JP2015210273A - Method for manufacturing laminate, laminate, polarizer, and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a laminate that is excellent in manufacturing stability, is capable of suppressing the generation of glare at remarkably high level while having a good antiglare property, and is capable of giving a display image excellent in high contrast.SOLUTION: A method for manufacturing a laminate including an antiglare layer having a rugged shape on a surface of one of sides of a light-permeable substrate includes a step of drying a coating film formed by coating an antiglare layer composition containing organic fine particles, inorganic fine particles, a binder resin and a solvent onto one of sides of the light-permeable substrate, and then forming the antiglare layer by curing the coating film. The antiglare layer composition is prepared by mixing the binder resin and the organic fine particles with the solvent, stirring the resultant mixture to prepare an intermediate composition, and then mixing the inorganic fine particles with the intermediate composition to allow the particles to disperse therein.

Description

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

In image display devices such as cathode ray tube display (CRT), liquid crystal display (LCD), plasma display (PDP), electroluminescence display (ELD), electronic paper, tablet PC, touch panel, etc. An optical laminate is provided.
Such an anti-reflection optical laminated body suppresses reflection of an image or reduces reflectance by scattering or interference of light.

As one of the antireflection optical laminates, an antiglare film is known in which an antiglare layer having an uneven shape is formed on the surface of a transparent substrate. This antiglare film can prevent external light from being scattered due to the uneven shape of the surface, thereby preventing a decrease in visibility due to reflection of external light or reflection of an image.
Moreover, since this optical laminated body is normally installed on the outermost surface of the image display device, it is also required to impart a hard coat property so as not to be damaged during handling.

As a conventional anti-glare film, for example, a film in which an anti-glare layer is formed by applying a resin containing a filler such as silicon dioxide (silica) to the surface of a light-transmitting substrate is known (for example, Patent Documents 1 and 2).
These antiglare films are a type that forms an uneven shape on the surface of the antiglare layer by agglomeration of particles such as cohesive silica, a type that forms an uneven shape on the layer surface by adding an organic filler to the resin, or There is a type in which an uneven shape is transferred by laminating a film having unevenness on the layer surface.

However, in any type of such conventional anti-glare film, the surface shape of the anti-glare layer is used to obtain light diffusion / anti-glare action. Although the shape needs to be rough and increased, there is a problem that when the unevenness is rough and increases, the haze (haze value) of the coating film increases and white blurring occurs and the contrast of the display image decreases.
In addition, the conventional type of antiglare film has a problem that the surface of the display screen is deteriorated because of a sparkle on the surface of the film, which is called “glare”. The glare is that when the image display device is turned on, when the transmitted light from the back reaches the screen, uneven brightness appears on the screen surface. This phenomenon appears to change, and is particularly noticeable when displaying a full white display or a full green display.

In particular, since the use of 4K panels and mobile terminals such as smartphones and tablets have become increasingly fine in recent years, glare cannot be controlled sufficiently with conventional anti-glare films.
For such a problem, for example, a method of improving glare of the antiglare layer with internal haze (see, for example, Patent Document 3 and Patent Document 4) is known. However, in the method using the internal haze of the anti-glare layer, if the internal haze is increased to suppress glare to cope with the recent ultra-high definition panel, the dark room contrast and resolution of the display image are deteriorated. was there.
In addition, for example, a method for improving glare and contrast by controlling the surface shape of the antiglare layer is also known (see, for example, Patent Document 5). However, in the method described in Patent Document 5, since a large amount of inorganic fine particles is added, there is a problem that the coating property of the composition for forming an antiglare layer is deteriorated and uneven coating and streaky coating defects are likely to occur. It was.

JP-A-6-18706 Japanese Patent Laid-Open No. 10-20103 Japanese Patent Laid-Open No. 11-305010 JP 2002-267818 A Japanese Patent No. 451124

In view of the above-mentioned present situation, the present invention is a laminate that is excellent in production stability, has a good antiglare property, can suppress the occurrence of glare at an extremely high level, and can obtain a display image with excellent high contrast. An object of the present invention is to provide a manufacturing method, a laminate, a polarizing plate and an image display device using the laminate.

The present invention relates to a method for producing a laminate having an antiglare layer having a concavo-convex shape on one surface of a light-transmitting substrate, which comprises an organic fine particle, an inorganic fine particle, a binder resin and a solvent. A step of forming the antiglare layer by drying and curing the coating film formed by applying the composition for the glare layer on one surface of the light-transmitting substrate, and for the antiglare layer The composition is prepared by mixing and dispersing 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. It is the manufacturing method of the laminated body characterized by these.

Further, the present invention is a laminate having an antiglare layer having an uneven shape on one surface of a light-transmitting substrate, wherein the uneven shape on the surface of the antiglare layer is the antiglare layer. Is divided into 100 μm square measurement areas, the arithmetic average roughness Sa in each measurement area is determined, the average value of the arithmetic average roughness Sa is Ma, and the standard deviation of the arithmetic average roughness Sa is Sq. The laminate is also characterized in that the ratio of Ma to Sq (Sq / Ma) is 0.15 or less.
In the laminate of the present invention, the antiglare layer preferably contains a binder resin, organic fine particles, and inorganic fine particles.

The present invention is also a laminate having an antiglare layer having a concavo-convex shape on one surface of a light-transmitting substrate, wherein the antiglare layer contains a binder resin, organic fine particles and inorganic fine particles. The inorganic fine particles are also a laminate characterized by being roughly distributed around the organic fine particles and uniformly distributed in the anti-glare layer except for the periphery of the organic fine particles. .

In the laminate of the present invention, the inorganic fine particles are preferably silica fine particles, and the average particle size of the aggregate of the silica fine particles is preferably 100 nm to 1 μm.
The binder resin preferably contains a polyfunctional acrylate monomer having no hydroxyl group in the molecule as a main material.
The organic fine particles may be made of at least one material selected from the group consisting of acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyethylene resin, epoxy resin, silicone resin, polyvinylidene fluoride resin and polyvinyl fluoride resin. It is preferable that it is a fine particle, and it is preferable that the surface is not hydrophilized.

This invention is also a polarizing plate provided with a polarizing element, Comprising: The said polarizing plate is a polarizing plate characterized by providing the above-mentioned laminated body on the polarizing element surface.
This invention is also an image display apparatus characterized by providing the above-mentioned laminated body or the above-mentioned polarizing plate in the outermost surface.
The present invention is described in detail below.

As a result of intensive studies on a laminate including an antiglare layer having a concavo-convex shape on the surface of a light-transmitting substrate, the present inventors have prepared an antiglare layer prepared by a specific method. By forming using the layer composition, the concavo-convex shape is formed more uniformly and evenly compared to the antiglare layer of the conventional laminate, and the laminate having such an antiglare layer is The inventors have found that the occurrence of glare can be suppressed at an extremely high level while having a good antiglare property, and that a display image with excellent high contrast can be obtained, and the present invention has been completed.
Further, as a result of intensive studies, the present inventors have found that the ratio (Sq / Ma) of the average value Ma of the arithmetic average roughness Sa of the uneven shape to the standard deviation Sq of the arithmetic average roughness Sa is within a predetermined range. It was found that the antiglare layer that was highly controlled so that the uneven shape was formed extremely uniformly and evenly, and the laminate of the present invention was completed.
Furthermore, as a result of intensive studies, the present inventors have found that the antiglare layer having a concavo-convex shape controlled so as to be more uniform and uniform as compared with the concavo-convex shape of the surface of the conventional antiglare layer, Has been found to be obtained by controlling the organic fine particles and the inorganic fine particles contained in a specific state, and has completed the laminate of the present invention according to another aspect.

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 surface of a light-transmitting base material.
The light transmissive substrate preferably has smoothness and heat resistance and is excellent in mechanical strength. Specific examples of the material forming the light-transmitting substrate include, for example, polyester (polyethylene terephthalate, polyethylene naphthalate), cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, polyester, polyamide, polyimide, polyethersulfone, poly Examples thereof include thermoplastic resins such as sulfone, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polymethyl methacrylate, polycarbonate, and polyurethane. Preferably, polyester (polyethylene terephthalate, polyethylene naphthalate) and cellulose triacetate are used.

The light-transmitting substrate preferably uses the thermoplastic resin as a flexible film-like body, but uses a plate of these thermoplastic resins depending on the use mode in which curability is required. It is also possible, or a plate-like body such as a glass plate may be used.

