a 5 μm square region of agglomerates containing a large amount of cerium oxide microparticles according to observation by a cross-sectional electron microscope (about 10,000 to 20,000 times). The particle size of the agglomerates of the cerium oxide microparticles in this region was measured, and the particle diameters of the aggregates of the ten cerium oxide microparticles having the largest particle diameter were averaged.

In addition, the "particle diameter of the aggregate of the cerium oxide microparticles" is obtained by sandwiching the cross section of the aggregate of the cerium oxide microparticles in two parallel straight lines, and the distance between the two straight lines is the largest. The form of the distance between the straight lines of the straight lines is measured. Further, the particle size of the agglomerates of the above-mentioned ceria microparticles can also be calculated using an image analysis software.

The aggregates and the organic fine particles which are connected by the pearl necklace in the specific state are contained in the composition for the antiglare layer, and the uneven shape in the antiglare layer in the laminated body produced is The uneven shape formed by a single fine particle or an agglomerate thereof is formed uniformly and uniformly. As a result, the produced laminate has good anti-glare properties, can suppress glare, and can improve contrast.

The unevenness is uniform and uniform, and although the anti-glare property is sufficiently provided, the convex portion which becomes a singular point disappears. Therefore, since the significant distortion of the transmitted light disappears, glare can be suppressed, and further, since the large diffusion can be eliminated, the contrast can be excellent.

It is speculated that this situation is caused by the reasons listed below.

In other words, after the composition for the anti-glare layer is applied and dried to evaporate the solvent, the ceria-containing fine particles which are appropriately agglomerated are uniformly dispersed, whereby the organic fine particles forming the irregularities are uniformly dispersed. Further, the inorganic fine particles are sparsely distributed around the organic fine particles, and the adhesive resin is hardened as compared with a portion where the inorganic fine particles are largely distributed. Since the shrinkage is increased, a convex portion which is sufficient for exhibiting good anti-glare property is stably formed. Therefore, it is estimated that the uneven shape (convex portion) formed on the surface of the antiglare layer by the organic fine particles is uniform and uniform as compared with the uneven shape (convex portion) formed by the fine particles.

As the binder resin, a polyfunctional acrylate monomer having no hydroxyl group in its molecule is preferably used as a main material. The above-mentioned "a multifunctional acrylate monomer having no hydroxyl group in the molecule as a main material" means that the content of the polyfunctional acrylate monomer having no hydroxyl group in the molecule is the largest among the raw material monomers of the above-mentioned binder resin.

Since the polyfunctional acrylate monomer having no hydroxyl group in the above molecule is a hydrophobic monomer, it is preferred that the binder resin constituting the antiglare layer is a hydrophobic resin in the laminate of the present invention. When a resin having a hydrophilicity of a hydroxyl group in the binder resin is a main component, a solvent having a relatively high polarity (for example, isopropyl alcohol) is less likely to evaporate, and there is a possibility that the inorganic fine particles are not sparsely distributed around the organic fine particles.

Examples of the polyfunctional acrylate monomer having no hydroxyl group in the above molecule include pentaerythritol tetraacrylate (PETTA), 1,6-hexanediol diacrylate (HDDA), and dipropylene glycol diacrylate ( DPGDA), tripropylene glycol diacrylate (TPGDA), PO modified neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate (TMPTA), trimethylolpropane Ethoxy triacrylate, dipentaerythritol hexaacrylate (DPHA), neopentyl alcohol ethoxy tetraacrylate, di-trimethylolpropane tetraacrylate, and the like. Among them, neopentyltetraol tetraacrylate (PETTA) can be suitably used.

Moreover, as another adhesive resin, it is preferable to be transparent, for example, it is preferable that the free radiation hardening type resin which is hardened by ultraviolet rays or electron beams is hardened by irradiation of ultraviolet rays or electron beams.

In addition, in the present specification, the term "resin" is a concept including a monomer, an oligomer, a polymer, etc., unless otherwise specified.

The above-mentioned free radiation-curable resin may, for example, be a compound having a functional group such as an acrylate or the like and having one or two or more unsaturated bonds.

Examples of the compound having one unsaturated bond include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, methylstyrene, and N-vinylpyrrolidone. Examples of the compound having two or more unsaturated bonds include trimethylolpropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, and diethylene glycol di(meth)acrylate. , pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth) acrylate, 1,6-hexanediol di(meth) acrylate, neopentyl glycol di(methyl) Acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol five ( Methyl) acrylate, tripentenol octa (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, iso-cyanuric acid tri(meth) acrylate, iso-cyanuric acid Di(meth)acrylate, polyester tri(meth)acrylate, polyester di(meth)acrylate, bisphenol di(meth)acrylate, di(meth)acrylate diglyceride, di( A polyfunctional compound such as adamantylmethyl methacrylate, isodecyl di(meth)acrylate, dicyclopentane di(meth)acrylate, or tricyclodecane di(meth)acrylate. In the present specification, "(meth) acrylate" means methacrylate and acrylate. Further, in the present invention, the above-mentioned compound may be modified by using PO, EO or the like as the above-mentioned free radiation curable resin.

In addition to the above compounds, a relatively low molecular weight polyester resin having an unsaturated double bond, a polyether resin, an acrylic resin, an epoxy resin, an amine ester resin, an alkyd resin, a acetal resin, a polybutadiene may also be used. Resin, polythiol polyene resin, etc. as the above-mentioned free radiation curing type Resin.

The above-mentioned free-radiation-curable resin may be used in combination with a solvent-drying resin (a resin such as a thermoplastic resin which is dried only by a solvent added to adjust a solid content during coating to form a film). When the solvent-dried resin is used in combination, when the antiglare layer is formed, the film defects on the coated surface of the coating liquid can be effectively prevented.

The solvent-drying resin which can be used in combination with the above-mentioned free radiation-curable resin is not particularly limited, and a thermoplastic resin can be usually used.

The thermoplastic resin is not particularly limited, and examples thereof include a styrene resin, a (meth)acrylic resin, a vinyl acetate resin, a vinyl ether resin, a halogen-containing resin, and an alicyclic olefin resin. A polycarbonate resin, a polyester resin, a polyamide resin, a cellulose derivative, a polyoxyn resin, a rubber or an elastomer. The above thermoplastic resin is preferably amorphous and soluble in an organic solvent (particularly a common solvent which can dissolve a plurality of polymers or hardening compounds). In particular, from the viewpoint of film formability, transparency, and weather resistance, a styrene resin, a (meth)acrylic resin, an alicyclic olefin resin, a polyester resin, or a cellulose derivative is preferable ( Cellulose esters, etc.).

Further, the composition for an antiglare layer may contain a thermosetting resin.

The thermosetting resin is not particularly limited, and examples thereof include a phenol resin, a urea resin, a diallyl phthalate resin, a melamine resin, a guanamine resin, an unsaturated polyester resin, a polyurethane resin, and a ring. An oxyresin, an amine alkyd resin, a melamine-urea co-condensation resin, an anthracene resin, a polydecane resin, or the like.

In the composition for an antiglare layer, the cerium oxide fine particles are preferably uniformly dispersed in the composition, and it is preferred to dilute the coating film as shown in FIG. The sparse ground is distributed around the above organic fine particles. 4 is a further cross-sectional STEM photograph of the laminate of Example 1.

