KR102365537B1 - 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 manufacturing a laminate that is excellent in manufacturing stability, has good anti-glare properties, can suppress generation of glare to an extremely high level, and can obtain a high-contrast display image. A method for manufacturing a laminate having an anti-glare layer having an uneven shape on the surface thereof on one side of a light-transmitting substrate, wherein a composition for an anti-glare layer containing organic fine particles, inorganic fine particles, a binder resin and a solvent is applied to one side of the light transmissive substrate After drying and curing the coating film formed by coating on it, 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, A method for producing a laminate, characterized in that it is prepared by mixing and dispersing the inorganic fine particles in the intermediate composition.

Description

The manufacturing method of a laminated body, a laminated body, a polarizing plate, an image display apparatus, and the method of improving the visibility of an image display apparatus TECHNICAL FIELD

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 image display devices such as cathode ray tube display (CRT), liquid crystal display (LCD), plasma display (PDP), light emitting element display (ELD), electronic paper, tablet PC, and touch panel, the outermost surface is generally antireflection An optical laminate is installed for

Such an optical laminate for antireflection suppresses projection of an image or reduces reflectance by scattering or interference of light.

As one of the optical laminates for antireflection, the anti-glare film which formed the glare-proof layer which has an uneven|corrugated shape on the surface of the transparent base material is known. This anti-glare film scatters external light with the uneven|corrugated shape of the surface, and can prevent the fall of the visibility by reflection of external light and projection of an image.

Moreover, since this optical laminated body is normally provided in the outermost surface of an image display apparatus, it is also calculated|required that hard-coat property may not arise at the time of handling so that a flaw may not arise.

As a conventional anti-glare film, for example, it is known that the surface of a light-transmitting base material was coated with resin containing fillers, such as silicon dioxide (silica), and what formed the anti-glare layer (for example, patent document 1) , see 2).

These anti-glare films are a type in which an uneven shape is formed on the surface of an anti-glare layer by aggregation of particles such as cohesive silica, a type in which an uneven shape is formed on the surface of the layer by adding an organic filler to a resin, or a type in which an uneven shape is formed on the surface of the layer There is a type in which an uneven shape is transferred by laminating a film with excitation.

However, in any of these conventional anti-glare films, light diffusion and anti-glare action are obtained by the action of the surface shape of the anti-glare layer. , when the unevenness was rough and increased, there was a problem that the haze value (haze value) of the coating film increased, white blur occurred, and the contrast of the displayed image was lowered.

Moreover, the conventional type anti-glare film generate|occur|produced on the film surface, what is called a dazzling luster, and also had the problem that the visibility of a display screen fell. Flashing is when the image display device is turned on, when the transmitted light from the back reaches the screen, a fine luminance unevenness appears on the screen surface, and when the viewer changes the viewing angle, the position of the luminance unevenness seems to change It is a phenomenon, and it is remarkable especially in the case of full-surface white display or full-surface green display.

In particular, in recent years, since adoption of a 4K panel and mobile terminals such as smartphones and tablets are becoming increasingly high-definition, it is no longer possible to sufficiently control glare with the conventional anti-glare film.

With respect to such a problem, for example, the method of improving the glare of an anti-glare layer by an internal haze (for example, refer patent document 3, patent document 4) is known. However, in the method of using the internal haze of the anti-glare layer, if the internal haze is increased in order to further suppress glare in order to cope with the recent ultra-high-definition panels, there is a problem that the darkroom contrast and resolution of the displayed image deteriorates.

Moreover, for example, the method of controlling the surface shape of a glare-proof layer and improving glare and contrast is also known (for example, refer patent document 5). However, in the method described in Patent Document 5, since the inorganic fine particles are added in a large amount, the applicability of the composition for forming an anti-glare layer deteriorates, and there is a problem that coating defects such as spots or stripes are likely to occur.

Japanese Patent Laid-Open No. 6-18706 Japanese Patent Laid-Open No. 10-20103 Japanese Patent Laid-Open No. 11-305010 Japanese Patent Laid-Open No. 2002-267818 Japanese Patent No. 4510124 Publication

In view of the above current situation, the present invention is excellent in manufacturing stability, has good anti-glare property, can suppress the occurrence of glare at an extremely high level, and is a method for manufacturing a laminate that can obtain an excellent display image with high contrast , a laminate, a polarizing plate formed using the laminate, an image display device, and a method for improving visibility of an image display device.

The present invention is a method for manufacturing a laminate having an anti-glare layer having a concave-convex shape on one side of a light-transmitting substrate, wherein a composition for an anti-glare layer containing organic fine particles, inorganic fine particles, a binder resin and a solvent is applied to the light transmissive substrate has a step of forming the anti-glare layer by drying and curing the coating film formed by applying it on one side of the After preparation, it is prepared by mixing and dispersing the said inorganic fine particle in the said intermediate composition, The manufacturing method of the laminated body characterized by the above-mentioned.

In addition, the present invention is a laminate having an anti-glare layer having an uneven shape on the surface on one side of a light-transmitting substrate, wherein the uneven shape of the surface of the anti-glare layer is a measurement area of 100 µm square on the surface of the anti-glare layer The ratio of Ma and Sq (Sq/Ma ) is also a laminate characterized in that 0.15 or less.

In the laminate of the present invention, the anti-glare layer preferably contains a binder resin, organic fine particles and inorganic fine particles.

The present invention also provides a laminate having, on one side of a light-transmitting substrate, an anti-glare layer having an uneven shape on the surface, wherein the anti-glare layer contains a binder resin, organic fine particles and inorganic fine particles, the inorganic fine particles comprising: It is also a laminate characterized by being sparsely distributed around the organic fine particles and uniformly distributed in the anti-glare layer except around the organic fine particles.

In the laminate of the present invention, the inorganic fine particles are preferably silica fine particles, and the average particle diameter of the aggregates of the silica fine particles is preferably 100 nm to 1 μm.

Moreover, it is preferable that the said binder resin uses the polyfunctional acrylate monomer which does not contain a hydroxyl group in a molecule|numerator as a main material.

In addition, the organic fine particles include at least one material selected from the group consisting of acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyethylene resins, epoxy resins, silicone resins, polyvinylidene fluoride resins, and polyethylene fluoride resins. It is preferable that it is microparticles|fine-particles containing it, and it is preferable that the surface hydrophilization process is not carried out.

This invention is also a polarizing plate provided with a polarizing element, The said polarizing plate is equipped with the laminated body mentioned above on the polarizing element surface, It is also a polarizing plate characterized by the above-mentioned.

This invention is also equipped with the laminated body mentioned above on the outermost surface, or the polarizing plate mentioned above, The image display apparatus characterized by the above-mentioned.

The present invention also provides a method for improving visibility of an image display device using a laminate having, on one side of a light-transmitting substrate, an anti-glare layer having an uneven shape on the surface, wherein the anti-glare layer of the laminate is organic fine particles, inorganic A coating film formed by applying a composition for an anti-glare layer containing fine particles, a binder resin and a solvent on one side of the light-transmitting substrate is dried and then cured, and the composition for an anti-glare layer is added to the solvent, the binder resin and the It is also a method for improving the visibility of an image display device, comprising mixing and stirring organic fine particles to prepare an intermediate composition, and then mixing and dispersing the inorganic fine particles in the intermediate composition.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

As a result of the present inventors earnestly examining about the laminated body which provided the glare-proof layer which has an uneven|corrugated shape on the surface on the light-transmitting base material, the glare-proof layer of the laminated body is formed using the composition for glare-proof layer prepared by the specific method, The unevenness|corrugation The shape is more uniformly and uniformly formed compared to the anti-glare layer of the conventional laminate, and the laminate having such an anti-glare layer can suppress the occurrence of glare to an extremely high level while having good anti-glare properties. , found that an excellent display image with high contrast could be obtained, and completed the present invention.

Furthermore, as a result of earnest examination, the present inventors have made the glare-proof layer highly controlled so that the ratio (Sq/Ma) of the average value Ma of the arithmetic mean roughness Sa of uneven|corrugated shape and the standard deviation Sq of the arithmetic mean roughness Sa becomes within a predetermined range. Silver discovered that the said uneven|corrugated shape became what was formed very uniformly and uniformly, and came to complete the laminated body of this invention.

In addition, as a result of intensive studies, the present inventors have found that the anti-glare layer having the concave-convex shape controlled to be more uniform and uniform compared to the concavo-convex shape of the surface of the conventional anti-glare layer is composed of organic and inorganic fine particles contained therein. It found out what was obtained by controlling so that it might become a specific state, and came to complete the laminated body of this invention which concerns on another form.

This invention is a manufacturing method of the laminated body which has the glare-proof layer which has an uneven|corrugated shape on the surface on one side of a light-transmissive base material.

It is preferable that the said light-transmitting base material is equipped with smoothness and heat resistance, and is excellent in mechanical strength. Specific examples of the material for forming the light-transmissive substrate include, for example, polyester (polyethylene terephthalate, polyethylene naphthalate), cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, polyester, polyamide, polyimide, and polyether. and thermoplastic resins such as sulfone, polysulfone, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polymethyl methacrylate, polycarbonate, or polyurethane. Preferably, polyester (polyethylene terephthalate, polyethylene naphthalate) and cellulose triacetate are mentioned.

As the light-transmitting substrate, it is preferable to use the above-mentioned thermoplastic resin as a film-like body with high flexibility, but depending on the usage form requiring curability, it is also possible to use a plate of these thermoplastic resins, or a plate-like body such as a glass plate. you can use that

In addition, examples of the light-transmitting substrate include an amorphous olefin polymer (Cyclo-Olefin-Polymer: COP) film having an alicyclic structure. This is a base material in which a norbornene-based polymer, a monocyclic cyclic olefin-based polymer, a cyclic conjugated diene-based polymer, a vinyl alicyclic hydrocarbon-based polymer, etc. are used, for example, Zeonex and Zeonoa (Norborne) manufactured by Nippon Zeon Corporation. Nene-based resin), Sumitomo Bakelite Co., Ltd. Sumilite FS-1700, JSR Co., Ltd. Aton (modified norbornene-based resin), Mitsui Chemicals Arpel (cyclic olefin copolymer), Ticona Co., Ltd. Topas (cyclic cyclic resin) olefin copolymer), Hitachi Chemical Co., Ltd. Optolet's OZ-1000 series (alicyclic acrylic resin), etc. are mentioned.