In addition, examples of the light transmissive substrate include an amorphous olefin polymer (Cyclo-Olefin-Polymer: COP) film having an alicyclic structure. This is a base material in which a norbornene polymer, a monocyclic olefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer, and the like are used. Zeonoa (norbornene-based resin), Sumitrite FS-1700 manufactured by Sumitomo Bakelite, Arton (modified norbornene-based resin) manufactured by JSR, Appel (cyclic olefin copolymer) manufactured by Mitsui Chemicals, Topas (cyclic) manufactured by Ticona Olefin copolymer), Optretz OZ-1000 series (alicyclic acrylic resin) manufactured by Hitachi Chemical Co., Ltd., and the like.
Further, the FV series (low birefringence, low photoelastic modulus film) manufactured by Asahi Kasei Chemicals is also preferable as an alternative base material for triacetylcellulose.

In the case of a film-like body, the thickness of the light-transmitting substrate is preferably 5 to 300 μm, more preferably the lower limit is 20 μm and the upper limit is 200 μm. When the light-transmitting substrate is a plate-like body, the thickness may exceed these thicknesses.
In forming the hard coat layer and the like on the light transmissive substrate, in order to improve adhesion, in addition to physical or chemical treatment such as corona discharge treatment and oxidation treatment, an anchor agent or Application of a paint called a primer may be performed in advance.
In addition, when triacetylcellulose, which is often used mainly as a light-transmitting substrate for LCD, is used as a material and a display thin film is desired, the thickness of the light-transmitting substrate is preferably 20 to 65 μm. .

The antiglare 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 an anti-glare layer.
In this step, a coating film formed by applying a composition for an antiglare layer containing organic fine particles, inorganic fine particles, a binder resin and a solvent on one surface of the light-transmitting substrate is dried and cured. To form the antiglare layer.

In the method for producing a laminate of the present invention, since the composition for forming an antiglare layer contains organic fine particles and inorganic fine particles, the uneven shape formed on the surface of the antiglare layer to be formed is Compared to the uneven shape formed on the surface of the anti-glare layer by a single fine particle (for example, organic fine particle) or an aggregate of single particles (for example, an aggregate of silica fine particles), it is formed more uniformly and evenly. It becomes the shape made. This is presumed to be because, in the laminate produced by the laminate production method of the present invention, the inorganic fine particles and the organic fine particles are distributed in a specific state in the antiglare layer, as will be described later. Is done.

The organic fine particles and inorganic fine particles are preferably spherical in shape in a single particle state. When the organic fine particles and the single particles of the inorganic fine particles are spherical in this way, a high-contrast display image can be obtained when the produced laminate is applied to an image display device.
In addition, the above “spherical” includes, for example, a true spherical shape, an elliptical spherical shape and the like, and has a meaning excluding so-called indefinite shape.

The organic fine particles are fine particles that mainly form the surface unevenness shape of the antiglare layer, and are fine particles whose refractive index and particle size can be easily controlled. By including such organic fine particles, it becomes easy to control the size of the uneven shape formed in the antiglare layer and the refractive index of the antiglare layer, and control the antiglare property and suppress the occurrence of glare and white blurring. Can do.

The organic fine particles are made of at least one material selected from the group consisting of acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyethylene resin, epoxy resin, silicone resin, polyvinylidene fluoride resin and polyvinyl fluoride resin. Fine particles are preferred. Of these, styrene-acrylic copolymer fine particles are preferably used.

The organic fine particles are preferably not subjected to surface hydrophilization treatment. When the organic fine particles are subjected to a surface hydrophilization treatment, the affinity with the inorganic fine particles is excessively increased, and it may be difficult to roughly distribute the inorganic fine particles around the organic fine particles. The “rough distribution” will be described in detail later.
The hydrophilic treatment is not particularly limited and may be a known method. Examples thereof include a method of copolymerizing a monomer having a functional group such as a carboxylic acid group or a hydroxyl group on the surface of the organic fine particles.

As content of the said organic fine particle, it is preferable that it is 1-50 mass% in solid content in the said composition for glare-proof layers. If it is less than 1% by mass, the antiglare performance of the laminate to be produced may be insufficient, and if it exceeds 50% by mass, there may be a problem of white blurring. When used in a display device, the contrast of the display image may be inferior. A more preferable lower limit is 5% by mass, and a more preferable upper limit is 20% by mass.

The organic fine particles are preferably fine particles having a relatively uniform particle size.
Here, the above-mentioned “fine particles having relatively uniform particle diameters” means that when the average particle diameter by weight average is MV, the cumulative 25% diameter is d25, and the cumulative 75% diameter is d75 (d75-d25) This means that / MV is 0.25 or less.
The cumulative 25% diameter refers to the particle diameter when counted from a particle having a small particle diameter in the particle size distribution and reaches 25% by mass. The cumulative 75% diameter is similarly counted to 75% by mass. The particle diameter when it becomes%.
The average particle diameter, cumulative 25% diameter and cumulative 75% diameter of the fine particles by the weight average can be measured as the weight average diameter by the Coulter counter method.
When the composition for forming an antiglare layer contains such organic fine particles, it becomes easy to suitably form a uniform and uniform uneven shape on the surface of the antiglare layer.

In addition, the size of the organic fine particles is appropriately determined according to the thickness of the antiglare layer to be formed, and the average particle size is preferably 0.3 to 6.0 μm, for example. If it is less than 0.3 μm, the dispersibility of the organic fine particles may not be controlled, and if it exceeds 6.0 μm, the uneven shape on the surface of the antiglare layer becomes large, which may cause a problem of surface glare. A more preferable lower limit is 2.0 μm, and a more preferable upper limit is 4.0 μm.
Moreover, it is preferable that the average particle diameter of the said organic fine particle is 20 to 90% with respect to the thickness of the glare-proof layer to form. If it exceeds 90%, the influence of the deviation of the film thickness on the uneven shape becomes strong, and the antiglare layer may be formed unevenly. If it is less than 20%, a sufficient uneven shape cannot be formed on the surface of the antiglare layer, and the antiglare performance may be insufficient.
The average particle diameter of the organic fine particles can be measured as a weight average diameter by a Coulter counter method when the organic fine particles are measured alone. On the other hand, the average particle diameter of the organic fine particles in the antiglare layer is obtained as a value obtained by averaging the maximum diameters of 10 particles in a transmission optical microscope observation of the antiglare layer. Or, if it is not suitable, in the observation of an electron microscope (transmission type such as TEM, STEM, etc., the same applies hereinafter) of a cross section passing through the vicinity of the center of the particle, it is observed as an almost the same particle size of any same kind. This is a value calculated as an average value by selecting 30 diffusing particles (the number of selected particles is increased because it is unclear which part of the particle is a cross section) and measuring the maximum particle diameter of the cross section. Since both are determined from the image, the image may be calculated by image analysis software.

The inorganic fine particles have a function of stably presenting the organic fine particles in the antiglare layer mainly in a state where a uniform uneven shape can be formed, and are uniformly dispersed in the antiglare layer composition. It is preferable.
As such inorganic fine particles, for example, silica fine particles are preferable. Hereinafter, the inorganic fine particles will be described as silica fine particles.
Since the silica fine particles are uniformly distributed in the composition for the antiglare layer, the silica particles are uniformly dispersed in the antiglare layer to be formed, and a uniform and uniform uneven shape is formed on the surface. Can do.
The above “uniformly distributed in the anti-glare layer” means that the organic fine particles in the thickness direction of the anti-glare layer are observed with an electron microscope (transmission type such as TEM, STEM, etc. is preferable) at a magnification of 10,000 times. When the area ratio of the silica fine particles in the observation area of 5 μm square is measured for each cross section when observing 10 arbitrary cross sections from the place where it is not, when the average value is M and the standard deviation is S, It means that S / M ≦ 0.1.
Such a distribution of silica fine particles can be easily determined by observation with a cross-sectional electron microscope in the thickness direction of the antiglare layer. For example, FIG. 2 is a cross-sectional STEM photograph of the laminate according to Example 1, and FIG. 3 is another cross-sectional STEM photograph of the laminate according to Example 1. In FIGS. In the cross section of the antiglare layer, the portion observed in black spots in the cross section of the antiglare layer is an aggregate of the silica fine particles, and the aggregate of silica fine particles is the antiglare layer. It can be clearly confirmed that the particles are uniformly dispersed. The area ratio of the aggregate of the silica fine particles can be calculated using, for example, image analysis software.