When the cerium oxide fine particles are not uniformly dispersed in the antiglare layer composition, the uniform dispersion in the formed antiglare layer cannot be achieved, and the composition for the antiglare layer is not contained. The aggregation is excessively carried out, and it becomes a large aggregate of the above-mentioned cerium oxide fine particles, and there is a case where the above-described antiglare layer having a uniform and uniform uneven shape cannot be formed.

Here, since the above-mentioned cerium oxide microparticles can be made of a material which is thickened by the composition for the antiglare layer, the presence of the above-mentioned cerium oxide microparticles can suppress precipitation of organic fine particles contained in the composition for an antiglare layer. . In other words, it is presumed that the above-mentioned cerium oxide fine particles have a function of promoting the formation of a specific distribution of the organic fine particles and the cerium oxide fine particles, and also have a function of improving the pot life of the composition for an anti-glare layer.

In addition, as a method of uniformly dispersing the above-mentioned cerium oxide fine particles in the composition for an antiglare layer and sparsely distributed around the organic fine particles in the coating film, for example, a specific amount of a polar group is contained. Further, a solvent having a faster volatilization rate is a method of adding a solvent to the composition for an antiglare layer. By containing such a solvent having a high polarity and a high volatilization rate, it is possible to prevent the cerium oxide fine particles from excessively agglomerating in the composition for an antiglare layer. On the other hand, when it is applied to the above-mentioned light-transmitting substrate and dried to form a coating film, since the solvent having a high polarity and a high volatilization rate is volatilized first compared with other solvents, when the coating film is formed, When the composition is modified, the hydrophobicity of the periphery of the organic fine particles is enhanced in the coating film, and the affinity with the above-mentioned ceria microparticles is lowered to make the ceria microparticles difficult to exist, thereby forming sparsely A state distributed around the above organic fine particles.

In the present specification, the term "solvent having a higher polarity" means a solvent having a solubility parameter of 10 [(cal/cm ³ ) ^1/2 ] or more, and the term "solvent having a relatively high volatilization rate" means A solvent having a relative evaporation rate of 150 or more. Therefore, the above-mentioned "solvent having a high polarity and a high volatilization rate" means a solvent which satisfies both of the above-mentioned "highly polar solvent" and "solvent having a high volatilization rate".

In the present specification, the above solubility parameters are calculated by the method of Fedors. The method of Fedors is described, for example, in "SP Value Fundamentals - Application and Calculation Methods" (issued by Yamamoto Hideki Information Corporation Co., Ltd., 2005). In the method of Fedors, the solubility parameter is calculated according to the following formula.

Solubility parameter = [Σ E _coh /Σ V] ²

In the above formula, E _coh is a cohesive energy density, and V is a molecular volume. Based on the determined E _coh and V of each atomic group, and is obtained as the sum of E _coh V [Sigma Σ E _coh and V, whereby the solubility parameter can be calculated.

In the present specification, the relative evaporation rate is the relative evaporation rate when the evaporation rate of n-butyl acetate is 100, and is determined by the evaporation rate according to ASTM D3539-87. The formula is calculated. Specifically, the evaporation time of n-butyl acetate under dry air at 25 ° C and the evaporation time of each solvent were measured.

Relative evaporation rate = (time required for evaporation of 90% by weight of n-butyl acetate) / (time required for evaporation of 90% by weight of solvent) × 100

Examples of the solvent having a high polarity and a high volatilization rate include ethanol and isopropyl alcohol. Among them, isopropyl alcohol can be suitably used.

Further, the content of the isopropyl alcohol in the solvent is preferably 10% by mass or more based on the total amount of the solvent. If it is less than 10% by mass, the cerium oxide microparticles are generated in the composition for an anti-glare layer. The case of agglomerates. The content of the above isopropyl alcohol is preferably 40% by mass or less. When it exceeds 40% by mass, the cerium oxide fine particles may not be sparsely distributed around the organic fine particles.

Examples of the other solvent contained in the composition for an antiglare layer include a ketone (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) and an ether (second). Alkane, tetrahydrofuran, etc., aliphatic hydrocarbons (such as hexane), alicyclic hydrocarbons (such as cyclohexane), aromatic hydrocarbons (such as toluene and xylene), and halogenated carbons (dichloromethane and dichloroethylene) Ethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), alcohols (butanol, cyclohexanol, etc.), cellosolve (methyl cellosolve, ethyl cellosolve) Etc.), cellosolve acetate, sulfonium (dimethyl hydrazine, etc.), guanamine (dimethylformamide, dimethylacetamide, etc.), etc., may also be a mixture thereof. .

It is preferable that the composition for an antiglare layer further contains a photopolymerization initiator.

The photopolymerization initiator is not particularly limited, and a known one can be used. Specific examples thereof include acetophenones, benzophenones, Michelin benzoyl benzoate, and α-pentyl groups. Base oxime ester, 9-oxygen sulphide Classes, propiophenones, diphenylethylenediones, benzoin, fluorenylphosphine oxides. Further, it is preferred to use a photosensitizer in combination, and specific examples thereof include n-butylamine, triethylamine, and poly-n-butylphosphine.

When the binder resin is a resin having a radical polymerizable unsaturated group, the photopolymerization initiator is preferably an acetophenone, a benzophenone or a 9-oxosulfide. The class, benzoin, benzoin methyl ether, etc. are used alone or in combination. In the case where the binder resin is a resin having a cationically polymerizable functional group, the photopolymerization initiator is preferably an aromatic diazonium salt, an aromatic sulfonium salt or an aromatic sulfonium salt. The metallocene compound, benzoin sulfonate or the like is used singly or in the form of a mixture.

The content of the photopolymerization initiator in the composition for an antiglare layer is preferably 0.5 to 10.0 parts by mass based on 100 parts by mass of the binder resin. When the amount is less than 0.5 part by mass, the hard coat performance of the formed antiglare layer may be insufficient. When the amount exceeds 10.0 parts by mass, the possibility of hardening may be adversely caused, which is not preferable.

The content ratio (solid content component) of the raw material in the composition for the antiglare layer is not particularly limited, but is usually preferably 5 to 70% by mass, and more preferably 25 to 60% by mass.

In the composition for an antiglare layer, a previously known dispersant, a surfactant, an antistatic agent, a decane coupling agent, or the like may be added for the purpose of improving the hardness of the antiglare layer, suppressing the hardening shrinkage, controlling the refractive index, and the like. Adhesives, anti-colorants, colorants (pigments, dyes), antifoaming agents, leveling agents, flame retardants, UV absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, slip agents Wait.

Examples of the leveling agent include a polyoxyphthalic acid oil and a fluorine-based surfactant, and it is preferable to contain a perfluoroalkyl group from the viewpoint of preventing the antiglare layer from being a Benard Cell structure. A fluorine-based surfactant or the like. When a resin composition containing a solvent is applied and dried, a surface tension difference or the like is generated in the coating film on the surface and the inner surface of the coating film, whereby a large amount of convection is caused in the coating film. The structure produced by this convection is called a Benadite flow structure, which causes problems such as orange peel or coating defects in the formed antiglare layer.

Further, regarding the Bernard's hole flow structure, the unevenness of the surface of the anti-glare layer is excessively large, resulting in white blurring, which adversely affects surface glare. When the leveling agent as described above is used, since the convection can be prevented, not only the uneven film having no defects or unevenness can be obtained, but also the uneven shape can be easily adjusted.

In addition, the composition for an anti-glare layer may be used by mixing a photosensitizer, and specific examples thereof include n-butylamine, triethylamine, and poly-n-butylphosphine.