Moreover, the FV series (low birefringence, low photoelasticity film) manufactured by Asahi Kasei Chemicals is also preferable as an alternative base material for triacetyl cellulose.

As thickness of the said light-transmitting base material, in the case of a film form, it is preferable that it is 5-300 micrometers, More preferably, the lower limit is 20 micrometers, and the upper limit is 200 micrometers. When the light-transmitting base material is a plate-shaped object, the thickness exceeding this thickness may be sufficient.

When the light-transmitting substrate is formed with the hard coating layer thereon, in addition to physical or chemical treatments such as corona discharge treatment and oxidation treatment to improve adhesion, an anchor agent or a paint called a primer is applied in advance. do.

In addition, when triacetyl cellulose, which is often used mainly as a light-transmitting substrate suitable for LCDs, is used as a material, and a display thinning is aimed at, the thickness of the light-transmitting substrate is preferably 20 to 65 µm.

The anti-glare layer is formed on one surface of the light-transmitting substrate, and has an uneven shape on the surface.

The manufacturing method of the laminated body of this invention has the process of forming such a glare-proof layer.

In this step, the anti-glare layer is formed by applying a composition for an anti-glare layer containing organic fine particles, inorganic fine particles, a binder resin and a solvent on one side of the light-transmissive substrate, drying and curing the coating film.

In the method for producing a laminate of the present invention, since the composition for forming an anti-glare layer contains organic fine particles and inorganic fine particles, the concavo-convex shape formed on the surface of the formed anti-glare layer is a single fine particle (eg, organic fine particles) or a single particle aggregate (eg, silica fine particle aggregate) to form a more uniformly and uniformly formed shape as compared with the uneven shape formed on the surface of the anti-glare layer. It is estimated that this is because, in the laminated body manufactured by the manufacturing method of the laminated body of this invention, the said inorganic fine particle and organic fine particle are distributed in a specific state in a glare-proof layer so that it may mention later.

In addition, the organic fine particles and inorganic fine particles preferably have a spherical shape in a state of single particles. When the layered product to be produced is applied to an image display device because the individual particles of the organic fine particles and the inorganic fine particles have such a spherical shape, a high-contrast display image can be obtained.

In addition, the said "spherical shape" includes, for example, a true spherical shape and an elliptical spherical shape, and is a meaning excluding so-called indefinite shapes.

The organic fine particles are fine particles that mainly form the surface uneven shape of the anti-glare layer, and are fine particles whose refractive index and particle size can be easily controlled. By including such organic microparticles|fine-particles, it becomes easy to control the size of the uneven shape formed in a glare-proof layer, and the refractive index of an anti-glare layer, and control of anti-glare property and generation|occurrence|production of glare and white blur can be suppressed.

The organic fine particles include at least one material selected from the group consisting of acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyethylene resins, epoxy resins, silicone resins, polyvinylidene fluoride resins and polyethylene fluoride resins. It is preferable that it is microparticles|fine-particles. Especially, styrene-acrylic copolymer microparticles|fine-particles are used preferably.

It is preferable that the said organic microparticles|fine-particles are not surface-hydrophilized. When the organic fine particles are subjected to a surface hydrophilization treatment, the affinity with the inorganic fine particles becomes too high, and there is a fear that it becomes difficult to sparsely distribute the inorganic fine particles around the organic fine particles. In addition, the said "sparse distribution" is demonstrated in detail later.

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

As content of the said organic microparticles|fine-particles, it is preferable that it is 1-50 mass % by solid content in the said composition for glare-proof layers. When it is less than 1 mass %, the anti-glare performance of the laminate to be produced may become insufficient, and when it exceeds 50 mass %, a problem of white blur may occur, and the produced laminate is used for an image display device. In this case, the contrast of the displayed image may be lowered. A more preferable lower limit is 5 mass %, and a more preferable upper limit is 20 mass %.

Moreover, it is preferable that the said organic microparticles|fine-particles are microparticles|fine-particles with a comparatively even particle diameter.

Here, the "fine particles having a relatively uniform particle diameter" means that when the average particle diameter of the particles according to the weight average is MV, the cumulative 25% diameter is d25, and the cumulative 75% diameter is d75, (d75-d25)/MV is 0.25 means the following cases.

Incidentally, the cumulative 25% diameter refers to the particle diameter when the particle size in the particle size distribution becomes 25 mass% by counting from the smallest particle size, and the cumulative 75% diameter refers to the particle size when the particle size becomes 75 mass% by counting similarly. say diameter.

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

When the composition for forming an anti-glare layer contains such organic fine particles, it becomes easy to preferably form a uniform and uniform concavo-convex shape on the surface of the anti-glare layer.

In addition, the size of the organic fine particles is appropriately determined according to the thickness of the anti-glare layer to be formed, for example, it is preferable that the average particle diameter is 0.3 to 6.0 µm. When it is less than 0.3 µm, there is a fear that the dispersibility of the organic fine particles cannot be controlled, and when it exceeds 6.0 µm, the uneven shape of the surface of the anti-glare layer becomes large, and the problem of surface glare may occur. A more preferable lower limit is 2.0 micrometers, and a more preferable upper limit is 4.0 micrometers.

Moreover, it is preferable that the average particle diameter of the said organic microparticles|fine-particles is 20 to 90 % with respect to the thickness of the glare-proof layer to form. When it exceeds 90 %, the influence which the dispersion|variation of a film thickness exerts on an uneven|corrugated shape becomes strong, and there exists a possibility that a glare-proof layer may be formed in uneven form. If it is less than 20 %, sufficient uneven|corrugated shape cannot be formed in the glare-proof layer surface, and glare-proof performance may become inadequate.

In addition, when measuring the average particle diameter of the said organic microparticles|fine-particles alone, it can measure as a weight average diameter by the Coulter counter method. On the other hand, the average particle diameter of the organic microparticles|fine-particles in a glare-proof layer WHEREIN: In transmission optical microscopy of an anti-glare layer, it makes the value which averaged the maximum diameter of 10 particle|grains, and is calculated|required. Or, if it is unsuitable, in electron microscope (preferably transmission type such as TEM or STEM, hereinafter the same) observation of a cross section passing near the particle center, diffuse particles of any same kind and substantially the same diameter are observed. It is a value calculated by selecting 30 pieces (the number of selected particles is increased because it is not clear which part of the cross-section of the particle is), measuring the maximum particle diameter of the cross-section, and calculating the average value. Since all are judged from an image, you may calculate with image analysis software.

It is preferable that the inorganic fine particles mainly have an effect of stably presenting the organic fine particles in the anti-glare layer in a state capable of forming a uniform concavo-convex shape, and are uniformly dispersed in the composition for the anti-glare layer.

As such inorganic fine particles, for example, it is preferable that they are silica fine particles. Hereinafter, the said inorganic fine particle is demonstrated as a silica fine particle.

When the silica fine particles are uniformly distributed in the composition for an anti-glare layer, they are uniformly dispersed in the anti-glare layer to be formed, and a uniform and uniform concavo-convex shape can be formed on the surface thereof.

The "uniform distribution in the anti-glare layer" means any cross-section from a location where organic particles in the thickness direction of the anti-glare layer are not observed under the condition of 10,000 times magnification with an electron microscope (transmission type such as TEM or STEM is preferable). When ten observations are made, the area ratio of silica fine particles in the observation region of 5 μm square is measured for each cross section, and when the average value is M and the standard deviation is S, it means that S/M≤0.1.

In addition, the distribution of such silica microparticles|fine-particles can be discriminate|determined easily by the cross-sectional electron microscope observation of the thickness direction of the said glare-proof layer. For example, FIG. 2 is a cross-sectional STEM photograph of the laminate according to Example 1, and FIG. 3 is another cross-sectional STEM photograph of the laminate according to Example 1. In FIGS. 2 and 3, It is clear that the dark band-shaped region is the cross section of the anti-glare layer, and in the cross section of the anti-glare layer, the portion observed as a black spot is the aggregate of the silica fine particles, and the aggregate of the silica fine particles is uniformly dispersed in the anti-glare layer. can be confirmed In addition, the area ratio of the aggregate of the said silica microparticles|fine-particles can be computed using image analysis software, for example.

In the present invention, the silica fine particles are preferably surface-treated. When the silica fine particles are surface-treated, the distribution of the silica fine particles in the composition for an anti-glare layer and the anti-glare layer to be formed can be preferably controlled, and the effect of sparse distribution around the organic fine particles can be controlled within an appropriate range. can do. Moreover, the improvement of the chemical-resistance and saponification resistance of silica microparticles|fine-particles itself can also be aimed at.

As said surface treatment, the hydrophobization treatment which makes the surface of microparticles|fine-particles hydrophobicity is preferable. Examples of the hydrophobic treatment include a method of treating the silica fine particles with a silane compound having an acryl group such as a methyl group or an octyl group.

Here, although hydroxyl groups (silanol groups) are usually present on the surface of the silica fine particles, the surface treatment reduces the hydroxyl groups on the surface of the silica fine particles, so that excessive aggregation of the silica fine particles can be prevented. The effect of preventing the microparticles|fine-particles from being non-uniformly disperse|distributing is exhibited.

Moreover, it is preferable that the said silica fine particle contains amorphous silica. When the silica fine particles contain crystalline silica, the Lewis acidity of the silica fine particles becomes strong due to lattice defects contained in the crystal structure, and excessive aggregation of the silica fine particles may become uncontrollable.