In the present invention, the silica fine particles are preferably surface-treated. Since the silica fine particles are surface-treated, the distribution of the silica fine particles in the composition for the antiglare layer and the antiglare layer to be formed can be suitably controlled, and the organic fine particles can be roughly distributed around the organic fine particles. The distributed effect can be controlled within an appropriate range. Further, the chemical resistance and saponification resistance of the silica fine particles themselves can be improved.

The surface treatment is preferably a hydrophobizing treatment that makes the surface of the fine particles hydrophobic. Examples of the hydrophobizing treatment include a method of treating the silica fine particles with a silane compound having an acrylic group such as a methyl group or an octyl group.
Here, normally, hydroxyl groups (silanol groups) exist on the surface of the silica fine particles, but the surface treatment reduces the hydroxyl groups on the surface of the silica fine particles, and the silica fine particles agglomerate excessively. This can prevent the silica fine particles from being dispersed unevenly.

The silica fine particles are preferably made of amorphous silica. When the silica fine particles are made of crystalline silica, the lattice acid contained in the crystal structure may increase the Lewis acidity of the silica fine particles, which may make it impossible to control excessive aggregation of the silica fine particles.

As such silica fine particles, fumed silica is preferably used, for example, because it itself easily aggregates and easily forms an aggregate having the above-mentioned particle diameter. Here, the fumed silica refers to amorphous silica having a particle size of 200 nm or less prepared by a dry method, and is obtained by reacting a volatile compound containing silicon in a gas phase. Specifically, for example, a silicon compound, for example, one produced by hydrolyzing SiCl ₄ in a flame of oxygen and hydrogen can be used. 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 the amount is less than 1.0% by mass, the organic fine particles described above may not be present so that a uniform uneven shape can be formed. If the amount exceeds 10.0% by mass, the viscosity of the antiglare layer composition may not be present. There is a possibility that the applicability of the coating becomes worse. A more preferred lower limit is 3.0% by mass, and a more preferred upper limit is 8.0% by mass.

The silica fine particles preferably have an average primary particle diameter of 1 to 100 nm. If the thickness is less than 1 nm, preferred aggregates may not be formed. If the thickness exceeds 100 nm, light is diffused by the silica fine particles, and the dark room contrast of the image display device using the produced laminate may be inferior. A more preferred lower limit is 5 nm, and a more preferred upper limit is 50 nm.
In addition, the average primary particle diameter of the silica fine particles is a value measured using an image processing software from an image of a cross-sectional electron microscope (TEM, STEM, etc., and preferably a magnification of 50,000 times or more). is there.

In the present invention, when the silica fine particles form an aggregate, the above-mentioned silica fine particles are formed in a pearl necklace shape in the cross-sectional electron microscope of the antiglare layer.
In the antiglare layer, the silica fine particles form an agglomerate of pearl necklaces, so that the organic fine particles can effectively exist in a state where a uniform uneven shape can be formed. Can be demonstrated.
The structure in which the silica fine particles are connected in a pearl necklace shape is, 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, An arbitrary structure such as a branched structure having one or more side chains in which a plurality of silica fine particles are continuously formed in the chain structure is included.

The aggregate of the silica fine particles preferably has an average particle diameter of 100 nm to 1 μm. If the thickness is less than 100 nm, the above-described effects may not be exhibited. If the thickness exceeds 1 μm, light is diffused by an aggregate of silica fine particles, and the dark room contrast of the image display device using the laminate to be manufactured may be inferior. is there. The more preferable lower limit of the average particle diameter of the aggregate is 200 nm, and the more preferable upper limit is 800 nm.
The average particle size of the silica fine particle aggregates was selected from a 5 μm square region containing a large amount of silica fine particle aggregates from a cross-sectional electron microscope observation (about 10,000 to 20,000 times). The particle diameter of the aggregate of fine particles was measured, and the average particle diameter of the aggregate of the top 10 silica fine particles was measured.
The “particle diameter of the aggregate of silica fine particles” is 2 so that the distance between the two straight lines becomes maximum when the cross section of the silica fine particle aggregate is sandwiched between any two parallel straight lines. It is measured as the distance between straight lines in a combination of straight lines. The particle diameter of the silica fine particle aggregate may be calculated using image analysis software.

In such a specific state, the antiglare layer in the laminate to be produced is a single layer by containing the aggregate of the silica particles in a pearl necklace shape and the organic fine particles contained in the composition for the antiglare layer. The concavo-convex shape is more uniformly and uniformly formed than the concavo-convex shape formed by the fine particles or the aggregates thereof. As a result, the laminate to be produced has good antiglare properties, can suppress glare, and can improve contrast.
Since the unevenness is uniform and uniform, an extremely large convex portion that becomes a singular point is eliminated while sufficiently providing an antiglare property. For this reason, since there is no significant distortion of transmitted light, glare can be suppressed, and furthermore, since large diffusion can be eliminated, the contrast can be improved.
This is presumed to be due to the following reasons.
That is, when the anti-glare layer composition is applied and then dried to evaporate the solvent, moderately aggregated silica fine particles are uniformly dispersed, so that the organic fine particles forming irregularities are also uniformly dispersed. Can keep. Furthermore, since the inorganic fine particles are roughly distributed around the organic fine particles, the curing shrinkage of the binder resin is larger than that of the portion where the inorganic fine particles are largely distributed. Sufficient protrusions can be stably formed. For this reason, it is estimated that the uneven | corrugated shape (convex part) formed in the surface of an anti-glare layer by the said organic fine particle becomes uniform and uniform compared with the uneven | corrugated shape (convex part) formed in single particle | grains.

As the binder resin, a polyfunctional acrylate monomer having no hydroxyl group in the molecule is preferably used as a main material. The above-mentioned "mainly a polyfunctional acrylate monomer that does not contain a hydroxyl group in the molecule" means that the content of the polyfunctional acrylate monomer that does not contain a hydroxyl group in the molecule is the largest among the raw material monomers of the binder resin. To do.
Since the polyfunctional acrylate monomer having no hydroxyl group in the molecule is a hydrophobic monomer, in the laminate of the present invention, the binder resin constituting the antiglare layer is preferably a hydrophobic resin. When the binder resin is mainly composed of a hydrophilic resin having a hydroxyl group, a highly polar solvent (for example, isopropyl alcohol) described later is difficult to evaporate, and inorganic fine particles can be roughly distributed around the organic fine particles. There is a risk of disappearing.

Examples of the polyfunctional acrylate monomer having no hydroxyl group in the molecule include pentaerythritol tetraacrylate (PETTA), 1,6-hexanediol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), and tripropylene glycol diester. Acrylate (TPGDA), PO-modified neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxytriacrylate, dipentaerythritol hexaacrylate (DPHA), pentaerythritol ethoxytetra Examples thereof include acrylate and ditrimethylolpropane tetraacrylate. Of these, pentaerythritol tetraacrylate (PETTA) is preferably used.

In addition, the other binder resin is preferably a transparent one, and for example, an ionizing radiation curable resin that is a resin curable by ultraviolet rays or electron beams is preferably cured by irradiation with ultraviolet rays or electron beams.
In the present specification, “resin” is a concept including monomers, oligomers, polymers and the like unless otherwise specified.

Examples of the ionizing radiation curable resin include compounds having one or more unsaturated bonds such as compounds having functional groups such as acrylates. Examples of the compound having one unsaturated bond include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone and the like. Examples of the compound having two or more unsaturated bonds include trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol. Hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meta Acrylate, isocyanuric acid tri (meth) acrylate, isocyanuric acid di (meth) acrylate, polyester tri (meth) acrylate, polyester di (meth) acrylate, bisphenol di (meth) acrylate, diglycerin tetra (meth) acrylate, adamantyl di ( Examples include polyfunctional compounds such as (meth) acrylate, isobornyl di (meth) acrylate, dicyclopentane di (meth) acrylate, and tricyclodecane di (meth) acrylate. In the present specification, “(meth) acrylate” refers to methacrylate and acrylate. In the present invention, as the ionizing radiation curable resin, a compound obtained by modifying the above-described compound with PO, EO or the like can also be used.

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, polythiol polyene resins, etc. It can be used as an ionizing radiation curable resin.