In the method for producing a laminate according to the present invention, the composition for an anti-glare layer is prepared by mixing and stirring the binder resin and the organic fine particles in the solvent to prepare an intermediate composition. The inorganic fine particles (cerium oxide fine particles) are mixed and dispersed in the intermediate composition.

In the present invention, the composition for an antiglare layer is one of the constituent materials necessary for the composition for an antiglare layer, and finally, inorganic fine particles are added. When the inorganic fine particles are added to a solvent to prepare a composition for an antiglare layer before the addition of the organic fine particles or the binder resin, excessive aggregation of inorganic fine particles due to solvent attack occurs, and An anti-glare layer having a uniform and uniform uneven shape is formed. Moreover, in order to make the above effect more reliable, when the inorganic fine particles are finally added, the inorganic fine particles are more preferably an inorganic fine particle dispersion dispersed in the solvent.

The method of preparing the intermediate composition is not particularly limited as long as the organic fine particles and the binder resin are uniformly mixed in the solvent. For example, a paint shaker, a bead mill, a kneader, a stirrer, or the like can be used. The device is carried out.

Further, a method of preparing the composition for an antiglare layer by adding inorganic fine particles to the intermediate composition may be the same as the above.

The method for applying the composition for an antiglare layer to a light-transmitting substrate is not particularly limited, and examples thereof include a spin coating method, a dipping method, a spray method, a die coating method, and a bar coating method. A known method such as a cloth method, a roll coater method, a liquid surface bending coating method, a soft printing method, a screen printing method, or a droplet coating method.

The composition for an anti-glare layer is applied by any of the above methods, and then transferred to a region heated to dry the formed coating film, and the coating film is dried by various known methods to thereby obtain a solvent. evaporation. Here, the distribution state of the organic fine particles and the inorganic fine particles can be adjusted by selecting the solvent relative evaporation rate, the solid content concentration, the coating liquid temperature, the drying temperature, the wind speed of the drying wind, the drying time, the solvent atmosphere concentration in the drying region, and the like. .

In particular, the method of adjusting the distribution state of the aggregates of the organic fine particles and the cerium oxide fine particles by selecting the drying conditions is simpler and more preferable. The specific drying temperature is preferably 30 to 120 ° C, and the drying wind speed is preferably 0.2 to 50 m/s, and the organic fine particles can be obtained by performing one or more drying treatments appropriately adjusted within the range. The distribution state of the agglomerates of the cerium oxide microparticles is adjusted to a desired state.

Moreover, as a method of irradiating the free radiation when the coating film after drying is cured, for example, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black lamp fluorescent lamp, or a metal halide lamp can be used. method.

Further, as the wavelength of the ultraviolet light, a wavelength region of 190 to 380 nm can be used. Specific examples of the electron beam source include a Cockcroft-Walton type, a Van de Graaff type, a resonant transformer type, an insulated core transformer type, or a linear type. Various electron beam accelerators such as a high-frequency high-voltage accelerator (dynamitron) type and a high-frequency type.

As described above, the layered body produced by the method for producing a layered product of the present invention is formed by the dispersion of inorganic fine particles (cerium oxide fine particles) in the composition for forming an antiglare layer as described above. The uneven shape of the surface of the anti-glare layer is extremely uniform and uniformly formed as compared with the uneven shape of the surface of the anti-glare layer of the conventional laminated body.

Regarding the antiglare layer having such a concavo-convex shape, since it is hardly formed on the surface thereof, Since the convex portion of the different point is formed, it is possible to obtain a laminate having excellent anti-glare properties and capable of suppressing glare at an extremely high level, and obtaining an excellent display image with high contrast.

Further, the laminate according to the present invention is one of the inventions, which is characterized in that the surface of the light-transmitting substrate has an anti-glare layer having a concave-convex shape on the surface thereof, and is characterized in that the surface of the anti-glare layer is divided into In the measurement area of 100 μm square, the arithmetic mean roughness Sa of each measurement area is obtained, and when the average value of the arithmetic mean roughness Sa is set to Ma, and the standard deviation of the arithmetic mean roughness Sa is Sq, The ratio of Ma to Sq (Sq/Ma) is 0.15 or less.

Since the resolution of the human eye is about 100 μm, if the unevenness per 100 μm square is large, the human eye recognizes the deformation of the transmitted light and is observed in the form of glare. Therefore, if the ratio (Sq/Ma) of the above Ma to Sq exceeds 0.15, the deformation of the light transmitted by the laminated body of the present invention is recognized and observed as glare. The above (Sq/Ma) is preferably 0.12 or less, more preferably 0.10 or less.

Further, in the laminate of the present invention, the average value (Ma) of the above Sa is preferably 0.10 μm or more and 0.40 μm or less. When the thickness is less than 0.10 μm, the layered body of the present invention may have insufficient antiglare properties. When the thickness exceeds 0.40 μm, the contrast of the layered body of the present invention may be deteriorated.

In addition, the arithmetic mean roughness Sa is obtained by three-dimensionally expanding the arithmetic mean roughness Ra of the two-dimensional roughness parameter described in JIS B0601:1994, and the orthogonal coordinate axes X and Y axes are set on the reference plane. When the roughness surface is Z (x, y) and the size of the measurement area is Lx or Ly, it is calculated by the following formula (a).

Further, in the above formula (a), A = Lx × Ly is shown.

Further, when the height of the _i-th position in the X-axis direction and the j-th point in the Y-axis direction is Z _i,j , the arithmetic mean roughness Sa is calculated by the following formula (b).

Further, in the above formula (b), N represents all the points.

Examples of the means for obtaining the arithmetic mean roughness Sa under such three-dimensional conditions include a contact surface roughness meter or a non-contact surface roughness meter (for example, an interference microscope, a coconcentrating microscope, an atomic force microscope, or the like). Among these, it is preferable to carry out measurement using an interference microscope in terms of the simplicity of measurement. Examples of such an interference microscope include the "New View" series manufactured by Zygo Corporation.

In the laminate of the present invention, it is preferable that the antiglare layer contains a binder resin, organic fine particles, and inorganic fine particles.

The binder resin, the organic fine particles, the inorganic fine particles, and the light-transmitting substrate are the same as those described in the above-described method for producing a laminate of the present invention.

In addition, the method of producing the laminated body of the present invention is not particularly limited as long as it can control the uneven shape of the surface of the antiglare layer so as to sufficiently satisfy the above requirements. For example, the laminate of the present invention can be used. The manufacturing method is carried out.

Further, the laminated body is another aspect of the present invention, which is characterized in that the one surface of the light-transmitting substrate has an anti-glare layer having a concave-convex shape on the surface, and the anti-glare layer contains Adhesive resin, organic fine particles and inorganic fine particles, the above inorganic fine particles are sparse The ground is distributed around the organic fine particles, and is uniformly distributed in the anti-glare layer except for the periphery of the organic fine particles.

In the above aspect, the laminated system of the present invention has an antiglare layer containing a binder resin, organic fine particles, and inorganic fine particles, and the inorganic fine particles are sparsely distributed around the organic fine particles.

Here, when the cross section of the anti-glare layer is observed by an electron microscope, it is observed that the inorganic fine particles sparsely distributed around the organic fine particles are not only sparsely distributed in the cross section passing through the center of the organic fine particles, but also sparsely distributed. A state of a profile that deviates from the center of the organic fine particles.