As such silica fine particles, for example, fumed silica is preferably used from the viewpoint of being easy to aggregate by itself and easy to form aggregates having the above-mentioned particle diameter. Here, the fumed silica refers to amorphous silica having a particle size of 200 nm or less produced by a dry method, and is obtained by reacting a volatile compound containing silicon in a gas phase. Specific examples thereof include those produced by hydrolyzing a silicon compound such as SiCl ₄ in the flame of oxygen and hydrogen. Specifically, AEROSIL R805 (made by Nippon Aerosil Co., Ltd.) etc. are mentioned, for example.

Although it does not specifically limit as content of the said silica fine particle, It is preferable that it is 1.0-10.0 mass % in the said glare-proof layer. If it is less than 1.0 mass %, the above-mentioned organic fine particles may not be able to be present so as to form a uniform concavo-convex shape. . A more preferable lower limit is 3.0 mass %, and a more preferable upper limit is 8.0 mass %.

The silica fine particles preferably have an average primary particle diameter of 1 to 100 nm. If it is less than 1 nm, a preferable aggregate may not be formed, and if it exceeds 100 nm, light is diffused by the silica fine particles, and the dark room contrast of the image display apparatus using the laminated body to manufacture may fall. A more preferable lower limit is 5 nm, and a more preferable upper limit is 50 nm.

The average primary particle diameter of the silica fine particles is a value measured using image processing software from an image of a cross-sectional electron microscope (transmission type such as TEM or STEM, preferably magnification of 50,000 times or more).

Further, in the present invention, when the silica fine particles form an aggregate, the above-mentioned silica fine particles in a cross-sectional electron microscope of the anti-glare layer form a structure connected to a pearl necklace shape.

In the anti-glare layer, since the silica fine particles form an agglomerate connected to a pearl necklace, it is possible to effectively exhibit the effect of stably presenting the organic fine particles in a state capable of forming a uniform concavo-convex shape.

In addition, the structure in which the silica fine particles are connected in a pearl necklace type means, for example, a structure in which the silica fine particles are continuously connected in a straight line (linear structure), a structure in which a plurality of the linear structures are entangled with each other, and a plurality of silica fine particles in the linear structure Arbitrary structures, such as a branched structure which has 1 or 2 or more side chains formed continuously, are mentioned.

Moreover, it is preferable that the average particle diameter of the aggregate of the said silica microparticles|fine-particles is 100 nm - 1 micrometer. When it is less than 100 nm, there is a fear that the above-mentioned effects cannot be exhibited, and when it exceeds 1 µm, light is diffused by the aggregate of silica fine particles, and the dark room contrast of the image display device using the laminate to be manufactured may be deteriorated. A more preferable lower limit of the average particle diameter of the aggregate is 200 nm, and a more preferable upper limit thereof is 800 nm.

In addition, as for the average particle diameter of the aggregates of the silica fine particles, from observation with a cross-sectional electron microscope (about 10,000 to 20,000 times), a 5 µm square region containing many silica fine aggregates is selected, and silica fine particles in the area are selected. The particle diameters of the aggregates were measured, and the particle diameters of the aggregates of the top ten silica fine particles were averaged.

In addition, the "particle diameter of the aggregate of silica fine particles" is a combination of two straight lines in which the distance between the two straight lines is maximized when the cross section of the aggregate of silica fine particles is sandwiched between two arbitrary straight lines. It is measured as the distance between straight lines in In addition, you may calculate the particle diameter of the aggregate of the said silica fine particle using image analysis software.

In such a specific state, since the aggregate and organic fine particles connected in a pearl necklace shape of silica fine particles are contained in the composition for an anti-glare layer, the anti-glare layer in the laminate to be produced has a more concave-convex shape formed by the single fine particles or the aggregate, The concavo-convex shape is formed uniformly and uniformly. As a result, the laminated body to manufacture has favorable anti-glare property, can suppress glare, and can improve contrast.

When the unevenness is uniform and uniform, the extremely large convex portion serving as a singularity is eliminated while sufficiently providing anti-glare properties. Therefore, since significant distortion of transmitted light is eliminated, glare can be suppressed, and large diffusion can be eliminated, so that it can be made excellent in contrast.

This is estimated to be based on the following reasons.

That is, when the composition for an anti-glare layer is applied and then dried and the solvent is evaporated, the appropriately aggregated silica fine particles are uniformly dispersed, so that the organic fine particles forming the unevenness can also be maintained in a uniformly dispersed state. In addition, since the inorganic fine particles are sparsely distributed around the organic fine particles, the curing shrinkage of the binder resin is increased compared to a location where the inorganic fine particles are widely distributed. formed stably. For this reason, it is estimated that the uneven|corrugated shape (convex part) formed on the surface of the glare-proof layer by the said organic fine particle becomes more uniform and uniform compared with the uneven|corrugated shape (convex part) formed by the fine particle single-piece|unit.

The binder resin is preferably a polyfunctional acrylate monomer containing no hydroxyl group in its molecule as a main material. The above "using a polyfunctional acrylate monomer that does not contain a hydroxyl group in a molecule as a main material" means that the content of the polyfunctional acrylate monomer that does not contain a hydroxyl group in the molecule is the highest among the raw material monomers of the binder resin.

Since the polyfunctional acrylate monomer which does not contain a hydroxyl group in the said molecule|numerator is a hydrophobic monomer, in the laminated body of this invention, it is preferable that the binder resin which comprises the said glare-proof layer is a hydrophobic resin. When the binder resin is mainly a hydrophilic resin having a hydroxyl group, it becomes difficult to evaporate a highly polar solvent (for example, isopropyl alcohol), which will be described later, and it becomes impossible to distribute the inorganic fine particles sparsely around the organic fine particles. There are concerns.

Examples of the polyfunctional acrylate monomer that does not contain a hydroxyl group in the 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, trimethylol propane triacrylate (TMPTA), trimethylol propane ethoxy triacrylate, di Pentaerythritol hexaacrylate (DPHA), pentaerythritol ethoxytetraacrylate, ditrimethylolpropane tetraacrylate, etc. are mentioned. Among them, pentaerythritol tetraacrylate (PETTA) is preferably used.

Moreover, as another binder resin, a transparent thing is preferable, for example, it is preferable that an ionizing-radiation-curable resin which is a resin hardening|cured by an ultraviolet-ray or an electron beam is what hardened|cured by irradiation of an ultraviolet-ray or an electron beam.

In addition, in this specification, unless otherwise indicated, "resin" is a concept including a monomer, an oligomer, a polymer, etc.

As said ionizing-radiation-hardening type resin, the compound which has 1 or 2 or more unsaturated bonds, such as a compound which has functional groups, such as an acrylate type, is mentioned, for example. As a compound which has the unsaturated bond of 1, ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, methylstyrene, N-vinylpyrrolidone etc. are mentioned, for example. As the compound having two or more unsaturated bonds, for example, trimethylolpropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, pentaerythritol tri(meth) Acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylol Propane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meth) acrylate , isocyanuric acid tri (meth) acrylate, isocyanuric acid di (meth) acrylate, polyester tri (meth) acrylate, polyester di (meth) acrylate, bisphenol di (meth) acrylate, diglycerin Polyfunctional compounds such as tetra(meth)acrylate, adamantyldi(meth)acrylate, isoboronyldi(meth)acrylate, dicyclopentanedi(meth)acrylate, and tricyclodecanedi(meth)acrylate and the like. In addition, in this specification, "(meth)acrylate" points out a methacrylate and an acrylate. Moreover, in this invention, what modified|denatured the above-mentioned compound with PO, EO, etc. can be used as said ionizing-radiation-hardening type resin.

In addition to the above compounds, relatively low molecular weight polyester resins having unsaturated double bonds, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiolpolyene resins, etc. It can be used as a curable resin.

The ionizing radiation curable resin may be used in combination with a solvent-dried resin (a resin that forms a film by simply drying a solvent added to adjust the solid content during coating, such as a thermoplastic resin). By using solvent drying type resin together, when forming a glare-proof layer, the film defect of the coating surface of a coating liquid can be prevented effectively.

It does not specifically limit as solvent-dried resin which can be used together with the said ionizing-radiation-hardening-type resin, Generally, a thermoplastic resin can be used.

The thermoplastic resin is not particularly limited and includes, for example, styrene-based resin, (meth)acrylic-based resin, vinyl acetate-based resin, vinyl ether-based resin, halogen-containing resin, alicyclic olefin-based resin, polycarbonate-based resin, poly and ester-based resins, polyamide-based resins, cellulose derivatives, silicone-based resins and rubber or elastomers. It is preferable that the said thermoplastic resin is amorphous and is soluble in an organic solvent (especially the common solvent which can melt|dissolve several polymer and a sclerosing|hardenable compound). In particular, from the viewpoints of film forming properties, transparency and weather resistance, styrene resins, (meth)acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (cellulose esters, etc.) are preferable.

Moreover, the said composition for glare-proof layers may contain the thermosetting resin.

The thermosetting resin is not particularly limited and includes, for example, a phenol resin, a urea resin, a diallyl phthalate resin, a melamine resin, a guanamine resin, an unsaturated polyester resin, a polyurethane resin, an epoxy resin, an aminoalkyd resin, and a melamine-urea ball. Condensation resin, silicon resin, polysiloxane resin, etc. are mentioned.

In the composition for the anti-glare layer, the silica fine particles are preferably uniformly dispersed in the composition, and as shown in FIG. 4, when the coating film is dried, it is sparsely distributed around the organic fine particles. it is preferable 4 is another cross-sectional STEM photograph of the laminate according to Example 1.

If the silica particles are not uniformly dispersed in the composition for an anti-glare layer, uniform dispersion in the anti-glare layer to be formed cannot be achieved, and aggregation occurs excessively in the composition for an anti-glare layer, and the silica particles becomes a large agglomerate, and it may not be possible to form the anti-glare layer having the above-mentioned uniform and uniform concavo-convex shape.