The ionizing radiation curable resin is used in combination with a solvent-drying resin (a thermoplastic resin or the like, which is a resin that forms a film only by drying the solvent added to adjust the solid content during coating). You can also. By using the solvent-drying resin in combination, film defects on the coating surface of the coating liquid can be effectively prevented when the antiglare layer is formed.
The solvent-drying resin that can be used in combination with the ionizing radiation curable resin is not particularly limited, and a thermoplastic resin can be generally used.
The thermoplastic resin is not particularly limited. For example, a styrene resin, a (meth) acrylic resin, a vinyl acetate resin, a vinyl ether resin, a halogen-containing resin, an alicyclic olefin resin, a polycarbonate resin, or a polyester resin. Examples thereof include resins, polyamide-based resins, cellulose derivatives, silicone-based resins, rubbers, and elastomers. The thermoplastic resin is preferably amorphous and soluble in an organic solvent (particularly a common solvent capable of dissolving a plurality of polymers and curable compounds). 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.) and the like are preferable.

Moreover, the said composition for glare-proof layers may contain the thermosetting resin.
The thermosetting resin is not particularly limited. For example, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation Examples thereof include resins, silicon resins, polysiloxane resins, and the like.

In the antiglare layer composition, the silica fine particles are preferably in a uniformly dispersed state in the composition. As shown in FIG. 4, the organic fine particles are dried when the coating film is dried. It is preferable that it is distributed roughly around the surface. FIG. 4 is still another cross-sectional STEM photograph of the laminate according to Example 1.
If the silica fine particles are not uniformly dispersed in the antiglare layer composition, uniform dispersion in the antiglare layer to be formed cannot be achieved, and aggregation in the antiglare layer composition is not possible. It progresses excessively and becomes a huge aggregate of the above-mentioned silica fine particles, and the above-mentioned uniform and uniform uneven shape cannot be formed.
Here, since the silica fine particles are materials that can thicken the anti-glare layer composition, the inclusion of the silica fine particles causes the organic fine particles contained in the anti-glare layer composition to settle. Can be suppressed. That is, the silica fine particles are presumed to have the function of promoting the formation of a predetermined distribution of the organic fine particles and the silica fine particles as described above and the function of improving the pot life of the composition for the antiglare layer.

Examples of the method for dispersing the silica fine particles uniformly in the antiglare layer composition and roughly distributing the organic fine particles around the organic fine particles in the coating film include, for example, Examples of the solvent added to the composition include a method of containing a predetermined amount of a solvent having a high polarity and a high volatilization rate. By containing such a solvent having a high polarity and a high volatilization rate, silica fine particles can be prevented from aggregating excessively in the antiglare layer composition. On the other hand, when a coating film is formed by applying and drying on the light-transmitting substrate, the solvent having the high polarity and the high volatilization rate is volatilized before other solvents. As a result, the periphery of the organic fine particles in the coating film becomes highly hydrophobic, the affinity with the silica fine particles is reduced, and the silica fine particles are less likely to be present. A state of being roughly distributed around the fine particles can be formed.
In the present specification, “a solvent having high polarity” means a solvent having a solubility parameter of 10 [(cal / cm ³ ) ^1/2 ] or more, and “a solvent having a high volatilization rate” means relative evaporation. It means a solvent having a speed of 150 or more. Therefore, the “solvent having a high polarity and a high volatilization rate” means a solvent satisfying the requirements of both the “solvent having a high polarity” and the “solvent having a high volatilization rate”.
In the present specification, the solubility parameter is calculated by the Fedors method. The Fedors method is described, for example, in “SP Value Basics / Applications and Calculation Methods” (Hideki Yamamoto, published by Information Technology Corporation, 2005). In the Fedors method, the solubility parameter is calculated from the following equation.
Solubility parameter = [ΣE _coh / ΣV] ²
In the above formula, _Ecoh 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 obtaining ΣE _coh and ΣV, which is the sum of E _coh and V.
Moreover, in this specification, the said relative evaporation rate means a relative evaporation rate when the evaporation rate of n-butyl acetate is set to 100, and is an evaporation rate measured based on ASTM D3539-87. Is calculated by Specifically, the evaporation time of n-butyl acetate and the evaporation time of each solvent in dry air at 25 ° C. are measured and calculated.
Relative evaporation rate = (time required for 90% by weight of n-butyl acetate to evaporate) / (time required for 90% by weight of the solvent to evaporate) × 100

Examples of the solvent having a high polarity and a high volatilization rate include ethanol and isopropyl alcohol. Among them, 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% by mass, an aggregate of silica fine particles may be produced in the composition for an antiglare layer. The content of isopropyl alcohol is preferably 40% by mass or less. If it exceeds 40% by mass, the silica fine particles may not be distributed roughly around the organic fine particles.

Other solvents contained in the antiglare layer composition include, for example, 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.), Examples include alcohols (butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethylsulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.), etc. In a mixture It may be.

The antiglare layer composition preferably further contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited, and known ones can be used. Specific examples include, for example, acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, thioxanthones, propio Examples include phenones, benzyls, benzoins, and acylphosphine oxides. In addition, it is preferable to use a mixture of photosensitizers, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine, and the like.

As the photopolymerization initiator, when the binder resin is a resin system having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, etc. may be used alone or in combination. preferable. When the binder resin is a resin system having a cationic polymerizable functional group, examples of the photopolymerization initiator include aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, benzoin sulfonate esters, and the like. Are preferably used alone or as a mixture.

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. If it is less than 0.5 part by mass, the hard coat performance of the antiglare layer to be formed may be insufficient, and if it exceeds 10.0 parts by mass, there is also a possibility of inhibiting curing. It is not preferable.

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

The antiglare layer composition includes conventionally known dispersants, surfactants, antistatic agents, depending on the purpose of increasing the hardness of the antiglare layer, suppressing curing shrinkage, controlling the refractive index, and the like. Silane coupling agent, thickener, anti-coloring agent, coloring agent (pigment, dye), antifoaming agent, leveling agent, flame retardant, UV absorber, adhesion-imparting agent, polymerization inhibitor, antioxidant, surface modification An agent, a lubricant, etc. may be added.
Examples of the leveling agent include silicone oil, fluorine-based surfactants, and the like. Preferably, a fluorine-based surfactant containing a perfluoroalkyl group avoids the antiglare layer from having a Benard cell structure. Therefore, it is preferable. When a resin composition containing a solvent is applied and dried, a surface tension difference or the like is generated between the coating film surface and the inner surface in the coating film, thereby causing many convections in the coating film. The structure generated by this convection is called a Benard cell structure, and causes problems such as the skin and coating defects in the antiglare layer to be formed.
Further, the Benard cell structure has an excessively large unevenness on the surface of the antiglare layer, which causes white blurring and adverse effects on surface glare. When the leveling agent as described above is used, this convection can be prevented, so that not only a concavo-convex film having no defects or unevenness can be obtained, but also the concavo-convex shape can be easily adjusted.

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

In the method for producing a laminate of the present invention, the antiglare layer composition is prepared by mixing and stirring the binder resin and the organic fine particles in the solvent and preparing an intermediate composition, and then adding the inorganic composition to the intermediate composition. It is prepared by mixing and dispersing fine particles (silica fine particles).
That is, in the present invention, the antiglare layer composition is one in which inorganic fine particles are added last among the essential constituent materials of the antiglare layer composition. When the composition for an antiglare layer is prepared by adding the inorganic fine particles to the solvent before adding the organic fine particles or the binder resin, excessive aggregation of the inorganic fine particles due to the solvent attack occurs, and the uniform and even It becomes impossible to form an antiglare layer having an uneven shape. Moreover, in order to make the above-mentioned effect more reliable, it is more preferable that the inorganic fine particles are an inorganic fine particle dispersion dispersed in the solvent when the inorganic fine particles are added last.

The 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, the intermediate composition is prepared using a known apparatus such as a paint shaker, a bead mill, a kneader, or a mixer. be able to.
Moreover, the method similar to the above is mentioned also about the method of preparing the composition for glare-proof layers by adding an inorganic fine particle to the said intermediate composition.

The method for applying the antiglare layer composition on the light-transmitting substrate is not particularly limited, and examples thereof include spin coating, dipping, spraying, die coating, bar coating, roll coater, and meniscus coater. And publicly known methods such as a method, a flexographic printing method, a screen printing method, and a bead coater method.
After applying the anti-glare layer composition by any of the above methods, it is transported to a heated zone to dry the formed coating film, and the coating film is dried by various known methods to evaporate the solvent. By selecting the solvent relative evaporation rate, solid content concentration, coating solution temperature, drying temperature, drying air velocity, drying time, solvent atmosphere concentration in the drying zone, etc., the distribution state of organic fine particles and inorganic fine particles can be adjusted. .
In particular, a method of adjusting the distribution state of the aggregates of organic fine particles and silica fine particles by selecting drying conditions is simple and preferable. Specifically, the drying temperature is preferably 30 to 120 ° C., and the drying wind speed is preferably 0.2 to 50 m / s, and the organic fine particles are obtained by performing drying treatment appropriately adjusted within this range once or plural times. In addition, the distribution state of the aggregates of silica fine particles can be adjusted to a desired state.