In addition, the above-mentioned "the above-mentioned inorganic fine particles are distributed sparsely around the organic fine particles" means a state in which an electron microscope (preferably a penetration type such as TEM or STEM) is used at a magnification of 10,000 times. When the cross section of the organic fine particles is observed in the thickness direction of the glare layer, the area ratio of the inorganic fine particles to the area other than the organic fine particles in the circumference of the outer side of the organic fine particles of 500 nm is Mn, When the area ratio of the inorganic fine particles in the region from the outer side of the outer side of the organic fine particles of 500 nm to the outer side is Mf, Mf/Mn is 1.5 or more.

In addition, the above-mentioned "distribution in the antiglare layer uniformly around the periphery of the organic fine particles" is the same as "sequentially distributed in the antiglare layer" described in the method for producing the laminated body of the present invention. The meaning.

In another aspect, the laminate of the present invention contains organic fine particles and inorganic fine particles in the antiglare layer by the relationship described in the composition for an antiglare layer in the method for producing a laminate according to the present invention. Anti-glare on the surface of the concave and convex shape and the conventional laminated body Compared with the uneven shape of the layer, it is extremely uniform and uniform. According to the laminated body of the present invention having another aspect of such an anti-glare layer, it has excellent anti-glare properties and can suppress generation of glare at an extremely high level, and an excellent display image with high contrast can be obtained.

In another aspect of the laminate of the present invention, the binder resin, the organic fine particles, the inorganic fine particles, and the light-transmitting substrate are the same as those described in the method for producing a laminate of the present invention. By.

In addition, the method of producing the laminate of the present invention in another aspect is not particularly limited as long as it can control the organic fine particles and the inorganic fine particles in the antiglare layer so as to be contained in the above state. For example, it can be manufactured by the manufacturing method of the laminated body of this invention mentioned above.

As described above, the laminate of the present invention and another aspect of the laminate of the present invention (hereinafter, these are integrated in the form of the laminate of the present invention) have a specific antiglare layer. The surface of the anti-glare layer is formed to have an extremely uniform and uniform uneven shape as compared with the antiglare layer of the conventional laminate.

Specifically, as the uneven shape of the surface of the anti-glare layer, it is preferable that the average interval of the unevenness on the surface of the anti-glare layer is Sm, and the average inclination angle of the uneven portion is θa, and the arithmetic mean of the unevenness is preferably When the roughness is Ra and the ten-point average roughness of the unevenness is Rz, the following formula is satisfied. If θa, Ra, and Rz do not reach the lower limit, there is a case where the reflection of external light cannot be suppressed. Further, when θa, Ra, and Rz exceed the upper limit, there is a decrease in bright room contrast due to an increase in diffused reflection of external light, or a decrease in dark room contrast due to an increase in stray light from penetrating image light. In the constitution of the present invention, if Sm is not reached to the lower limit, there is a problem that the contrast is poor. On the other hand, if Sm exceeds the upper limit, there is a possibility that glare cannot be sufficiently suppressed.

50μm<Sm<300μm

0.5°<θa<4.0°

0.05μm<Ra<0.40μm

0.30μm<Rz<2.50μm

Moreover, it is more preferable that the uneven shape of the above-mentioned antiglare layer satisfies the following formula from the above viewpoint.

50μm<Sm<200μm

0.8°<θa<2.0°

0.10μm<Ra<0.25μm

0.50μm<Rz<1.80μm

The uneven shape of the antiglare layer further preferably satisfies the following formula.

70μm<Sm<100μm

1.0°<θa<1.5°

0.12μm<Ra<0.18μm

0.80μm<Rz<1.30μm

Furthermore, in the present specification, the above Sm, Ra and Rz are obtained by the method according to JIS B 0601-1994, and θa is by the surface roughness measuring device: operating instructions of SE-3400 (1995.07.20) The value obtained by the definition described in (Revision), as shown in Fig. 1, can be obtained by the sum of the heights of the convex portions existing on the reference length L (h ₁ + h ₂ + h ₃ +‧‧‧+h _n ) is obtained by arc tangent θa=tan ^-1 {(h ₁ +h ₂ +h ₃ +‧‧‧+h _n )/L}.

Such Sm, θa, Ra, Rz can be, for example, by surface roughness measuring device: SE-3400/小坂研 It is determined by measuring the production of the company.

Further, the thickness of the antiglare layer is preferably 2.0 to 7.0 μm. If it is less than 2.0 μm, the surface of the antiglare layer may be easily damaged. When the thickness exceeds 7.0 μm, the antiglare layer may be easily broken. A more preferable range of the thickness of the above antiglare layer is 2.0 to 5.0 μm. Further, the thickness of the antiglare layer can be measured by a cross-sectional microscope.

The laminate of the present invention preferably has a total light transmittance of 85% or more. If it is less than 85%, when the laminated body of the present invention is attached to the surface of the image display device, the color reproducibility or visibility is impaired. The above total light transmittance is more preferably 90% or more, and still more preferably 91% or more. In addition, the total light transmittance can be measured by "HM-150" manufactured by Murakami Color Research Institute Co., Ltd., etc. according to JIS K7361.

Further, it is preferred that the laminate of the present invention has a haze of less than 40%. The anti-glare layer may be composed of an internal haze caused by internal diffusion of the contained microparticles and an external haze caused by the uneven shape of the outermost surface, and the internal haze due to internal diffusion is preferably 5 % or more and 30% or less. If it is less than 5%, the glare of the laminated body of the present invention cannot be sufficiently suppressed, and if it exceeds 30%, the contrast of the laminated body of the present invention is inferior. Moreover, the internal haze of the laminate of the present invention is more preferably in the range of 5% or more and 20% or less, and still more preferably in the range of 5% or more and 15% or less. The outer haze of the outermost surface is preferably in the range of 5% or more and 30% or less. If it is less than 5%, the laminated body of the present invention has insufficient antiglare property, and if it exceeds 30%, the laminate of the present invention has a poor contrast. The outer haze of the laminate of the present invention is more preferably in the range of 5% or more and 20% or less, and still more preferably in the range of 7% or more and 15% or less.

Further, in the laminated body of the present invention, the internal haze and the external haze of the antiglare layer can be independently controlled by using the oxidized cerium oxide as the inorganic fine particles. For example, by making Since the cerium oxide is scented, since the average particle diameter of the cerium oxide is small, the internal haze is not exhibited, and only the external haze can be adjusted. Further, the adjustment of the internal haze can be adjusted by changing the ratio of the refractive index of the organic fine particles to the refractive index of the binder resin, or by impregnating the organic fine particles with the monomer of the binder resin. The refractive index of the particle interface.

The haze can be measured by "HM-150" manufactured by Murakami Color Research Institute, etc., in accordance with JIS K7136.

Further, the internal haze is obtained as follows.

In the unevenness on the surface of the antiglare layer of the laminate, the thickness of the dried film is 8 μm (the thickness of the surface is completely lost, and the surface can be made flat) by the wire bar coater. A resin having a refractive index equal to that of the resin forming the surface unevenness or a refractive index difference of 0.02 or less was applied, and after drying at 70 ° C for 1 minute, it was cured by irradiation with ultraviolet rays of 100 mJ/cm ² . Thereby, the unevenness on the surface is flattened, and a film which becomes a flat surface can be obtained. In the case where a leveling agent or the like is added to the composition for forming the antiglare layer having the uneven shape, the resin applied to the surface of the antiglare layer is easily water-repellent and is not easily wetted, and may be used in advance. The surface of the anti-glare layer was immersed in a 2 mol/L NaOH (or KOH) solution at 55 ° C for 3 minutes, and then washed with water, and the water droplets were completely removed by Kimwipe (registered trademark) or the like, and the oven was dried at 50 ° C. It is dried for 1 minute), and a hydrophilic treatment can be carried out.