Here, since the silica fine particles are a material capable of thickening the composition for an antiglare layer, it is possible to suppress settling of the organic fine particles contained in the composition for an antiglare layer by containing the silica fine particles. That is, it is estimated that the said silica fine particle also has the function of improving the pot life of the composition for glare-proof layer with the formation promotion function of the predetermined|prescribed distribution of the organic fine particle and silica fine particle mentioned above.

In addition, as a method in which the silica fine particles are uniformly dispersed in the composition for an anti-glare layer and sparsely distributed around the organic fine particles in the coating film, for example, as a solvent added to the composition for an anti-glare layer, A method of containing a predetermined amount of a solvent having high polarity and a high volatilization rate is exemplified. By containing the solvent having such high polarity and a high volatilization rate, it is possible to prevent excessive aggregation of the silica fine particles in the composition for the anti-glare layer. On the other hand, when applying on the light-transmitting substrate and drying to form a coating film, the solvent having a high polarity and a high volatilization rate volatilizes earlier than other solvents, so the composition at the time of forming the coating film is modified, as a result , in the coating film, the periphery of the organic fine particles becomes more hydrophobic, the affinity with the silica fine particles is lowered, and the silica fine particles are difficult to exist, so that a sparsely distributed state can be formed around the organic fine particles. .

In addition, in this specification, "a solvent with high polarity" means a solvent having a solubility parameter of 10 [(cal/cm 3 ) ^1/2 ] or more, and a “solvent with a high volatilization rate” is a solvent having a relative evaporation rate of 150 or more. means solvent. Therefore, the said "a solvent with high polarity and a fast volatilization rate" means a solvent which satisfies both the requirements of the said "solvent with high polarity" and "a solvent with a fast volatilization rate".

In this specification, the said solubility parameter is calculated by Fedors' method. Fedors' method is described, for example, in "SP value basics, application and calculation method" (published by Johokiko Johokiko Co., Ltd., published by Hideki Yamamoto, 2005). In Fedors' method, the solubility parameter is computed from the following formula.

Solubility parameter=[ΣE _coh /ΣV] ²

In the above formula, E _coh is the cohesive energy density, and V is the molar molecular volume. Based on E _coh and V determined for each atomic group, the solubility parameter can be calculated by calculating ?E _coh and ?V, which are the sum of E _coh and V.

In addition, in this specification, the said relative evaporation rate means a relative evaporation rate when the evaporation rate of n-butyl acetate is 100, is an evaporation rate measured based on ASTM D3539-87, and is calculated by the following formula do. Specifically, it calculates by measuring the evaporation time of n-butyl acetate and the evaporation time of each solvent in 25 degreeC and dry air.

Relative evaporation rate = (time required to evaporate 90% by weight of n-butyl acetate)/(time required for 90% by weight to evaporate to the measurement solvent) x 100

Examples of the solvent having high polarity and a high volatilization rate include ethanol and isopropyl alcohol, and among these, isopropyl alcohol is preferably used.

Moreover, it is preferable that content of the isopropyl alcohol in the said solvent is 10 mass % or more in all the solvents. If it is less than 10 mass %, the aggregate of silica microparticles|fine-particles may generate|occur|produce in the composition for glare-proof layers. It is preferable that content of the said isopropyl alcohol is 40 mass % or less. If it is more than 40 mass %, there exists a possibility that it may become impossible to distribute the said silica fine particle sparsely around the said organic fine particle.

Examples of other solvents contained in the composition for the anti-glare layer include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons. (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.) , alcohols (butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethyl sulfoxide, etc.), amides (dimethylformamide, dimethylacetamide etc.), etc. can be illustrated, and these mixtures may be sufficient.

It is preferable that the said composition for glare-proof layers contains a photoinitiator further.

It does not specifically limit as said photoinitiator, A well-known thing can be used, For example, acetophenones, benzophenones, Michler benzoyl benzoate, (alpha)-amyloxime ester, thioxanthone, propiophe Non-stains, benzyls, benzoins, and acylphosphine oxides are mentioned. Moreover, it is preferable to mix and use a photosensitizer, and as the specific example, n-butylamine, triethylamine, poly-n-butylphosphine, etc. are mentioned, for example.

As the photoinitiator, when the binder resin is a resin having a radically polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, etc. are preferably used alone or in combination. Do. In addition, when the binder resin is a resin having a cationically polymerizable functional group, as the photopolymerization initiator, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, a benzoinsulfonic acid ester, etc. alone or a mixture It is preferable to use it as

It is preferable that content of the said photoinitiator in the said composition for glare-proof layers is 0.5-10.0 mass parts with respect to 100 mass parts of said binder resins. Since the hard-coat performance of the glare-proof layer to form may become inadequate as it is less than 0.5 mass part, and since hardening may be inhibited conversely when it exceeds 10.0 mass part also arises, it is unpreferable.

Although it does not specifically limit as content rate (solid content) of the raw material in the said composition for glare-proof layers, Usually, it is 5-70 mass %, It is preferable to set it as 25-60 mass % especially.

In the composition for the anti-glare layer, according to the purpose of increasing the hardness of the anti-glare layer, suppressing cure shrinkage, or controlling the refractive index, conventionally known dispersants, surfactants, antistatic agents, silane coupling agents, thickeners, color inhibitors, A coloring agent (pigment, dye), an antifoaming agent, a leveling agent, a flame retardant, an ultraviolet absorber, an adhesion imparting agent, a polymerization inhibitor, an antioxidant, a surface modifier, a lubricant, and the like may be added.

As said leveling agent, silicone oil, a fluorine-type surfactant, etc. are mentioned, for example, Preferably, the fluorine-type surfactant etc. containing a perfluoroalkyl group avoid the glare-proof layer from becoming a Bernard cell structure. desirable. When a resin composition containing a solvent is coated and dried, a difference in surface tension or the like is generated between the surface and the inner surface of the coating film in the coating film, thereby causing a large number of convection in the coating film. The structure generated by this convection is called a Bernard cell structure, and causes problems such as orange peel and coating defects in the anti-glare layer to be formed.

In addition, in the above-mentioned Bernard cell structure, the unevenness of the surface of the anti-glare layer becomes too large, which adversely affects white blur and surface glare. When the leveling agent as described above is used, since this convection can be prevented, not only an uneven film without defects or unevenness can be obtained, but also adjustment of the uneven shape becomes easy.

Moreover, the said composition for glare-proof layers may mix and use a photosensitizer, As the specific example, n-butylamine, triethylamine, poly-n-butylphosphine, etc. are mentioned, for example.

In the method for manufacturing a laminate of the present invention, the composition for the antiglare 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 adding the inorganic fine particles (silica fine particles) to the intermediate composition. It is prepared by mixing and dispersing.

That is, in the present invention, in the composition for an anti-glare layer, inorganic fine particles are added last among essential constituent materials of the composition for an anti-glare layer. When the composition for an anti-glare layer is prepared by adding the inorganic fine particles to a solvent before adding the organic fine particles or the binder resin, excessive aggregation of the inorganic fine particles due to solvent attack occurs, which has a uniform and uniform concave-convex shape It becomes impossible to form a glare-proof layer. Further, in order to ensure the above-mentioned effect, when the inorganic fine particles are finally added, it is more preferable that the inorganic fine particles are dispersions of inorganic fine particles dispersed in the above solvent.

A method for preparing the intermediate composition is not particularly limited as long as the organic fine particles and the binder resin can be uniformly mixed with the solvent. For example, a known apparatus such as a paint shaker, bead mill, kneader, or mixer is used. can be done by

In addition, the method similar to the method of adding the inorganic fine particle to the said intermediate composition and preparing the composition for glare-proof layer is mentioned above.

The method for applying the composition for the anti-glare layer on the light-transmitting substrate is not particularly limited, and for example, a spin coating method, an immersion method, a spray method, a die coating method, a bar coating method, a roll coater method, a meniscus coater method, Well-known methods, such as the flexographic printing method, the screen printing method, the bead coater method, are mentioned.

After applying the composition for an anti-glare layer by any of the above methods, it is transferred to a heated zone to dry the formed coating film, and the coating film is dried by various known methods to evaporate the solvent. Here, 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 concentration of the solvent atmosphere in the drying zone, and the like, the distribution state of the organic fine particles and the inorganic fine particles can be adjusted.

In particular, the method of adjusting the distribution state of the aggregate of organic fine particles and silica fine particles by selection of drying conditions is simple and preferable. As a specific drying temperature, it is preferable that it is 30-120 degreeC, and it is 0.2-50 m/s at a dry wind speed, and distribution of aggregates of organic microparticles|fine-particles and silica microparticles|fine-particles is carried out once or multiple times by performing the drying process suitably adjusted within this range once or multiple times. You can adjust the state to the desired state.

In addition, as a method of irradiating ionizing radiation for curing the dried coating film, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp. can be heard

In addition, as a wavelength of an ultraviolet-ray, the wavelength range of 190-380 nm can be used. As a specific example of an electron beam source, various electron beam accelerators, such as a Cockcroft Walton type, a Van der Graft type, a resonance transformer type, an insulated core transformer type, or a linear type, a dynamtron type, and a high frequency type, are mentioned.

As described above, in the laminate produced by the method for producing a laminate of the present invention, the dispersion of inorganic fine particles (silica fine particles) in the composition for forming an anti-glare layer is highly controlled, so that it is formed on the surface of the anti-glare layer. Compared with the uneven shape of the surface of the glare-proof layer of the conventional laminated body, the uneven|corrugated shape used becomes a thing formed extremely uniformly and uniformly.

Since the anti-glare layer having such a concave-convex shape has almost no convex portions serving as singularities on its surface, glare can be suppressed to an extremely high level while having good anti-glare properties, and a high-contrast display image can be obtained. It can be made into a laminate with

In addition, a laminate having an anti-glare layer having an uneven shape on its surface on one side of the light-transmitting substrate, wherein the uneven shape of the surface of the anti-glare layer divides the surface of the anti-glare layer into a measurement area of 100 µm square, , when the arithmetic mean roughness Sa is obtained in each measurement area, and the average value of the arithmetic mean roughness Sa is Ma and the standard deviation of the arithmetic mean roughness Sa is Sq, the ratio of Ma to Sq (Sq/Ma) is 0.15 The laminated body characterized by the following is also one of this invention.