In addition, as a method of irradiating ionizing radiation when curing the coating film after drying, for example, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp is used. A method is mentioned.
Moreover, as a wavelength of an ultraviolet-ray, the wavelength range of 190-380 nm can be used. Specific examples of the electron beam source include various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type.

As described above, the laminate produced by the method for producing a laminate of the present invention has a highly controlled dispersion of inorganic fine particles (silica fine particles) in the composition for forming an antiglare layer. The concavo-convex shape formed on the surface of the antiglare layer is extremely uniform and uniform compared to the concavo-convex shape on the surface of the antiglare layer of the conventional laminate.
Since the antiglare layer having such a concavo-convex shape has few convex portions that form singular points on its surface, it can suppress glare at an extremely high level while having good antiglare properties, It can be set as the laminated body which can obtain the display image excellent in contrast.

Further, the laminate having an antiglare layer having a concavo-convex shape on one surface of a light-transmitting substrate, wherein the concavo-convex shape of the surface of the antiglare layer has a surface of the antiglare layer of 100 μm. Dividing into four measurement areas, calculating the arithmetic average roughness Sa in each measurement area, when the average value of the arithmetic average roughness Sa is Ma and the standard deviation of the arithmetic average roughness Sa is Sq, A laminate having a ratio to Sq (Sq / Ma) of 0.15 or less is also one aspect of the present invention.
Since the resolution of the human eye is about 100 μm, if there is a large variation in every 100 μm square, 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 transmitted light of the laminate of the present invention is recognized and observed as glare. The (Sq / Ma) is preferably 0.12 or less, and more preferably 0.10 or less.
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 μm, the antiglare property of the laminate of the present invention may be insufficient, and if it exceeds 0.40 μm, the contrast of the laminate of the present invention may be deteriorated.
The arithmetic average roughness Sa is obtained by expanding the arithmetic average roughness Ra, which is a two-dimensional roughness parameter described in JIS B0601: 1994, into three dimensions, and the orthogonal coordinate axes X and Y axes on the reference plane. And the roughness curved surface is Z (x, y), and the size of the measurement region surface is Lx, Ly, the following equation (a) is calculated.
In the above formula (a), A = Lx × Ly is represented.
When 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 average roughness Sa is calculated by the following formula (b).
In the above formula (b), N represents the total number of points.
As a device for obtaining such arithmetic average roughness Sa in three dimensions, a contact type surface roughness meter or a non-contact type surface roughness meter (for example, an interference microscope, a confocal microscope, an atomic force microscope, etc.) is used. Can be mentioned. Among these, it is preferable to measure using an interference microscope from the simplicity of measurement. Examples of such an interference microscope include “New View” series manufactured by Zygo.

In the laminate of the present invention, the antiglare layer preferably contains a binder resin, organic fine particles, and inorganic fine particles.
Examples of the binder resin, the organic fine particles and the inorganic fine particles, and the light-transmitting substrate include the same materials as those described in the above-described method for producing a laminate of the present invention.
Further, the method for producing the laminate of the present invention is not particularly limited as long as the uneven shape on the surface of the antiglare layer can be controlled so as to satisfy the above requirements. For example, the laminate of the present invention described above is used. It can manufacture with the manufacturing method of.

Further, the laminate having an antiglare layer having a concavo-convex shape on one surface of the light-transmitting substrate, the antiglare layer containing a binder resin, organic fine particles and inorganic fine particles, The laminate is characterized in that the inorganic fine particles are roughly distributed around the organic fine particles and are uniformly distributed in the anti-glare layer except for the periphery of the organic fine particles. This is one of the aspects of the present invention.

The laminate of the present invention according to another aspect has an antiglare layer, and the antiglare layer contains a binder resin, organic fine particles and inorganic fine particles, and the inorganic fine particles are disposed around the organic fine particles. It is distributed roughly.
Here, when the cross section of the antiglare layer is observed with an electron microscope, the inorganic fine particles roughly distributed around the organic fine particles are not only cross sections passing through the center of the organic fine particles, but also a cross section shifted from the center of the organic fine particles. A state of coarse distribution is also observed.
The above-mentioned “the inorganic fine particles are roughly distributed around the organic fine particles” means that the antiglare layer has a magnification of 10,000 times under an electron microscope (preferably a transmission type such as TEM or STEM). When the cross section where the organic fine particles in the thickness direction are observed is observed with a microscope, the area ratio of the inorganic fine particles in the region outside the organic fine particles within the circumference of 500 nm and excluding the organic fine particles is Mn, When the area ratio of the inorganic fine particles in the region outside the circumference 500 nm outside the fine particles is Mf, it means that Mf / Mn is 1.5 or more.
In addition, the above-mentioned “uniformly distributed in the antiglare layer except for the periphery of the organic fine particles” means “uniformly distributed in the antiglare layer” described in the method for producing a laminate of the present invention described above. It has the same meaning as

In the laminate of the present invention according to another aspect, the organic fine particles and the inorganic fine particles are contained in the antiglare layer in the relationship described in the composition for an antiglare layer in the above-described method for producing a laminate of the present invention. The concavo-convex shape formed on the surface becomes extremely uniform and uniform as compared with the concavo-convex shape of the antiglare layer of the conventional laminate. According to the laminate of the present invention relating to another embodiment having such an antiglare layer, the occurrence of glare can be suppressed at an extremely high level while having good antiglare properties, and a display image with excellent high contrast can be obtained. be able to.

In the laminate of the present invention according to another aspect, the binder resin, the organic fine particles and the inorganic fine particles, and the light transmissive substrate are the same as those described in the method for producing the laminate of the present invention described above. Things.
In addition, the method for producing the laminate of the present invention according to another embodiment is not particularly limited as long as it can be controlled to contain the organic fine particles and the inorganic fine particles in the antiglare layer in the state described above. It can manufacture with the manufacturing method of the laminated body of this invention mentioned above.

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 antiglare layer as described above. The surface of the antiglare layer has a very uniform and uniform uneven shape as compared with the antiglare layer of the conventional laminate.
Specifically, the uneven shape on the surface of the antiglare layer is, specifically, the average interval of the unevenness on the surface of the antiglare layer is Sm, the average inclination angle of the uneven portion is θa, and the arithmetic average roughness of the unevenness is Ra. When the ten-point average roughness of irregularities is Rz, it is preferable that the following formula is satisfied. If θa, Ra, and Rz are less than the lower limit, reflection of external light may not be suppressed. If θa, Ra, and Rz exceed the upper limit, the bright room contrast may decrease due to an increase in diffuse reflection of external light, or the dark room contrast may decrease due to an increase in stray light from transmitted video light. In the configuration of the present invention, if Sm is less than the lower limit, the contrast may be inferior. On the other hand, if Sm exceeds the upper limit, glare may not be sufficiently suppressed.
50 μm <Sm <300 μm
0.5 ° <θa <4.0 °
0.05 μm <Ra <0.40 μm
0.30 μm <Rz <2.50 μm

Further, the uneven shape of the antiglare layer preferably satisfies the following formula from the above viewpoint.
50 μm <Sm <200 μm
0.8 ° <θa <2.0 °
0.10 μm <Ra <0.25 μm
0.50 μm <Rz <1.80 μm
More preferably, the uneven shape of the antiglare layer satisfies the following formula.
70 μm <Sm <100 μm
1.0 ° <θa <1.5 °
0.12 μm <Ra <0.18 μm
0.80 μm <Rz <1.30 μm
In the present specification, Sm, Ra and Rz are values obtained by a method according to JIS B 0601-1994, and θa is a surface roughness measuring instrument: SE-3400 instruction manual (1995.07). .20 revision) (Osaka Laboratory Co., Ltd.), which is a value obtained by the definition described in FIG. 1. As shown in FIG. 1, the sum of the heights of the convex portions existing in the reference length L (h ₁ + h ₂ + h ₃ + ... + H _n ) arc tangent θa = tan ⁻¹ {(h ₁ + h ₂ + h ₃ +... + H _n ) / L}.
Such Sm, θa, Ra, and Rz can be determined by measuring with, for example, a surface roughness measuring instrument: SE-3400 / manufactured by Kosaka Laboratory Ltd.