Since the film whose surface is flattened does not have surface unevenness, it exhibits a state of having only internal haze. The haze of the film can be measured by the same method as the haze according to JIS K-7136, thereby obtaining the internal haze.

Further, the external haze can be obtained in the form of (haze - internal haze).

Further, with regard to the laminated body of the present invention, it is possible to more suitably prevent the occurrence of white blurring From the viewpoint of life, it is preferred to have a low refractive index layer on the above antiglare layer.

The low refractive index layer is a layer that functions to reduce the reflectance when it is reflected from the surface of the optical layered body (for example, a fluorescent lamp or natural light). The low refractive index layer is preferably composed of any one of the following: 1) a resin containing low refractive index particles such as cerium oxide or magnesium fluoride; 2) a fluorine-based resin as a low refractive index resin; and 5) A fluorine-based resin of cerium oxide or magnesium fluoride, or a film of a low refractive index material such as cerium oxide or magnesium fluoride. As the resin other than the fluorine-based resin, the same resin as the binder resin constituting the above-described antiglare layer can be used.

Further, the above-mentioned cerium oxide is preferably hollow cerium oxide fine particles, and such hollow cerium oxide fine particles can be produced, for example, by the production method described in the examples of JP-A-2005-099778.

The refractive index of the low refractive index layer is preferably 1.45 or less, and particularly preferably 1.42 or less.

In addition, the thickness of the low refractive index layer is not particularly limited, and may be appropriately set in the range of about 30 nm to 1 μm.

Further, although the low refractive index layer can obtain an effect in a single layer, in order to adjust a lower minimum reflectance or a higher minimum reflectance, two or more low refractive index layers may be appropriately provided. In the case where the above two or more low refractive index layers are provided, it is preferable to provide a difference in refractive index and thickness of each of the low refractive index layers.

As the fluorine-based resin, a polymerizable compound containing at least a fluorine atom in a molecule or a polymer thereof can be used. The polymerizable compound is not particularly limited, and for example, it is preferably a base having a curing reactive property such as a functional group which is cured by free radiation or a polar group which is thermally cured. Further, it may be a compound having both of these reactivity groups. The polymer is not a reactive group as described above, as opposed to the polymerizable compound.

As the polymerizable compound having a functional group which is hardened by free radiation, a fluorine-containing monomer having an ethylenically unsaturated bond can be widely used. More specifically, a fluoroolefin (for example, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluorobutadiene, perfluoro-2,2-dimethyl-1,3-di) Oxeene, etc.). As the (meth) propylene oxime group, there are also, for example, 2,2,2-trifluoroethyl (meth)acrylate and 2,2,3,3,3-pentafluoropropyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 2-(perfluorooctyl)ethyl (meth)acrylate, (methyl) a (meth) acrylate compound having a fluorine atom in a molecule of 2-(perfluorodecyl)ethyl acrylate, α-trifluoromethyl methacrylate or α-trifluoromethyl acrylate; Fluorinated polyfunctional (meth)acrylic acid having at least 3 fluorine atoms having a fluorinated alkyl group having 1 to 14 carbon atoms, a fluorocycloalkyl group or a fluoroalkylene group, and at least 2 (meth) propylene fluorenyloxy groups Ester compound and the like.

The polar group to be thermally cured is preferably a hydrogen bond forming group such as a hydroxyl group, a carboxyl group, an amine group or an epoxy group. These are excellent not only in adhesion to a coating film, but also in affinity with inorganic ultrafine particles such as cerium oxide. Examples of the polymerizable compound having a thermosetting polar group include a 4-fluoroethylene-perfluoroalkyl vinyl ether copolymer; a vinyl fluoride-hydrocarbon vinyl ether copolymer; epoxy, polyurethane, cellulose, phenol, and the like. Fluorine modified product of each resin such as polyimine.

The polymerizable compound having both a functional group which is cured by free radiation and a polar group which is thermally cured may, for example, be a part of acrylic acid or methacrylic acid, a completely fluorinated alkyl group, an alkenyl group or an aryl ester, Full or partial fluorinated vinyl ethers, fully or partially fluorinated vinyl esters, fully or partially fluorinated ketenes, and the like.

In addition, examples of the fluorine-based resin include the following.

Fluorine (methyl) containing at least one of the above polymerizable compounds having an exothermic radiation curable group a polymer of a monomer or a monomer mixture of an acrylate compound; at least one of the above fluorine-containing (meth) acrylate compounds and such as methyl (meth) acrylate, ethyl (meth) acrylate, (methyl) a copolymer of a (meth) acrylate compound having no fluorine atom in a molecule of propyl acrylate, butyl (meth) acrylate or ethyl hexyl (meth) acrylate; such as vinyl fluoride or vinylidene fluoride Homopolymerization of fluoromonomers of trifluoroethylene, chlorotrifluoroethylene, 3,3,3-trifluoropropene, 1,1,2-trichloro-3,3,3-trifluoropropene and hexafluoropropylene Or a copolymer or the like. It is also possible to use a polyfluorene-containing vinylidene fluoride copolymer containing a polyfluorene oxide component in the copolymer. As the polyoxo component in this case, (poly)dimethyloxane, (poly)dimethoxydecane, (poly)diphenyloxirane, (poly)methylphenyl group can be exemplified. Alkoxysilane, alkyl modified (poly)dimethyloxane, azo-containing (poly)dimethyloxane, dimethylpolyphosphonium, phenylmethylpolyoxyl, alkyl -Aralkyl modified polyfluorene oxide, fluoropolyoxyl, polyether modified polyoxyl, fatty acid ester modified polyoxyl, methylhydrogenpolyoxy, decyl alcohol-containing polyoxyn, alkane Oxygen polyoxynium oxide, phenyl group-containing polyfluorene oxide, methacrylic acid modified polyfluorene oxide, acrylic acid modified polyfluorene oxide, amine modified polyoxymethylene, carboxylic acid modified polyoxyl, methanol modification Polyfluorene oxide, epoxy modified polyfluorene oxide, sulfhydryl modified polyfluorene oxide, fluorine modified polyfluorene oxide, polyether modified polyfluorene oxide and the like. Among them, those having a dimethyl fluorene structure are preferred.

Further, a non-polymer or a polymer composed of a compound described below can also be used as the fluorine-based resin. That is, a compound obtained by reacting a fluorine-containing compound having at least one isocyanate group in the molecule with a compound having at least one functional group reactive with an isocyanate group such as an amine group, a hydroxyl group or a carboxyl group in the molecule; Fluorinated Polyether Polyol, Fluorinated Alkyl Polyol, Fluorinated Polyester Polyol, Fluorinated ε-Caprolactone Modified Polyol Fluorinated Polyol and Compound with Isocyanate Group And the obtained compound and the like.

Further, the above polymerizable compound having a fluorine atom or a polymer may be as above Each of the binder resins described in the antiglare layer is mixed and used. Further, a curing agent for curing a reactive group or the like, and various additives and solvents for improving coating properties or imparting antifouling properties can be suitably used.

In the formation of the low refractive index layer, it is preferable that the viscosity of the composition for a low refractive index layer obtained by adding a low refractive index agent and a resin is 0.5 to 5 mPa ‧ which can obtain a preferable coating property ( 25 ° C), preferably in the range of 0.7 to 3 mPa ‧ (25 ° C). The antireflection layer excellent in visible light can be realized, and a film which is uniform and has no uneven coating can be formed, and a low refractive index layer which is particularly excellent in adhesion can be formed.