Since the resolution of the human eye is about 100 mu m, if the fluctuation in every 100 mu m is large, distortion of transmitted light is recognized by the human eye and observed as glare. For this reason, when the ratio of Ma to Sq (Sq/Ma) exceeds 0.15, distortion of the transmitted light of the laminate of the present invention is recognized and observed as glare. It is preferable that it is 0.12 or less, and, as for said (Sq/Ma), it is more preferable that it is 0.10 or less.

Further, in the laminate of the present invention, the average value (Ma) of Ra is preferably 0.10 µm or more and 0.40 µm or less. If it is less than 0.10 micrometer, the anti-glare property of the laminated body of this invention may become inadequate, and if it is more than 0.40 micrometer, the contrast of the laminated body of this invention may deteriorate.

In addition, the arithmetic mean roughness Sa is a three-dimensional extension of the arithmetic mean roughness Ra, which is a two-dimensional roughness parameter described in JIS B0601:1994. , y), assuming that the size of the measurement area plane is Lx, Ly, it is calculated by the following formula (a).

In addition, in said Formula (a), A=LxxLy is shown.

In addition, assuming that the height at the position of the i-th point 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).

In addition, in said Formula (b), N represents the total score.

As an apparatus for obtaining such three-dimensional arithmetic mean roughness Sa, a contact type surface roughness meter and a non-contact type surface roughness meter (for example, an interference microscope, a confocal microscope, an atomic force microscope, etc.) are mentioned. Among these, it is preferable to measure using an interference microscope from the viewpoint of the simplicity of a measurement. As such an interference microscope, the "New View" series by Zygo Corporation, etc. are mentioned.

In the laminate of the present invention, the anti-glare layer preferably contains a binder resin, organic fine particles and inorganic fine particles.

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

The method for manufacturing the laminate of the present invention is not particularly limited as long as it is a method capable of controlling the concavo-convex shape of the surface of the anti-glare layer to satisfy the above requirements. It can be manufactured by a method.

Further, a laminate having an anti-glare layer having an uneven shape on its surface on one side of a light-transmitting substrate, wherein the anti-glare layer contains a binder resin, organic fine particles and inorganic fine particles, and the inorganic fine particles include the organic fine particles. Another aspect of the present invention is also a laminate characterized in that it is sparsely distributed around the glare-proof layer and is uniformly distributed outside the periphery of the organic fine particles in the anti-glare layer.

The laminate of the present invention according to the other aspect has an anti-glare layer, the anti-glare layer contains 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 with an electron microscope, the inorganic fine particles sparsely distributed around the organic fine particles are sparse not only in the cross section passing through the center of the organic fine particles but also in the cross section shifted from the center of the organic fine particles. A state of distribution is observed.

In addition, the above-mentioned "the inorganic fine particles are sparsely distributed around the organic fine particles" means the organic matter in the thickness direction of the anti-glare layer under the condition of 10,000 times the magnification with an electron microscope (transmission type such as TEM or STEM is preferable). When microscopic observation of the cross section in which the fine particles are observed, the area ratio of the inorganic fine particles occupied within the circumference 500 nm outside from the organic fine particles and in the region excluding the organic fine particles is Mn, and outside the circumference 500 nm outside from the organic fine particles When the area ratio of the inorganic fine particles in the region of Mf is Mf, it means that Mf/Mn is 1.5 or more.

In addition, the said "distributed uniformly in the glare-proof layer except around the periphery of the organic fine particles" has the same meaning as "uniformly distributed in the glare-proof layer" described in the manufacturing method of the laminate of the present invention. .

In the laminate of the present invention according to another aspect, since organic fine particles and inorganic fine particles are contained in the anti-glare layer composition in the above-described method for manufacturing a laminate of the present invention in the anti-glare layer, the unevenness formed on the surface thereof is contained. The shape becomes extremely uniform and uniform compared with the uneven shape of the glare-proof layer of the conventional laminated body. According to the laminate of the present invention according to another aspect having such an anti-glare layer, the occurrence of glare can be suppressed to an extremely high level while having good anti-glare properties, and a high-contrast excellent display image can be obtained.

In the laminate of the present invention according to another aspect, examples of the binder resin, the organic fine particles and the inorganic fine particles, and the light-transmitting substrate include the same ones as those described in the manufacturing method of the laminate of the present invention described above.

In addition, as a method of manufacturing the laminate of the present invention according to another aspect, it is not particularly limited as long as it is a method capable of controlling the organic fine particles and inorganic fine particles in the anti-glare layer to be contained in the above-described state, but for example, It can manufacture with the manufacturing method of the laminated body of this invention.

The laminate of the present invention described above and the laminate of the present invention according to another aspect (hereinafter, collectively described as the laminate of the present invention) have a specific anti-glare layer as described above, and the surface of the anti-glare layer , an extremely uniform and uniform concavo-convex shape is formed as compared with the anti-glare layer of the conventional laminate.

Specifically, as the concavo-convex shape of the surface of the anti-glare layer, the average spacing of the concavities and convexities on the surface of the anti-glare layer is Sm, the average inclination angle of the concavo-convex portions is θa, the arithmetic mean roughness of the concavities and convexities is Ra, 10 points for concavities and convexities When average roughness is made into Rz, it is preferable to satisfy|fill the following formula. When θa, Ra, and Rz are less than the lower limit, projection of external light cannot be suppressed in some cases. Moreover, when θa, Ra, and Rz exceed the upper limit, there is a risk that the contrast in the dark room may decrease due to a decrease in the bright room contrast due to an increase in the diffuse reflection of external light or an increase in the stray light from the transmitted image light. In the structure of this invention, when Sm is less than a lower limit, there exists a possibility that contrast may fall. On the other hand, when Sm exceeds an upper limit, there exists a possibility that glare cannot fully be suppressed.

50㎛<Sm<300㎛

0.5°<θa<4.0°

0.05㎛<Ra<0.40㎛

0.30㎛<Rz<2.50㎛

Moreover, from the said viewpoint, More preferably, the uneven|corrugated shape of the said glare-proof layer satisfies the following formula.

50㎛<Sm<200㎛

0.8°<θa<2.0°

0.10㎛<Ra<0.25㎛

0.50㎛<Rz<1.80㎛

More preferably, the concavo-convex shape of the anti-glare layer satisfies the following formula.

70㎛<Sm<100㎛

1.0°<θa<1.5°

0.12㎛<Ra<0.18㎛

0.80㎛<Rz<1.30㎛

In addition, in this specification, the said Sm, Ra, and Rz are the values obtained by the method based on JISB0601-1994, θa is a surface roughness measuring instrument: SE-3400 Instruction Manual (revised on July 20, 1995) (KKKKK) It is a value obtained by the definition described in Geisha Kosaka Genkyusho), and as shown in FIG. 1 , the arc of the sum of the heights of the convex portions (h ₁ +h ₂ +h ₃ +… +h _n ) existing in the reference length L It can be calculated as tangent θa=tan ^-1 {(h ₁ +h ₂ +h ₃ +… +h _n )/L}.

Such Sm, θa, Ra, and Rz can be obtained by, for example, measuring with a surface roughness measuring instrument: SE-3400/Kosaka Genkyusho Co., Ltd. or the like.

Moreover, as thickness of the said glare-proof layer, it is preferable that it is 2.0-7.0 micrometers. If it is less than 2.0 micrometers, the surface of an anti-glare layer may become easily damaged, and when it exceeds 7.0 micrometers, the anti-glare layer may become easily broken. The more preferable range of the thickness of the said glare-proof layer is 2.0-5.0 micrometers. In addition, the thickness of the said glare-proof layer can be measured by cross-sectional microscope observation.

It is preferable that the laminated body of this invention has a total light transmittance of 85 % or more. If it is less than 85 %, when the laminated body of this invention is attached to the surface of an image display apparatus, there exists a possibility of impairing color reproducibility and visibility. As for the said total light transmittance, it is more preferable that it is 90 % or more, and it is still more preferable that it is 91 % or more.

In addition, the said total light transmittance can be measured by "HM-150" by the Murakami Shikisai Kijutsu Genkyusho company etc. according to JISK7361.

Moreover, it is preferable that haze is less than 40 % of the laminated body of this invention. The anti-glare layer may include an internal haze due to internal diffusion due to the fine particles contained therein and an external haze due to the concavo-convex shape of the outermost surface, and the internal haze due to internal diffusion is in the range of 5% or more and 30% or less. desirable. If it is less than 5 %, there exists a possibility that the glare of the laminated body of this invention may not fully be suppressed, and when it exceeds 30 %, there exists a possibility that the contrast of the laminated body of this invention may fall. Moreover, as for the internal haze of the laminated body of this invention, it is more preferable that it is the range of 5 % or more and 20 % or less, It is still more preferable that it is the range of 5 % or more and 15 % or less. It is preferable that the external haze of an outermost surface is the range of 5 % or more and 30 % or less. If it is less than 5 %, there exists a possibility that the anti-glare property of the laminated body of this invention may not be enough, and when it exceeds 30 %, there exists a possibility that the contrast of the laminated body of this invention may fall. As for the external haze of the laminated body of this invention, it is more preferable that it is the range of 5 % or more and 20 % or less, It is still more preferable that it is the range of 7 % or more and 15 % or less.

Further, in the laminate of the present invention, by using fumed silica as the inorganic fine particles, the internal haze and the external haze of the anti-glare layer can be controlled independently, respectively. For example, by using fumed silica, since the average particle diameter of the fumed silica is small, internal haze is not expressed and only external haze can be adjusted. In addition, the adjustment of the internal haze can be adjusted by controlling the ratio of the refractive index of the organic fine particles and the refractive index of the binder resin, or by changing the refractive index of the organic particle interface by impregnating the organic fine particles with a monomer of the binder resin.