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 μm, the surface of the antiglare layer may be easily damaged, and if it exceeds 7.0 μm, the antiglare layer may be easily broken. A more preferable range of the thickness of the antiglare layer is 2.0 to 5.0 μm. In addition, the thickness of the said glare-proof layer can be measured by cross-sectional microscope observation.

The laminate of the present invention preferably has a total light transmittance of 85% or more. If it is less than 85%, color reproducibility and visibility may be impaired when the laminate of the present invention is mounted on the surface of an image display device. The total light transmittance is more preferably 90% or more, and still more preferably 91% or more.
The total light transmittance can be measured by “HM-150” manufactured by Murakami Color Research Laboratory according to JIS K7361.

The laminate of the present invention preferably has a haze of less than 40%. The anti-glare layer may be composed of internal haze due to internal diffusion due to the contained fine particles and external haze due to the uneven shape on the outermost surface, and the internal haze due to internal diffusion is preferably in the range of 5% to 30%. If it is less than 5%, glare of the laminate of the present invention may not be sufficiently suppressed, and if it exceeds 30%, the contrast of the laminate of the present invention may be inferior. Further, the internal haze of the laminate of the present invention is more preferably in the range of 5% to 20%, and still more preferably in the range of 5% to 15%. The outermost haze on the outermost surface is preferably in the range of 5% to 30%. If it is less than 5%, the antiglare property of the laminate of the present invention may not be sufficient, and if it exceeds 30%, the contrast of the laminate of the present invention may be inferior. The external haze of the laminate of the present invention is more preferably in the range of 5% to 20%, and still more preferably in the range of 7% to 15%.
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 antiglare layer can be independently controlled. For example, by using fumed silica, since the average particle diameter of the fumed silica is small, internal haze does not appear and only external haze can be adjusted. The internal haze is adjusted by controlling the ratio of the refractive index of the organic fine particles to 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 the binder resin monomer. You can do it.
The haze can be measured with “HM-150” manufactured by Murakami Color Research Laboratory according to JIS K7136.
The internal haze is determined as follows.
On the unevenness on the surface of the antiglare layer of the laminate, a resin having a refractive index equal to that of the resin forming the surface unevenness or a refractive index difference of 0.02 or less is dried with a wire bar to a thickness of 8 μm (completely surface The film is coated so as to have a film thickness that allows the surface to be flattened, and dried at 70 ° C. for 1 minute, and then cured by irradiating with 100 mJ / cm 2 of ultraviolet rays. Thereby, the unevenness on the surface is crushed and a film having a flat surface is obtained. However, if the resin applied to the surface of the antiglare layer is easily repelled and difficult to wet due to the presence of a leveling agent or the like in the composition for forming the antiglare layer having the uneven shape, the antiglare layer is preliminarily used. The surface of the layer was saponified (2 mol / L NaOH (or KOH) solution at 55 ° C. for 3 minutes, washed with water, completely removed with Kimwipe (registered trademark), etc. Hydrophilic treatment is preferably performed by drying for 1 minute.
Since the film having a flat surface does not have surface irregularities, it has only an internal haze. The internal haze can be determined by measuring the haze of this film in accordance with JIS K-7136 in the same manner as haze.
The external haze can be obtained as (haze-internal haze).

Moreover, since the laminated body of this invention can prevent generation | occurrence | production of white blur more suitably, it is preferable to have a low-refractive-index layer on the said glare-proof layer.
The low refractive index layer is a layer that plays a role of reducing the reflectance when light from the outside (for example, a 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 and magnesium fluoride, 2) a fluorine-based resin which is a low refractive index resin, and 3) fluorine containing silica or magnesium fluoride. 4) a resin, 4) a thin film of a low refractive index material such as silica or magnesium fluoride, or the like. For resins other than the fluorine-based resin, the same resin as the binder resin constituting the antiglare layer described above can be used.
Moreover, it is preferable that the silica mentioned above is a hollow silica fine particle, and such a hollow silica fine particle can be produced by, for example, a production method described in Examples of JP-A-2005-099778.
These low refractive index layers preferably have a refractive index of 1.45 or less, particularly 1.42 or less.
Further, the thickness of the low refractive index layer is not limited, but it may be set appropriately from the range of about 30 nm to 1 μm.
In addition, although the low refractive index layer is effective as a single layer, it is possible to provide two or more low refractive index layers as appropriate for the purpose of adjusting a lower minimum reflectance or a higher minimum reflectance. . When the two or more low refractive index layers are provided, it is preferable to provide a difference in the refractive index and thickness of each low refractive index layer.

As the fluororesin, a polymerizable compound containing a fluorine atom in at least a molecule or a polymer thereof 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 ionizing radiation, and a polar group thermally cured, is preferable. Moreover, the compound which has these reactive groups simultaneously may be sufficient. In contrast to this polymerizable compound, a polymer has no reactive groups as described above.

As the polymerizable compound having a functional group that is cured by ionizing radiation, fluorine-containing monomers having an ethylenically unsaturated bond can be widely used. More specifically, to illustrate fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluorobutadiene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.) Can do. 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) ethyl (meth) acrylate, α-trifluoro (Meth) acrylate compounds having a fluorine atom in the molecule, such as methyl methacrylate and α-trifluoroethyl methacrylate; a C 1-14 fluoroalkyl group having at least 3 fluorine atoms in the molecule, fluoro A cycloalkyl group or a fluoroalkylene group and at least two (medium There are also fluorine-containing polyfunctional (meth) acrylic acid ester compounds having an acryloyloxy group.

Preferable examples of the thermosetting polar group include 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 adhesion to the coating film but also in affinity with inorganic ultrafine particles such as silica. Examples of the polymerizable compound having a thermosetting polar group include 4-fluoroethylene-perfluoroalkyl vinyl ether copolymer; fluoroethylene-hydrocarbon vinyl ether copolymer; epoxy, polyurethane, cellulose, phenol, polyimide, and the like. Examples include fluorine-modified products of each resin.
Examples of the polymerizable compound having both a functional group curable by ionizing radiation and a polar group curable by heat include acrylic or methacrylic acid moieties and fully fluorinated alkyl, alkenyl, aryl esters, fully or partially fluorinated vinyl ethers, fully Alternatively, partially fluorinated vinyl esters, fully or partially fluorinated vinyl ketones and the like can be exemplified.

Moreover, as a fluorine resin, the following can be mentioned, for example.
Polymer of monomer or monomer mixture containing at least one fluorine-containing (meth) acrylate compound of a polymerizable compound having an ionizing radiation curable group; at least one fluorine-containing (meth) acrylate compound; and methyl (meth) Copolymers with (meth) acrylate compounds that do not contain fluorine atoms in the molecule such as acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; fluoroethylene , Fluorine-containing compounds such as vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, 3,3,3-trifluoropropylene, 1,1,2-trichloro-3,3,3-trifluoropropylene, hexafluoropropylene Monomer homopolymer or Copolymer such as. Silicone-containing vinylidene fluoride copolymers obtained by adding a silicone component to these copolymers can also be used. The silicone components in this case include (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 Over emissions, fluorine-modified silicones, polyether-modified silicone and the like. Of these, those having a dimethylsiloxane structure are preferred.

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

Moreover, each binder resin as described in the said glare-proof layer can also be mixed and used with the polymeric compound and polymer which have the above-mentioned fluorine atom. Furthermore, various additives and solvents can be used as appropriate in order to improve the curing agent for curing reactive groups and the like, to improve the coating property, and to impart antifouling properties.

In the formation of the low refractive index layer, 0.5 to 5 mPa · s (25 ° C.) at which a preferable coating property is obtained for the viscosity of the composition for a low refractive index layer obtained by adding a low refractive index agent and a resin, It is preferable to set it as the range of 0.7-3 mPa * s (25 degreeC) preferably. An antireflection layer excellent in visible light can be realized, a uniform thin film with no coating unevenness can be formed, and a low refractive index layer particularly excellent in adhesion can be formed.

The resin curing means may be the same as that described for the antiglare layer described above. When a heating means is used for the curing treatment, it is preferable to add a thermal polymerization initiator that generates, for example, a radical by heating to start polymerization of the polymerizable compound, to the fluororesin composition.

The layer thickness (nm) d _A of the low refractive index layer is expressed 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 a wavelength, preferably a value in the range of 480 to 580 nm)
Those satisfying these conditions are preferred.

In the present invention, the low refractive index layer is represented by the following formula (2):
_{120 <n A d A <145} (2)
It is preferable from the viewpoint of low reflectivity.