The hardening means of the resin may be the same as those described in the above antiglare layer. In the case where the heating means is used for the hardening treatment, it is preferred to add a thermal polymerization initiator which starts polymerization of the polymerizable compound by heating, for example, to generate a radical, to the fluorine-based resin composition.

The layer thickness (nm) d _{A of the} low refractive index layer is preferably one satisfying the following formula (1): d _A = mλ / (4n _A ) (1)

(In the above formula, n _A represents the refractive index of the low refractive index layer, m represents a positive odd number, preferably represents 1, and λ is a wavelength, preferably a value in the range of 480 to 580 nm).

Further, in the present invention, from the viewpoint of low reflectance, the low refractive index layer preferably satisfies the following formula (2): 120 < n _A d _A < 145 (2).

Further, in the range which does not impair the effects of the present invention, the laminate of the present invention may suitably form another layer (antistatic layer, antifouling layer, adhesive layer, other hard coat layer, etc.) as needed. Layer or more than 2 layers. Among them, it is preferred to have at least one of an antistatic layer and an antifouling layer. These layers may also be the same as those of the known antireflection laminate.

The contrast ratio of the laminate of the present invention is preferably 40% or more, more preferably 60% or more. If it is less than 40%, when the laminated body of the present invention is mounted on the surface of the display, the contrast of the dark room is poor and the visibility is impaired. Further, the above-described contrast ratios in the present specification are values measured by the methods described in the following examples.

In the laminate of the present invention, the laminate of the present invention can be placed on the surface of the laminate opposite to the surface on which the antiglare layer is present on the surface of the polarizing element to form a polarizing plate. Such a polarizing plate is also one of the inventions.

The polarizing element is not particularly limited, and for example, a polyvinyl alcohol film obtained by dyeing and stretching with iodine or the like, a polyvinyl formal film, a polyvinyl acetal film, an ethylene-vinyl acetate copolymer can be used. A saponified film or the like. In the lamination treatment of the polarizing element and the laminated body of the present invention, it is preferred to subject the light-transmitting substrate (triethylene cellulose film) to a saponification treatment. By the saponification treatment, the subsequent properties become good, and an antistatic effect can also be obtained.

The present invention is also an image display device comprising the laminate or the polarizing plate on the outermost surface.

The image display device may be an image display device such as an LCD, a PDP, an FED, an ELD (organic EL, an inorganic EL), a CRT, a tablet PC, a touch panel, or an electronic paper.

The LCD system of the above-described representative example includes a transmissive display body and a light source device that irradiates the transmissive display body from the back surface. In the case where the image display device of the present invention is an LCD, the laminate of the present invention or the polarizing plate of the present invention is formed on the surface of the penetrating display.

In the case where the present invention is a liquid crystal display device having the above laminated body, the light source of the light source device is irradiated from the lower side of the laminated body. Further, a phase difference plate can be inserted between the liquid crystal display element and the polarizing plate. An adhesive layer may be provided between the layers of the liquid crystal display device as needed.

A PDP as the image display device includes a substrate glass substrate (electrodes formed on the surface) and a back glass substrate (electrodes and minute grooves are formed on the surface, and red, green, and blue are formed in the grooves. The phosphor layer is disposed so as to face the surface glass substrate and enclose a discharge gas therebetween. In the case where the image display device of the present invention is a PDP, the laminate may be provided on the surface of the surface glass substrate or the front panel (glass substrate or film substrate).

The image display device may be an ELD device that vaporizes a voltage applied to a glass substrate, that is, a light-emitting zinc sulfide, a diamine substance: an illuminant, controls a voltage applied to the substrate, or converts the electrical signal into light. An image display device such as a CRT that produces an image visible to the human eye. In this case, the laminated body is provided on the outermost surface of each display device or the surface of the front panel thereof as described above.

The image display device of the present invention can be used for display display of televisions, computers, electronic papers, touch panels, tablet PCs, and the like in any case. In particular, it can be suitably used for the surface of a display for high-definition images such as a CRT, a liquid crystal panel, a PDP, an ELD, an FED, or a touch panel.

The image display device has excellent anti-glare properties, can suppress generation of glare at an extremely high level, is excellent in high contrast, and has improved visibility. Such a method of improving visibility using the image display device of the present invention is also one of the inventions.

That is, the visibility improving method of the image display device of the present invention is used for visible image display devices having a laminate having an anti-glare layer having a concave-convex shape on one surface of a light-transmitting substrate. And a coating film formed by applying a composition for an antiglare layer containing organic fine particles, inorganic fine particles, a binder resin, and a solvent onto one surface of the light-transmitting substrate. After drying, the anti-glare layer is formed, and the composition for the anti-glare layer is prepared by mixing and stirring the binder resin and the organic fine particles in the solvent to prepare an intermediate composition, and then mixing the inorganic fine particles. Prepared by dispersing in the above intermediate composition.

In the method for improving the visibility of the image display device of the present invention, the laminate having the antiglare layer having the uneven shape on the surface of one surface of the light-transmitting substrate and the composition for the antiglare layer are exemplified. The same as those described in the method for producing a laminate of the present invention described above.

Since the method for producing a laminate according to the present invention is constituted by the above-described configuration, it is possible to produce the present invention which has excellent anti-glare properties and can suppress the occurrence of glare at an extremely high level, and can obtain a display image excellent in high contrast. The layered body.

Therefore, the laminate of the present invention can be suitably applied to a cathode ray tube display device (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED), and an electron. Paper, touch panel, tablet PC, etc.

Θa‧‧‧ average tilt angle

h ₁ , h ₂ , h ₃ , h ₄ , h _n ‧‧‧ convex height

L‧‧‧base length

Fig. 1 is an explanatory view showing a method of measuring θa.

Fig. 2 is a cross-sectional electron micrograph of the laminate of Example 1.

Fig. 3 is another cross-sectional electron micrograph of the laminate of Example 1.

Fig. 4 is a further cross-sectional electron micrograph of the laminate of Example 1.

The contents of the present invention are described by the following examples, but the contents of the present invention are not limited to the embodiments. Unless otherwise stated, "parts" and "%" are quality benchmarks.

(Preparation of composition 1 for antiglare layer)

The intermediate composition was obtained by dispersing the composition shown below using a bead mill.

Next, the composition shown below was dispersed by a bead mill to obtain an inorganic fine particle dispersion.

Then, while the intermediate composition was stirred by a disperser, the inorganic fine particle dispersion was slowly added to obtain the composition 1 for an antiglare layer.