The said haze can be measured by "HM-150" by a Murakami Shikisai Kijutsu Genkyusho company, etc. according to JISK7136.

In addition, the said internal haze is calculated|required as follows.

On the unevenness on the surface of the anti-glare layer of the laminate, a resin having the same refractive index as the resin forming the surface unevenness or a refractive index difference of 0.02 or less is dried with a wire bar to a film thickness of 8 µm (the surface uneven shape is completely eliminated, and the surface is It is applied so as to have a film thickness that can be said to be flat), dried at 70° C. for 1 minute, and then cured by irradiation with ultraviolet rays at 100 mJ/cm 2 . Thereby, the unevenness|corrugation in the surface is crushed, and the film which became a flat surface is obtained. However, when a leveling agent or the like is contained in the composition for forming the anti-glare layer having the concave-convex shape, so that the resin applied to the surface of the anti-glare layer is easily repelled and is difficult to adhere, the surface of the anti-glare layer is preliminarily subjected to a saponification treatment ( After immersion at 55° C. for 3 minutes with 2 mol/L NaOH (or KOH) solution, wash with water, completely remove water droplets with Kimwipe (registered trademark), etc., and then dry in an oven at 50° C. for 1 minute). should be carried out

Since the film which flattened this surface does not have surface unevenness|corrugation, it is in the state which has only an internal haze. An internal haze can be calculated|required by measuring the haze of this film by the method similar to a haze according to JISK-7136.

In addition, the said external haze can be calculated|required as (haze-internal haze).

Moreover, it is preferable that the laminated body of this invention has a low-refractive-index layer on the said glare-proof layer at the point which can prevent generation|occurrence|production of white blur more preferably.

The low refractive index layer is a layer that lowers the reflectance when light from the outside (eg, fluorescent lamp, natural light, etc.) is reflected on the surface of the optical laminate. The low-refractive-index layer is preferably 1) a resin containing low-refractive-index particles such as silica or magnesium fluoride, 2) a fluorine-based resin that is a low-refractive-index resin, 3) a fluorine-based resin containing silica or magnesium fluoride, 4) silica, fluoride It is composed of any one of a thin film of a low refractive index material such as magnesium. For resins other than the fluorine-based resin, the same resin as that of the binder resin constituting the anti-glare layer described above can be used.

In addition, it is preferable that the above-mentioned silica is a hollow silica fine particle, and such a hollow silica fine particle can be produced by the manufacturing method described in the Example of Unexamined-Japanese-Patent No. 2005-099778, for example.

The refractive index of these low-refractive-index layers is 1.45 or less, It is preferable that it is especially 1.42 or less.

In addition, although the thickness of a low-refractive-index layer is not limited, Usually, what is necessary is just to set suitably within the range of about 30 nm - about 1 micrometer.

In addition, although the effect is acquired with a single layer of the said low-refractive-index layer, it is also possible to provide suitably two or more layers of low-refractive-index layers for the purpose of adjusting a lower minimum reflectance or a higher minimum reflectance. When providing the two or more low-refractive-index layers, it is preferable to set a difference in the refractive index and thickness of each low-refractive-index layer.

As said fluorine-type resin, the polymeric compound which contains a fluorine atom at least in a molecule|numerator, or its polymer can be used. Although it does not specifically limit as a polymeric compound, For example, what has hardening-reactive groups, such as a functional group hardened|cured by an ionizing radiation, and a thermosetting polar group, is preferable. Moreover, the compound which simultaneously has this reactive group may be sufficient. With respect to this polymeric compound, a polymer does not have the above reactive groups etc. at all.

As the polymerizable compound having a functional group cured by ionizing radiation, a fluorine-containing monomer having an ethylenically unsaturated bond can be widely used. More specifically, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluorobutadiene, perfluoro-2,2-dimethyl-1,3 -dioxol, etc.) can be exemplified. As those having a (meth)acryloyloxy group, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluoropropyl (meth)acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl ) (meth)acrylate compounds having a fluorine atom in the molecule, such as ethyl (meth)acrylate, α-trifluoromethyl methacrylate, and α-trifluoroethyl methacrylate; Fluorine-containing polyfunctional (meth)acrylic acid having a fluoroalkyl group, fluorocycloalkyl group or fluoroalkylene group having at least 3 fluorine atoms, a fluorocycloalkyl group or fluoroalkylene group having at least 3 fluorine atoms, and at least two (meth)acryloyloxy groups in the molecule There are also ester compounds and the like.

Preferred examples of the thermosetting polar group are hydrogen bond forming groups such as a hydroxyl group, a carboxyl group, an amino group, and an epoxy group. These are excellent not only in adhesiveness with a coating film but also affinity with inorganic ultrafine particles, such as silica. As a polymeric compound which has a thermosetting polar group, For example, 4-fluoroethylene- perfluoroalkyl vinyl ether copolymer; fluoroethylene-hydrocarbon-based vinyl ether copolymer; and fluorine-modified products of each resin such as epoxy, polyurethane, cellulose, phenol and polyimide.

Examples of the polymerizable compound having both a functional group cured by ionizing radiation and a polar group to be thermally cured include a partial acrylic or methacrylic acid and partially fluorinated alkyl, alkenyl, aryl esters, fully or partially fluorinated vinyl ethers, and fully or partially fluorinated vinyl ethers. Vinyl fluoride esters, fully or partially fluorinated vinyl ketones, etc. can be illustrated.

Moreover, as a fluorine-type resin, the following is mentioned, for example.

a polymer of a monomer or a mixture of monomers containing at least one fluorine-containing (meth)acrylate compound of the polymerizable compound having an ionizing radiation curable group; At least one of the fluorine-containing (meth)acrylate compounds, and methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth) copolymers with (meth)acrylate compounds that do not contain a fluorine atom in a molecule such as acrylate; Fluoroethylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, 3,3,3-trifluoropropylene, 1,1,2-trichloro-3,3,3-trifluoropropylene, Homopolymers or copolymers of fluorine-containing monomers such as hexafluoropropylene. A silicone-containing vinylidene fluoride copolymer in which these copolymers contain a silicone component can also be used. As the silicone component in this case, (poly)dimethylsiloxane, (poly)diethylsiloxane, (poly)diphenylsiloxane, (poly)methylphenylsiloxane, alkyl-modified (poly)dimethylsiloxane, azo group-containing (poly)dimethylsiloxane, dimethyl Silicone, phenylmethyl silicone, alkyl/aralkyl-modified silicone, fluorosilicone, polyether-modified silicone, fatty acid ester-modified silicone, methyl hydrogen silicone, silanol group-containing silicone, alkoxy group-containing silicone, phenol group-containing silicone, methacryl-modified silicone , acrylic modified silicone, amino modified silicone, carboxylic acid modified silicone, carbinol modified silicone, epoxy modified silicone, mercapto modified silicone, fluorine modified silicone, polyether modified silicone, etc. are illustrated. Especially, what has a dimethylsiloxane structure is preferable.

Furthermore, a non-polymer or polymer containing the following compounds can also be used as a fluororesin. That is, a compound obtained by reacting a fluorine-containing compound having at least one isocyanato group in the molecule with a compound having at least one functional group that reacts with an isocyanato group such as an amino group, a hydroxyl group or a carboxyl group in a molecule; A compound obtained by reacting a compound having an isocyanato group with a fluorine-containing polyol such as a fluorine-containing polyether polyol, a fluorine-containing alkyl polyol, a fluorine-containing polyester polyol, and a fluorine-containing ε-caprolactone-modified polyol can be used.

Moreover, each binder resin described in the said glare-proof layer can also be mixed and used with the polymeric compound and polymer which have said fluorine atom. Moreover, in order to improve the hardening|curing agent for hardening a reactive group etc., coatability, or to provide antifouling property, various additives and a solvent can be used suitably.

In the formation of the low-refractive-index layer, 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·s (25° C.), preferably 0.7 to 3 mPa·s ( It is preferable to set it as the thing in the range of 25 degreeC). An excellent antireflection layer for visible light can be realized, and a thin film that is uniform and free from coating unevenness can be formed, and a low refractive index layer with particularly excellent adhesion can be formed.

The curing means for the resin may be the same as that described for the anti-glare layer described above. When a heating means is used for curing treatment, it is preferable that a thermal polymerization initiator that generates radicals and initiates polymerization of the polymerizable compound by heating, for example, is added to the fluororesin composition.

The layer thickness (nm) d _A of the low refractive index layer is obtained by 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 1,

λ is the wavelength, preferably a value in the range of 480 to 580 nm)

It is desirable to satisfy

In addition, in the present invention, the low refractive index layer has the following formula (2):

120<n _A d _A <145 (2)

It is preferable to satisfy the low reflectance.

In the laminate of the present invention, one layer or two or more layers of other layers (antistatic layer, antifouling layer, adhesive layer, other hard coating layer, etc.) are suitably applied as needed within the range in which the effects of the present invention are not impaired. can be formed Among these, it is preferable to have at least one layer of an antistatic layer and an antifouling layer. As these layers, the same thing as a well-known antireflection laminated body can also be employ|adopted.

It is preferable that the contrast ratio of the laminated body of this invention is 40 % or more, More preferably, it is 60 % or more. If it is less than 40 %, when the laminated body of this invention is mounted|worn on the display surface, there exists a possibility that a darkroom contrast may fall and visibility may be impaired. In addition, in this specification, the said contrast ratio is a value measured by the method as described in the Example mentioned later.

The laminated body of this invention can be set as a polarizing plate by providing the laminated body by this invention in the surface opposite to the surface in which the glare-proof layer in the laminated body exists on the surface of a polarizing element. Such a polarizing plate is also one of the present invention.