The laminated body of the present invention is also one of other layers (an antistatic layer, an antifouling layer, an adhesive layer, other hard coat layers, etc.) as necessary within the range where the effects of the present invention are not impaired. A layer or two or more layers can be formed as appropriate. Among these, it is preferable to have at least one of an antistatic layer and an antifouling layer. These layers may be the same as those of a known antireflection laminate.

The laminate of the present invention preferably has a contrast ratio of 40% or more, more preferably 60% or more. When it is less than 40%, when the laminate of the present invention is mounted on the display surface, the dark room contrast is inferior and the visibility may be impaired. In addition, the said contrast ratio in this specification is the value measured by the method as described in the below-mentioned Example.

The laminate of the present invention can be made into a polarizing plate by providing the laminate according to the present invention on the surface of the polarizing element opposite to the surface on which the antiglare layer is present. Such a polarizing plate is also one aspect 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 saponified film, etc. dyed and stretched with iodine or the like can be used. In the laminating process of the polarizing element and the laminate of the present invention, it is preferable to saponify the light-transmitting substrate (triacetyl cellulose film). By the saponification treatment, the adhesiveness is improved and an antistatic effect can be obtained.

This invention is also an image display apparatus provided with the said laminated body or the said polarizing plate on the outermost surface.
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, and electronic paper.

The LCD, which is a typical example of the above, includes a transmissive display body and a light source device that irradiates the transmissive display body from the back. When the image display device of the present invention is an LCD, the laminate of the present invention or the polarizing plate of the present invention is formed on the surface of the transparent display.

In the case where the present invention is a liquid crystal display device having the above laminate, the light source of the light source device is irradiated from below the laminate. Note that a retardation plate may be inserted between the liquid crystal display element and the polarizing plate. An adhesive layer may be provided between the layers of the liquid crystal display device as necessary.

The PDP, which is the image display device, has a front glass substrate (electrode is formed on the surface) and a rear glass substrate (disposed with electrodes and minute grooves) disposed with a discharge gas sealed between the front glass substrate and the front glass substrate. Formed on the surface and forming red, green and blue phosphor layers in the grooves). When the image display device of the present invention is a PDP, the above-described laminate is provided on the surface of the surface glass substrate or the front plate (glass substrate or film substrate).

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

In any case, the image display device of the present invention can be used for display display of a television, a computer, electronic paper, a touch panel, a tablet PC, or the like. In particular, it can be suitably used for the surface of high-definition image displays such as CRT, liquid crystal panel, PDP, ELD, FED, and touch panel.

Since the method for producing a laminate of the present invention has the above-described configuration, it is possible to suppress the occurrence of glare at an extremely high level while having good anti-glare properties, and to obtain a display image with excellent high contrast. The laminated body of the present invention that can be manufactured can be manufactured.
For this reason, the laminate of the present invention includes a cathode ray tube display (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED), electronic paper, a touch panel, and a tablet. It can be suitably applied to a PC or the like.

It is explanatory drawing of the measuring method of (theta) a. 2 is a cross-sectional electron micrograph of a laminate according to Example 1. 4 is another cross-sectional electron micrograph of the laminate according to Example 1; 4 is still another cross-sectional electron micrograph of the laminate according to Example 1.

The contents of the present invention will be described with reference to the following examples, but the contents of the present invention should not be construed as being limited to these embodiments. Unless otherwise specified, “part” and “%” are based on mass.

(Preparation of composition 1 for anti-glare layer)
The composition shown below was dispersed by a bead mill to obtain an intermediate composition.
Next, the following formulation was dispersed with a bead mill to obtain an inorganic fine particle dispersion.
Then, while stirring the intermediate composition with a disper, the inorganic fine particle dispersion was gradually added to obtain a composition 1 for an antiglare layer.

(Intermediate composition)
Organic fine particles (non-hydrophilic treatment acrylic-styrene copolymer particles, average particle size 3.5 μm, refractive index 1.55, manufactured by Sekisui Plastics Co., Ltd.) 14 parts by mass pentaerythritol tetraacrylate (PETTA) (product name: PETA 65 parts by weight urethane acrylate (product name “V-4000BA”, manufactured by DIC) 35 parts by weight Irgacure 184 (manufactured by BASF Japan) 5 parts by weight polyether-modified silicone (TSF4460, Momentive Performance) 0.025 parts by mass Toluene 100 parts by mass Isopropyl alcohol 35 parts by mass Cyclohexanone 20 parts by mass

(Inorganic fine particle dispersion)
Fumed silica (octylsilane treatment; average primary particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.) 6 parts by mass Toluene 45 parts by mass Isopropyl alcohol 20 parts by mass

(Preparation of composition 2 for antiglare 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 for this, a composition 2 for an antiglare layer was obtained in the same manner as the composition 1 for an antiglare layer.

(Preparation of composition 3 for antiglare layer)
An antiglare layer composition 3 was obtained in the same manner as the antiglare layer composition 1 except that the amount of isopropyl alcohol in the intermediate composition was 5 parts by mass and the amount of cyclohexanone was 50 parts by mass.

(Preparation of composition 4 for anti-glare layer)
An antiglare layer composition 4 was obtained in the same manner as the antiglare layer composition 1 except that the amount of fumed silica in the inorganic fine particle dispersion was changed to 4 parts by mass.

(Preparation of composition 5 for anti-glare layer)
Each composition shown in the intermediate composition and the inorganic fine particle dispersion in the antiglare layer composition 1 was simultaneously dispersed by a bead mill to obtain an antiglare layer composition 5.

(Preparation of composition 6 for antiglare layer)
The composition shown below was dispersed by a bead mill to obtain a composition 6 for an antiglare layer.
Organic fine particles (non-hydrophilic polystyrene particles, average particle diameter 3.5 μm, refractive index 1.59, manufactured by Soken Chemical Co., Ltd.) 14 parts by mass pentaerythritol triacrylate (PETA) (product name “PETIA”, manufactured by Daicel-Cytec) ) 100 parts by mass acrylic polymer (molecular weight 75,000, manufactured by Mitsubishi Rayon Co., Ltd.) 10 parts by mass polymerization initiator (product name “Irgacure 184”, manufactured by BASF Japan) 5 parts by mass polyether-modified silicone (product name “TSF4460”, 0.025 parts by mass Toluene 120 parts by mass Cyclohexanone 30 parts by mass

(Preparation of composition 7 for anti-glare layer)
Except that the organic fine particles in the antiglare layer composition 6 are non-hydrophilic treated acrylic-styrene copolymer particles (average particle size 3.5 μm, refractive index 1.55, manufactured by Sekisui Plastics Co., Ltd.). The antiglare layer composition 7 was obtained in the same manner as the antiglare layer composition 6.

Example 1
The composition 1 for an antiglare layer was applied to one side of a light-transmitting substrate (thickness 60 μm triacetylcellulose resin film, manufactured by Fuji Film, TD60UL) to form a coating film. Next, 70 ° C. dry air was passed through the formed coating film at a flow rate of 0.2 m / s for 15 seconds, and then 70 ° C. dry air was passed through for 30 seconds at a flow rate of 10 m / s. By evaporating the solvent in the coating film, the coating film is cured by irradiating with an ultraviolet ray so that the integrated light amount is 100 mJ / cm ² , thereby forming an antiglare layer having a thickness of 6 μm (during curing), The laminated body which concerns on Example 1 was produced.

(Examples 2 to 4)
The laminated body which concerns on Examples 2-4 was produced like Example 1 except having used the compositions 2-4 for glare-proof layers instead of the composition 1 for glare-proof layers, respectively.

(Comparative Example 1)
A laminate according to Comparative Example 1 was produced in the same manner as in Example 1 except that the antiglare layer composition 5 was used instead of the antiglare layer composition 1.

(Comparative Examples 2-3)
Comparative Examples 2-3 were used in the same manner as in Example 1 except that the antiglare layer compositions 6-7 were used in place of the antiglare layer composition 1 and the thickness at curing was 4.5 μm. Such a laminate was produced.

The laminates according to the obtained Examples, Comparative Examples, and Reference Examples were evaluated for the following items.
All the results are shown in Table 1.