(intermediate composition)

Organic fine particles (non-hydrophilic treated acrylic-styrene copolymer particles, average particle diameter 3.5 μm, refractive index 1.55, manufactured by Sekisui Kogyo Seiko Co., Ltd.) 14 parts by mass

Neopentyltetraol tetraacrylate (PETTA) (product name: PETA, manufactured by Daicel Cytec Co., Ltd.) 65 parts by mass

Ammonium acrylate (product name "V-4000BA", manufactured by DIC Corporation) 35 parts by mass

Irgacure 184 (manufactured by BASF Japan) 5 parts by mass

Polyether modified polyfluorene (TSF4460, manufactured by Momentive Performance Materials) 0.025 parts by mass

Toluene 100 parts by mass

Isopropyl alcohol 35 parts by mass

Cyclohexanone 20 parts by mass

(Inorganic microparticle dispersion)

Oxidized cerium oxide (octyl decane treatment; average primary particle diameter 12 nm, manufactured by Nippon Aerosil Co., Ltd.) 6 parts by mass

Toluene 45 parts by mass

Isopropyl alcohol 20 parts by mass

(Preparation of composition 2 for anti-glare layer)

The organic fine particles in the intermediate composition were made into non-hydrophilic-treated acrylic-styrene copolymer particles (average particle diameter: 5.0 μm, refractive index: 1.55, manufactured by Sekisui Kogyo Seisakusho Co., Ltd.), and the blending amount was set to 16 parts by mass. In addition, the composition 2 for an anti-glare layer was obtained in the same manner as the composition 1 for an anti-glare layer.

(Preparation of composition 3 for antiglare layer)

The anti-glare is obtained in the same manner as the composition 1 for the anti-glare layer, except that the amount of the isopropyl alcohol in the intermediate composition is 5 parts by mass, and the amount of the cyclohexanone is 50 parts by mass. The composition 3 is used for the layer.

(Preparation of composition 4 for antiglare layer)

The composition 4 for an anti-glare layer was obtained in the same manner as the composition 1 for an anti-glare layer, except that the amount of the oxidized cerium oxide in the inorganic fine particle dispersion was 4 parts by mass.

(Preparation of composition 5 for antiglare layer)

At the same time, the composition for the antiglare layer is dispersed by the bead mill to disperse the respective components shown in the intermediate composition and the inorganic fine particle dispersion in the composition 1 to obtain an antiglare layer composition 5.

(Preparation of composition 6 for antiglare layer)

The composition for the antiglare layer 6 was obtained by dispersing the composition shown below by a bead mill.

Organic microparticles (non-hydrophilic treated polystyrene particles, average particle size 3.5 μm, refractive index 1.59, manufactured by Xiayan Chemical Co., Ltd.) 14 parts by mass

Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by Daicel Cytec Co., Ltd.) 100 parts by mass

Acrylic polymer (molecular weight 75,000, manufactured by Mitsubishi Rayon Co., Ltd.) 10 parts by mass

Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan) 5 parts by mass

Polyether modified polyfluorene (product name "TSF4460", manufactured by Momentive Performance Materials) 0.025 parts by mass

Toluene 120 parts by mass

Cyclohexanone 30 parts by mass

(Preparation of composition 7 for antiglare layer)

The organic fine particles in the composition for antiglare layer 6 are non-hydrophilic-treated acrylic-styrene copolymer particles (average particle diameter: 3.5 μm, refractive index: 1.55, manufactured by Sekisui Kogyo Seisakusho Co., Ltd.), and The antiglare layer composition 7 is obtained in the same manner as the composition 6 .

(Example 1)

The composition 1 for an anti-glare layer was applied to one surface of a light-transmitting substrate (thickness: 60 μm, triethylenesulfon cellulose resin film, manufactured by Fuji Film Co., Ltd., TD60 UL) to form a coating film. Then, the dried air of 70 ° C was circulated for 15 seconds at a flow rate of 0.2 m/s, and then dried at 70 ° C for 30 seconds at a flow rate of 10 m/s to dry. The solvent in the coating film was evaporated, and the coating film was cured by irradiating ultraviolet rays so as to have an integrated light amount of 100 mJ/cm ² to form an antiglare layer having a thickness of 6 μm (at the time of curing), thereby producing the layered body of Example 1. .

(Examples 2 to 4)

The laminates of Examples 2 to 4 were produced in the same manner as in Example 1 except that the components 1 to 4 for the antiglare layer were used instead of the composition 1 for the antiglare layer.

(Comparative Example 1)

A laminate of Comparative Example 1 was produced in the same manner as in Example 1 except that the composition 1 for the antiglare layer was used instead of the composition 1 for the antiglare layer.

(Comparative examples 2 to 3)

In the same manner as in Example 1, except that the antiglare layer composition 6 to 7 was used instead of the antiglare layer composition 1 and the thickness at the time of curing was 4.5 μm, Comparative Examples 2 to 3 were produced. Laminated body.

The laminates of the obtained examples, comparative examples, and reference examples were evaluated for the following items.

All results are shown in Table 1.

(anti-glare)

Regarding the anti-glare property of the obtained laminated body, a black acrylic resin plate, a transparent adhesive, and a laminated body (the non-coated surface of the light-transmitting substrate on the adhesive side) are attached in order, at 1.5 m. In the bright room environment in which the illumination of the three-wavelength fluorescent lamp is arranged at about 1000 Lx, the evaluation of the fluorescent lamp is unobtrusive by the following reference.

◎: The image of the fluorescent lamp is completely blurred and cannot be recognized.

○: Although the image of the fluorescent light is reflected, the outline is blurred and the boundary of the outline cannot be recognized.

×: Reflects the image of the fluorescent light, and clearly recognizes the outline

(glare evaluation)

The surface glare of the obtained laminate was evaluated in the following manner.

A sample having no antiglare layer formed on the laminate and a glass surface of a black matrix (glass thickness: 0.7 mm) which was not formed into a matrix was bonded by a transparent adhesive to obtain a sample.

To the sample thus obtained, a white surface light source (manufactured by HAKUBA Co., Ltd., LIGHTBOX, average luminance: 1000 cd/m ² ) was placed on the side of the black matrix, thereby artificially generating glare.

The side of the laminated body was photographed using a CCD camera (KP-M1, C mounting adapter, close-up ring; PK-11A Nikon, camera lens; 50 mm, F1.4s NIKKOR). The distance between the CCD camera and the laminated body is set to 250 mm, and the focus of the CCD camera is adjusted in conformity with the laminated body. The image captured by the CCD camera was imported into a personal computer, and analyzed by the image processing software (ImagePro Plus ver. 6.2; manufactured by Media Cybernetics) in the following manner.

First, an evaluation portion of 200 × 160 pixels is selected from the imported images, and converted into 16-bit gradation in the evaluation portion. Next, low-pass filtering is selected from the emphasis label of the filtering instruction, and filtering is applied under the condition of "3 × 3, the number of times 3, and the intensity of 10". Thereby, the components from the black matrix pattern are removed.

Next, select the flattening and perform shading correction under the condition of "background: darker, target width 10".

Next, contrast enhancement is performed by setting "Contrast: 96, Brightness: 48" in the contrast emphasis command.

The obtained image is converted into an 8-bit gradation, and for each of 150 × 110 pixels, the variation of the value of each pixel is calculated as a standard deviation value, thereby grading the glare. It can be considered that the smaller the glare value of the numerical value, the less the glare is. Furthermore, the measurement is based on a black matrix corresponding to a pixel density of 200. The ppi is carried out.

The measured glare value was evaluated by the following criteria.

◎: The above glare value is 14 or less

○: The above glare value exceeds 14 and is 18 or less.

×: The above glare value exceeds 18

(contra rate)

In the measurement of the contrast ratio, a polarizing plate was used as a backlight unit in a cold cathode tube light source, and two polarizing plates (AMN-3244TP manufactured by Samsung Co., Ltd.) were used to set the polarizing plate on a parallel polarizer. The L _max of the brightness of the light is divided by the L _min of the light passing through the orthogonal polarizer, and the obtained value (L _max /L _min ) is set as the contrast, and the laminated body is obtained. The contrast ratio (L ₁ ) when the substrate is placed on the outermost surface and the contrast (L ₂ ) when only the light-transmitting substrate is placed on the outermost surface, and is calculated (L ₁ /L) ₂ ) × 100 (%), thereby calculating the contrast ratio.