The polarizing element is not particularly limited, and for example, a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, an ethylene-vinyl acetate copolymer-based saponified film, etc. which have been dyed and stretched with iodine or the like can be used. In the lamination process of the said polarizing element and the laminated body of this invention, it is preferable to perform a saponification process to a light transmissive base material (triacetyl cellulose film). By the saponification treatment, the adhesiveness becomes good and the antistatic effect can also be obtained.

This invention is also an image display apparatus which equips the outermost surface with the said laminated body or the said polarizing plate.

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

The LCD which is the said representative example is provided with a transmissive display body, and the light source device which irradiates the said transmissive display body from the back side. When the image display device of this invention is LCD, the laminated body of this invention or the polarizing plate of this invention is formed in the surface of this transmissive display body.

In the case of the liquid crystal display device having the above-mentioned laminate according to the present invention, the light source of the light source device is irradiated from the lower side of the laminate. Moreover, a retardation plate may be inserted between a liquid crystal display element and a polarizing plate. An adhesive bond layer may be provided between each layer of this liquid crystal display device as needed.

The PDP, which is the image display device, has a surface glass substrate (electrodes formed on the surface) and a rear glass substrate (electrodes and microgrooves are formed on the surface to face the surface glass substrate) and arranged with a discharge gas enclosed therebetween, Red, green, and blue phosphor layers are formed in the groove). When the image display apparatus of this invention is a PDP, it is also to provide the above-mentioned laminated body on the surface of the said surface glass substrate, or its front plate (glass substrate or a film substrate).

The image display device is an ELD device that emits light when a voltage is applied, such as zinc sulfide or a diamine substance: a light emitting material is deposited on a glass substrate, and displays by controlling the voltage applied to the substrate, or by converting an electrical signal into light, It may be an image display device such as a CRT that generates a visible image of In this case, the above-mentioned laminate is provided on the outermost surface of each display device as described above or the surface of the front plate thereof.

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

The above-mentioned image display apparatus can suppress generation|occurrence|production of glare to an extremely high level while having favorable anti-glare property, it is excellent in high contrast, and becomes a thing with improved visibility. The method of improving visibility by such an image display device of the present invention is also one of the present invention.

That is, the method for improving the visibility of an image display device of the present invention is 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 one surface of a light-transmitting substrate, organic particulates, inorganic The anti-glare layer is formed by applying a composition for an anti-glare layer containing fine particles, a binder resin, and a solvent on one side of the light-transmitting substrate, drying and curing the coating film formed thereon, and the composition for the anti-glare layer is in the solvent It is characterized in that it is prepared by mixing and stirring the binder resin and the organic fine particles to prepare an intermediate composition, and then mixing and dispersing the inorganic fine particles in the intermediate composition.

In the method for improving the visibility of an image display device of the present invention, the laminate having an anti-glare layer having a concave-convex shape on the surface on one side of the light-transmitting substrate, and the composition for the anti-glare layer, the laminate of the present invention described above The same thing as what was demonstrated in the manufacturing method is mentioned.

Since the manufacturing method of the laminated body of this invention includes the structure mentioned above, this invention can suppress the generation|occurrence|production of glare to an extremely high level while having favorable anti-glare property, and can obtain the display image excellent in high contrast of the laminate can be prepared.

For this reason, the laminated body of this invention is a cathode ray tube display device (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescent display (ELD), a field emission display (FED), an electronic paper, It can be preferably applied to a touch panel, a tablet PC, and the like.

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing of the measuring method of (theta)a.
FIG. 2 is a cross-sectional electron micrograph of the laminate according to Example 1. FIG.
3 is another cross-sectional electron micrograph of the laminate according to Example 1. FIG.
4 is another cross-sectional electron micrograph of the laminate according to Example 1. FIG.

Although the content of this invention is demonstrated with the following Example, the content of this invention is limited to this embodiment and is not interpreted. Unless otherwise specified, "part" and "%" are based on mass.

(Preparation of composition 1 for anti-glare layer)

The formulation shown below was dispersed with a bead mill to obtain an intermediate composition.

Then, the formulation shown below was dispersed with a bead mill to obtain an inorganic fine particle dispersion.

And the inorganic fine particle dispersion was added gradually, stirring an intermediate composition with a disper, and the composition 1 for glare-proof layers was obtained.

(intermediate composition)

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

65 parts by mass of pentaerythritol tetraacrylate (PETTA) (product name: PETA, manufactured by Daicel Cytec)

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

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

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

100 parts by mass of toluene

35 parts by mass of isopropyl alcohol

20 parts by mass of cyclohexanone

(inorganic particulate dispersion)

6 parts by mass of fumed silica (octylsilane treatment; average primary particle diameter of 12 nm, manufactured by Nippon Aerosil)

45 parts by mass of toluene

20 parts by mass of isopropyl alcohol

(Preparation of composition 2 for anti-glare layer)

The organic fine particles in the intermediate composition were non-hydrophilic treated acrylic-styrene copolymer particles (average particle diameter 5.0 µm, refractive index 1.55, manufactured by Sekisui Plastics Co., Ltd.), and the blending amount was 16 parts by mass, except that the composition 1 for anti-glare layer It carried out similarly to the glare-proof layer composition 2 was obtained.

(Preparation of composition 3 for anti-glare layer)

Except having made the compounding quantity of 5 mass parts and cyclohexanone into 50 mass parts for the compounding quantity of isopropyl alcohol in an intermediate composition, it carried out similarly to the composition 1 for glare-proof layers, and the composition 3 for glare-proof layers was obtained.

(Preparation of composition 4 for anti-glare layer)

Except having made the compounding quantity of the fumed silica in an inorganic fine particle dispersion into 4 mass parts, it carried out similarly to the composition 1 for anti-glare layers, and obtained the composition 4 for anti-glare layers.

(Preparation of composition 5 for anti-glare layer)

Each composition shown in the intermediate composition and inorganic fine particle dispersion in the composition 1 for glare-proof layer was simultaneously disperse|distributed with a bead mill, and the composition 5 for glare-proof layer was obtained.

(Preparation of composition 6 for anti-glare layer)

The composition shown below was disperse|distributed with a bead mill, and the composition 6 for glare-proof layer was obtained.

14 parts by mass of organic fine particles (non-hydrophilic treated polystyrene particles, average particle diameter 3.5 μm, refractive index 1.59, manufactured by Soken Chemical)

100 parts by mass of pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by Daicel Cytec)

10 parts by mass of acrylic polymer (molecular weight 75,000, manufactured by Mitsubishi Rayon)

5 parts by mass of polymerization initiator (product name "irgacure 184", manufactured by BASF Japan)

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

120 parts by mass of toluene

30 parts by mass of cyclohexanone

(Preparation of composition 7 for anti-glare layer)

Anti-glare in the same manner as in composition 6 for anti-glare layer, except that organic fine particles in composition 6 for anti-glare layer were non-hydrophilized treated acrylic-styrene copolymer particles (average particle diameter of 3.5 µm, refractive index of 1.55, manufactured by Sekisui Plastics). Layer composition 7 was obtained.

(Example 1)

Composition 1 for an anti-glare layer was applied to one side of a light-transmitting base material (triacetyl cellulose resin film with a thickness of 60 µm, TD60UL manufactured by Fujifilm) to form a coating film. Subsequently, after flowing dry air at 70° C. for 15 seconds at a flow rate of 0.2 m/s to the formed coating film, dry air at 70° C. was evaporated, and the coating film was cured by irradiating UV light so that the accumulated light amount was 100 mJ/cm 2 , thereby forming an anti-glare layer having a thickness of 6 μm (at the time of curing), thereby preparing a laminate according to Example 1.

(Examples 2 to 4)

A laminate according to Examples 2 to 4 was prepared in the same manner as in Example 1, except that compositions 2 to 4 for an antiglare layer were used instead of the composition 1 for an antiglare layer.

(Comparative Example 1)

A laminate according to Comparative Example 1 was prepared in the same manner as in Example 1 except that the composition 5 for the anti-glare layer was used instead of the composition 1 for the anti-glare layer.

(Comparative Examples 2-3)

Laminates according to Comparative Examples 2 to 3 were prepared in the same manner as in Example 1 except that the compositions 6 to 7 for the antiglare layer were used instead of the composition 1 for the antiglare layer, and the thickness at the time of curing was set to 4.5 μm.

The obtained laminates according to 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 properties of the obtained laminate, a black acrylic plate, a transparent adhesive, and a laminate (the adhesive side is the non-coated surface of the light-transmitting substrate) were adhered in this order, and the three-wavelength fluorescent lamp was placed 1.5 m above and had an illuminance of about 1000 Lx. The following criteria evaluated the degree to which projection of a fluorescent lamp is not concerned in a bright room environment.

(double-circle): The image of a fluorescent lamp is completely blurred and cannot be recognized

○: The image of a fluorescent lamp is projected, but the outline is blurred and the boundary of the outline cannot be recognized

x: The image of the fluorescent lamp is projected, and the outline can also be clearly recognized

(flashing evaluation)

The surface glare of the obtained laminate was evaluated as follows.

The surface on which the anti-glare layer of the laminate was not formed, and the glass surface on which the matrix of the black matrix (glass thickness 0.7mm) was not formed were bonded together with the transparent adhesive, and the sample was obtained.

With respect to the sample thus obtained, by providing a white surface light source (manufactured by HAKUBA, LIGHTBOX, average luminance of 1000 cd/m 2 ) on the black matrix side, pseudo glare was generated.

This was photographed from the laminate side with a CCD camera (KP-M1, C mount adapter, macro ring; PK-11A Nikon, camera lens; 50 mm, F 1.4s NIKKOR). The distance between the CCD camera and the laminate was set to 250 mm, and the focus of the CCD camera was adjusted to fit the laminate. An image photographed with a CCD camera was introduced into a personal computer, and analysis was performed as follows with image processing software (ImagePro Plus ver. 6.2; manufactured by Media Cybernetics).