Further, the measurement of the luminance was carried out in a dark room environment having an illuminance of 5 Lx or less using a color luminance meter (BM-5A manufactured by TOPCON Corporation). The measurement angle of the color luminance meter was set to 1°, and the measurement was performed with a field of view φ 5 mm on the sample. The amount of light of the backlight is set such that the brightness when the two polarizing plates are placed on the parallel polarizer is 3600 cd/m ² in a state where no sample is provided.

◎: The above contrast ratio is 60% or more

○: The above contrast ratio is 40% or more and less than 60%

×: The above contrast ratio is less than 40%

(Sq/Ma)

The surface on the side opposite to the surface on which the antiglare layer was formed on each of the obtained laminates was attached to a glass plate via a transparent adhesive to prepare a sample, and a white interference microscope (New View 7300, manufactured by Zygo Co., Ltd.) was used. The surface shape of the antiglare layer was measured and analyzed under the following conditions. In addition, the measurement and analysis software uses MetroPro ver 8.3.2 Microscope Application.

(measurement conditions)

Objective lens: 50 times

Zoom: 1x

Measurement area: 414 μm × 414 μm

Resolution (interval between 1 point): 0.44μm

(analysis conditions)

Removed: Sphere

Filter: Low Pass

Filter Type: Gauss Spline

High wavelength: 2.5μm

Remove spikes: On

Spike Height (xRMS): 2.5

The data measured under the above measurement conditions were divided into 16 regions of 100 μm × 100 μm by using "Mask Editor", and each region was read and displayed on the Surface Map screen under the above analysis conditions. The value of "Ra" is set to the value of Sa. Then, the average value of these is set to Ma, the standard deviation of these is set to Sq, and (Sq/Ma) is calculated.

(haze, internal haze)

For the haze of each laminate, a haze meter (manufactured by Murakami Color Technology Research Institute, model name) HM-150) was measured by the method according to JIS K-7136 (haze). The internal haze was measured by the above method.

(The average interval (Sm) of the unevenness, the arithmetic mean roughness (Ra) of the unevenness, the average inclination angle (θa) of the uneven portion, and the ten-point average roughness (Rz))

The average interval (Sm) of the unevenness, the arithmetic mean roughness (Ra) of the unevenness, and the ten-point average roughness (Rz) were measured in accordance with JIS B 0601-1994, and the average tilt angle of the uneven portion was measured by the method shown in FIG. (θa). In addition, the measurement of the above Sm, Ra, θa, and Rz was performed using the surface roughness measuring instrument: SE-3400 / Otaru Research Co., Ltd., and the measurement was performed under the following conditions.

(1) The stylus of the surface roughness detecting section:

Model / SE2555N (2μ stylus), manufactured by Otaru Research Institute Co., Ltd.

(Front radius of curvature 2μm / apex angle: 90 degrees / material: diamond)

(2) Measurement conditions of the surface roughness measuring device:

Base length (threshold value of roughness curve λc): 0.8mm

Evaluation length (reference length (threshold value λc) × 5): 4.0 mm

Feeding speed of the stylus: 0.5mm/s

Preliminary length: (threshold λc) × 2

Vertical magnification: 2000 times

Horizontal magnification: 10 times

As shown in Table 1, the glare, the contrast ratio, and the anti-glare property of any of the laminates of the examples were excellent, and the production stability was also excellent.

On the other hand, since the layered system of Comparative Example 1 was produced by using the composition for the antiglare layer in which the respective components of the intermediate composition and the inorganic fine particle dispersion were dispersed, the evaluation of glare was inferior. Further, since the laminated body of Comparative Example 2 did not use inorganic fine particles, the uneven shape was not uniformly formed uniformly, and therefore the evaluation of glare was inferior. Further, in the laminate of Comparative Example 3, since the internal haze was large, although the glare was good, the evaluation of the contrast ratio was inferior.

[Industrial availability]

The laminate of the present invention can be suitably applied to a cathode ray tube display device (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED), and a touch panel. , electronic paper, tablet PC, etc.

Claims (12)

A method for producing a laminate, which is a method for producing a laminate having an antiglare layer having a concavo-convex shape on one surface of a light-transmitting substrate, and characterized in that it has a step of: containing organic fine particles, a composition for an anti-glare layer of inorganic fine particles, a binder resin, and a solvent is applied onto one surface of the light-transmitting substrate, and the formed coating film is cured after drying to form the anti-glare layer; and the anti-glare layer The composition is prepared by mixing the binder resin and the organic fine particles in the solvent and stirring them to prepare an intermediate composition, and then mixing and dispersing the inorganic fine particles in the intermediate composition. A laminated body which has an antiglare layer having a concavo-convex shape on one surface of a light-transmitting substrate, and is characterized in that the surface of the anti-glare layer is divided into measurement areas of 100 μm square, and each of the layers is obtained. The arithmetic mean roughness Sa of the measurement region is a ratio of the Ma to the Sq when the average value of the arithmetic mean roughness Sa is set to Ma, and the standard deviation of the arithmetic mean roughness Sa is Sq (Sq/Ma) ) is 0.15 or less. The laminate according to claim 2, wherein the antiglare layer contains a binder resin, organic fine particles, and inorganic fine particles. A laminated body having an antiglare layer having a concave-convex shape on a surface of a light-transmitting substrate, wherein the anti-glare layer contains a binder resin, organic fine particles, and inorganic fine particles, and the inorganic layer The fine particles are sparsely distributed around the organic fine particles, and are uniformly distributed in the anti-glare layer except for the periphery of the organic fine particles. The laminate according to claim 3 or 4, wherein the inorganic fine particles are cerium oxide fine particles. The laminate according to claim 5, wherein the aggregate of the cerium oxide microparticles has an average particle diameter of 100 nm to 1 μm. The laminate of claim 3, 4, 5 or 6, wherein the binder resin has a polyfunctional acrylate monomer having no hydroxyl group in its molecule as a main material. The laminate of claim 3, 4, 5, 6 or 7 wherein the organic microparticles are selected from the group consisting of acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyethylene resins, epoxy resins, A fine particle composed of at least one of a group consisting of a silicone resin, a polyvinylidene fluoride resin, and a polyvinyl fluoride resin. The laminate of claim 3, 4, 5, 6, 7, or 8 wherein the organic microparticles are not surface hydrophilized. A polarizing plate comprising a polarizing element, wherein the polarizing plate has a laminated body of the second, third, fourth, fifth, sixth, seventh, eighth or ninth aspect of the patent application in the surface of the polarizing element. An image display device comprising a laminate of the second, third, fourth, fifth, sixth, seventh, eighth or ninth aspect of the patent application or a polarizing plate of claim 10 of the patent application on the outermost surface. A method for improving the visibility of an image display device using a laminate having an anti-glare layer having a concave-convex shape on a surface of a light-transmitting substrate, and characterized in that it contains organic fine particles, a composition for an anti-glare layer of inorganic fine particles, a binder resin, and a solvent is applied onto one surface of the light-transmitting substrate, and the formed coating film is cured after drying to form the anti-glare layer of the laminate, and After the binder resin and the organic fine particles are mixed in the solvent and stirred to prepare an intermediate composition, the inorganic fine particles are mixed and dispersed in the intermediate composition to prepare the composition for an antiglare layer.