First, an evaluation site of 200 x 160 pixels was selected from the introduced image, and the evaluation site was converted into 16-bit grayscale. Next, a low-pass filter was selected from the highlight tab of the filter command, and the filter was applied under the conditions of “3×3, 3 times, 10 intensity”. Thereby, the component derived from the black matrix pattern was removed.

Next, flattening was selected and shading correction was performed under the conditions of "background: dark, object width 10".

Next, using the contrast enhancement command, "Contrast: 96, Brightness: 48" was used to enhance contrast.

The obtained image was converted to an 8-bit grayscale, and the glare was digitized by calculating the variation of the value for each pixel as a standard deviation value for 150x110 pixels among them. It can be said that there is little glare, so that this numerical-ized glare value is small. In addition, the black matrix performed the measurement with the thing equivalent to 200 ppi of pixel density.

About the measured glare value, the following reference|standard evaluated.

◎: the flashing value is 14 or less

○: The flashing value is greater than 14 and less than or equal to 18

×: the flashing value exceeds 18

(contrast ratio)

In the measurement of the contrast ratio, a light having a diffuser plate installed in a cold cathode tube light source is used as a backlight unit, two polarizing plates (AMN-3244TP manufactured by Samsung Corporation) are used, and the luminance of light passing when the polarizing plate is installed in parallel nicol. The value (L max /L min ) obtained by dividing L _max by the luminance L _min of the light that passes when it is installed with cross nicol (L _max /L _min ) is the contrast, The contrast ratio was computed by calculating| _requiring L< ₁ > and _the contrast (L2) when only the transparent base material is mounted on the outermost surface, and calculating (L1/L2)* ₁₀₀ (%).

In addition, for the measurement of the luminance, a color luminance meter (BM-5A manufactured by Topcon Corporation) was used, and illuminance was performed in a dark room environment of 5 Lx or less. The measurement angle of the color luminance meter was set to 1 DEG , and measurement was performed in a field of view phi 5 mm on the sample. The amount of light of the backlight was installed so that the luminance when two polarizing plates were installed in parallel nicol in a state in which the sample was not provided was 3600 cd/m 2 .

(double-circle): said contrast ratio 60% or more

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

x: said contrast ratio is less than 40%

(Sq/Ma)

On the surface opposite to the surface on which the anti-glare layer is formed of each obtained laminate, it is attached to a glass plate through a transparent adhesive to make a sample, and using a white interference microscope (New View7300, manufactured by Zygo), the following Under the conditions, measurement and analysis of the surface shape of the anti-glare layer were performed. In addition, Microscope Application of MetroPro ver 8.3.2 was used for measurement and analysis software.

(Measuring conditions)

Objective Lens: 50x

Zoom: 1x

Measurement area: 414 μm × 414 μm

Resolution (space per point): 0.44 µm

(analysis conditions)

Removed: Sphere

Filter: LowPass

FilterType: GaussSpline

High wavelength: 2.5㎛

Remove spikes: on

Spike Height (xRMS): 2.5

The data measured in the above measurement conditions are divided into 16 regions with a size of 100 μm × 100 μm using “Mask Editor”, and the numerical value of “Ra” displayed on the Surface Map screen under the analysis conditions for each area is calculated It was read, and it was set as the value of Sa. And their average value was made into Ma, and their standard deviation was made into Sq, and (Sq/Ma) was computed.

(haze, internal haze)

About the haze of each laminated body, it measured by the method based on JISK-7136 (haze) using the haze meter (made by Murakami Shikisai Kijutsu Genkyujo, product name; HM-150). About the internal haze, it measured by the method mentioned above.

(Average spacing of irregularities (Sm), arithmetic mean roughness of irregularities (Ra), average inclination angle of irregularities (θa), 10-point average roughness (Rz))

In accordance with JIS B 0601-1994, the average interval (Sm) of the unevenness, the arithmetic average roughness (Ra) and the 10-point average roughness (Rz) of the unevenness are measured, and the average inclination angle (θa) of the uneven portion is measured by the method shown in FIG. was measured. In addition, for the measurement of the said Sm, Ra, (theta)a, and Rz, the surface roughness measuring instrument: SE-3400/Kosaka Genkyusho Co., Ltd. was used and it measured under the following conditions.

(1) The stylus of the surface roughness detection unit:

Model number/SE2555N (2μ stylus), manufactured by Kosaka Genkyusho, Ltd.

(The radius of curvature of the tip is 2㎛ / Vertex angle: 90 degrees / Material: Diamond)

(2) Measurement conditions of the surface roughness meter:

Reference length (cutoff value λc of roughness curve): 0.8mm

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

Feed rate of stylus: 0.5mm/s

Spare length: (cutoff value λc)×2

Vertical magnification: 2000x

Horizontal magnification: 10x

As shown in Table 1, all of the laminates according to Examples were excellent in evaluation of glare, contrast ratio, and anti-glare properties, and also excellent in manufacturing stability.

On the other hand, since the laminate according to Comparative Example 1 was manufactured using a composition for an anti-glare layer formed by simultaneously dispersing each composition of the intermediate composition and the inorganic fine particle dispersion, the evaluation of glare was inferior. In addition, since the laminate according to Comparative Example 2 did not use inorganic fine particles and the uneven shape was not formed uniformly and uniformly, the evaluation of glare was inferior. Moreover, since the laminated body concerning Comparative Example 3 had a large internal haze, although glare was favorable, the evaluation of contrast ratio was inferior.

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

Claims (13)

A method for producing a laminate having, on one surface of a light-transmitting substrate, an anti-glare layer having an uneven shape on the surface, the method comprising:
a step of forming the anti-glare layer by applying a composition for an anti-glare layer containing organic fine particles, inorganic fine particles, a binder resin and a solvent on one side of the light-transmitting substrate, drying and curing the coating film,
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 and dispersing the inorganic fine particles in the intermediate composition,
The uneven shape of the surface of the anti-glare layer divides the surface of the anti-glare layer into 100 µm square measurement areas, obtains the arithmetic average roughness Sa in each measurement area, and the average value of the arithmetic mean roughness Sa is Ma, the arithmetic When the standard deviation of the average roughness Sa is Sq, the ratio of Ma and Sq (Sq/Ma) is controlled to be 0.15 or less,
The laminate has an internal haze of 5% or more and 30% or less, and an external haze of 5% or more and 30% or less.
Method for producing a laminate, characterized in that. A laminate having an anti-glare layer having an uneven shape on the surface on one side of a light-transmitting substrate, the laminate comprising:
As for the uneven shape of the surface of the anti-glare layer, the surface of the anti-glare layer is divided into 100 µm square measurement areas, the arithmetic mean roughness Sa in each measurement area is obtained, and the average value of the arithmetic mean roughness Sa is Ma, the arithmetic When the standard deviation of the average roughness Sa is Sq, the ratio of Ma to Sq (Sq/Ma) is 0.15 or less,
The laminate has an internal haze of 5% or more and 30% or less, and an external haze of 5% or more and 30% or less.
A laminate, characterized in that. The laminate according to claim 2, wherein the anti-glare layer contains a binder resin, organic fine particles and inorganic fine particles. A laminate having an anti-glare layer having an uneven shape on the surface on one side of a light-transmitting substrate, the laminate comprising:
The anti-glare layer contains a binder resin, organic fine particles and inorganic fine particles,
The inorganic fine particles are sparsely distributed around the organic fine particles, and are uniformly distributed in the anti-glare layer except around the organic fine particles,
The uneven shape of the surface of the anti-glare layer divides the surface of the anti-glare layer into 100 µm square measurement areas, obtains the arithmetic average roughness Sa in each measurement area, and the average value of the arithmetic mean roughness Sa is Ma, the arithmetic When the standard deviation of the average roughness Sa is Sq, the ratio of Ma to Sq (Sq/Ma) is 0.15 or less,
The laminate has an internal haze of 5% or more and 30% or less, and an external haze of 5% or more and 30% or less.
A laminate, characterized in that. The laminate according to claim 3 or 4, wherein the inorganic fine particles are silica fine particles. The laminate according to claim 5, wherein the aggregates of the silica fine particles have an average particle diameter of 100 nm to 1 µm. The laminate according to claim 3 or 4, wherein the binder resin contains a polyfunctional acrylate monomer containing no hydroxyl group in its molecule as a main material. 5. The organic fine particles according to claim 3 or 4, wherein the organic fine particles are selected from the group consisting of acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyethylene resins, epoxy resins, silicone resins, polyvinylidene fluoride resins and polyethylene fluoride resins. A laminate which is microparticles|fine-particles containing at least 1 sort(s) of material which becomes The laminate according to claim 3 or 4, wherein the organic fine particles are not subjected to surface hydrophilization treatment. A polarizing plate comprising a polarizing element, comprising:
The said polarizing plate is equipped with the laminated body in any one of Claims 2-4 on the polarizing element surface, The polarizing plate characterized by the above-mentioned. An image display device comprising the laminate according to any one of claims 2 to 4 on the outermost surface. A method for improving visibility of an image display device using a laminate having an anti-glare layer having an uneven shape on the surface on one side of a light-transmitting substrate, the method comprising:
The anti-glare layer of the laminate is formed by applying a composition for an anti-glare layer containing organic particulates, inorganic particulates, a binder resin and a solvent on one side of the light-transmitting substrate, drying and curing the coating film,
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 and dispersing the inorganic fine particles in the intermediate composition,
The uneven shape of the surface of the anti-glare layer divides the surface of the anti-glare layer into 100 µm square measurement areas, obtains the arithmetic average roughness Sa in each measurement area, and the average value of the arithmetic mean roughness Sa is Ma, the arithmetic When the standard deviation of the average roughness Sa is Sq, the ratio of Ma and Sq (Sq/Ma) is controlled to be 0.15 or less,
The laminate has an internal haze of 5% or more and 30% or less, and an external haze of 5% or more and 30% or less.
A method for improving visibility of an image display device, characterized in that. The polarizing plate of Claim 10 is provided in an outermost surface, The image display apparatus characterized by the above-mentioned.

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