(Anti-glare)
About the anti-glare property of the obtained laminate, the three-wave fluorescent lamp is 1.5 m above, with a black acrylic plate, a transparent adhesive, and a laminate (the adhesive side is the non-coated surface of the light-transmitting substrate). In a bright room environment with an illuminance of about 1000 Lx, the extent to which the reflection of the fluorescent lamp was not anxious was evaluated according to the following criteria.
◎: The image of the fluorescent lamp is completely blurred and cannot be recognized ○: The image of the fluorescent lamp is reflected, but the outline is blurred and the boundary of the outline cannot be recognized ×: The image of the fluorescent lamp is reflected The outline can also be recognized clearly

(Glare evaluation)
About the surface glare of the obtained laminated body, it evaluated as follows.
A surface of the laminate, on which the antiglare layer was not formed, and a glass surface on which the black matrix (glass thickness 0.7 mm) was not formed were bonded together with a transparent adhesive to obtain a sample.
For the sample thus obtained, a white surface light source (manufactured by HAKUBA, LIGHTBOX, average luminance of 1000 cd / m ² ) was installed on the black matrix side, thereby generating pseudo glare.
This was photographed from the laminate side with a CCD camera (KP-M1, C mount adapter, close-up ring; PK-11A Nikon, camera lens; 50 mm, F1.4s NIKOR). The distance between the CCD camera and the laminated body was 250 mm, and the focus of the CCD camera was adjusted to match the laminated body. Images taken with a CCD camera were taken into a personal computer and analyzed with image processing software (ImagePro Plus ver. 6.2; manufactured by Media Cybernetics) as follows.
First, an evaluation location of 200 × 160 pixels was selected from the captured image, and converted to a 16-bit gray scale at the evaluation location. Next, the low-pass filter was selected from the enhancement tab of the filter command, and the filter was applied under the conditions of “3 × 3, number of times 3, strength 10”. As a result, components derived from the black matrix pattern were removed.
Next, flattening was selected, and shading correction was performed under the condition of “background: dark, object width 10”.
Next, contrast enhancement was performed with “contrast: 96, brightness: 48” using a contrast enhancement command.
The obtained image was converted to an 8-bit gray scale, and the variation in the value for each pixel was calculated as a standard deviation value for 150 × 110 pixels in the image, thereby glaring was digitized. It can be said that the smaller the numerical value of the glare value, the less the glare. The measurement was performed with a black matrix equivalent to a pixel density of 200 ppi.
The measured glare value was evaluated according to the following criteria.
A: The glare value is 14 or less. B: The glare value is more than 14, 18 or less. X: The glare value is more than 18.

(Contrast ratio)
In contrast ratio measurement, when a cold cathode tube light source with a diffusion plate installed as a backlight unit was used, two polarizing plates (AMN-3244TP manufactured by Samsung) were used, and the polarizing plates were installed in parallel Nicols. the luminance of _{L max} of light that passes through, divided by the brightness of _{L min} of light passing through when installed in a cross nicol state with _(L max _{/ L min)} and contrast, the laminate (light-transmitting substrate + The contrast (L ₁ ) when the antiglare layer is placed on the outermost surface and the contrast (L ₂ ) when only the light-transmitting substrate is placed on the outermost surface are determined, and (L ₁ / L ₂ ) × 100 (%) to calculate the contrast ratio.
The luminance was measured using a color luminance meter (BM-5A manufactured by Topcon Corporation) in a dark room environment with an illuminance of 5 Lx or less. The measurement angle of the color luminance meter was set to 1 °, and the measurement was performed with a visual field of 5 mm on the sample. The amount of light of the backlight was set such that the luminance when the two polarizing plates were set in parallel Nicol was 3600 cd / m ² without the sample being set.
A: The contrast ratio is 60% or more. B: The contrast ratio is 40% or more and less than 60%. X: The contrast ratio is less than 40%.

(Sq / Ma)
A surface of the obtained laminated body opposite to the surface on which the antiglare layer is formed is attached to a glass plate via a transparent adhesive to prepare a sample, and a white interference microscope (New View 7300, manufactured by Zygo) ) Was used to measure and analyze the surface shape of the antiglare layer under the following conditions. In addition, Microscope Application 8.3.2 Microscope Application was used as measurement / analysis software.
(Measurement condition)
Objective lens: 50 × Zoom: 1 × Measurement area: 414 μm × 414 μm
Resolution (interval per point): 0.44 μm
(Analysis conditions)
Removed: Sphere
Filter: LowPass
FilterType: GaussSpline
High wavelength: 2.5 μm
Remove spikes: on
Spike Height (xRMS): 2.5
The data measured under the above measurement conditions are divided into 16 regions of 100 μm × 100 μm using “Mask Editor”, and “Ra” is displayed on the Surface Map screen under the above analysis conditions for each region. The value of Sa was read and used as the value of Sa. Then, the average value thereof was Ma, and the standard deviation thereof was Sq, and (Sq / Ma) was calculated.

(Haze, Internal haze)
About the haze of each laminated body, it measured by the method based on JISK-7136 (haze) using the haze meter (the Murakami Color Research Laboratory make, model name; HM-150). About internal haze, it measured by the method mentioned above.

(Average interval of unevenness (Sm), arithmetic average roughness of unevenness (Ra), average inclination angle of unevenness (θa), 10-point average roughness (Rz))
According to JIS B 0601-1994, the average interval (Sm) of unevenness, the arithmetic average roughness (Ra) and the 10-point average roughness (Rz) of unevenness were measured, and the average of unevenness was measured by the method shown in FIG. The inclination angle (θa) was measured. In addition, the measurement of said Sm, Ra, (theta) a, and Rz was performed on condition of the following using the surface roughness measuring device: SE-3400 / made by Kosaka Laboratory.
(1) The stylus of the surface roughness detector:
Model No./SE2555N (2μ stylus), manufactured by Kosaka Laboratory Ltd. (tip radius of curvature 2μm / vertical angle: 90 degrees / material: diamond)
(2) Measurement conditions of surface roughness measuring instrument:
Reference length (cutoff value of roughness curve λc: 0.8 mm
Evaluation length (reference length (cut-off value λc) × 5): 4.0 mm
Feeding speed of stylus: 0.5 mm / s
Preliminary length: (cutoff value λc) × 2
Vertical magnification: 2000 times Horizontal magnification: 10 times

As shown in Table 1, the laminates according to the examples were all excellent in evaluation of glare, contrast ratio and antiglare property, and were excellent in production stability.
On the other hand, since the laminated body which concerns on the comparative example 1 was manufactured using the composition for glare-proof layers which disperse | distributes each composition of an intermediate | middle composition and inorganic fine particle dispersion simultaneously, it was inferior to the evaluation of glare. Moreover, since the laminated body which concerns on the comparative example 2 is not using inorganic fine particles and uneven | corrugated shape is not formed uniformly and uniformly, it was inferior to the evaluation of glare. Moreover, since the laminated body which concerns on the comparative example 3 had large internal haze, although the glare was favorable, it was inferior to evaluation of contrast ratio.

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

Claims (11)

On one surface of the light-transmitting substrate, a method for producing a laminate having an antiglare layer having an uneven shape on the surface,
The anti-glare layer is formed by drying and curing a coating film 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 surface of the light-transmitting substrate. Forming a layer,
The anti-glare layer composition 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. A method for producing a laminate, wherein On one surface of the light-transmitting substrate, a laminate having an antiglare layer having an uneven shape on the surface,
The uneven shape of the surface of the antiglare layer is obtained by dividing the surface of the antiglare layer into 100 μm square measurement regions, obtaining the arithmetic average roughness Sa in each measurement region, and calculating the average value of the arithmetic average roughness Sa as Ma. When the standard deviation of the arithmetic mean roughness Sa is Sq, the ratio of Ma to Sq (Sq / Ma) is 0.15 or less. The laminate according to claim 2, wherein the antiglare layer contains a binder resin, organic fine particles, and inorganic fine particles. On one surface of the light-transmitting substrate, a laminate having an antiglare layer having an uneven shape on the surface,
The antiglare layer contains a binder resin, organic fine particles and inorganic fine particles,
The inorganic fine particles are roughly distributed around the organic fine particles, and are uniformly distributed in the anti-glare layer except for the periphery of the organic fine particles. The laminate according to claim 3 or 4, wherein the inorganic fine particles are silica fine particles. The laminate according to claim 5, wherein the average particle size of the aggregate of silica fine particles is 100 nm to 1 μm. The laminate according to claim 3, 4, 5, or 6, wherein the binder resin is mainly composed of a polyfunctional acrylate monomer having no hydroxyl group in the molecule. The organic fine particles are fine particles made of at least one material selected from the group consisting of acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyethylene resin, epoxy resin, silicone resin, polyvinylidene fluoride resin and polyvinyl fluoride resin. The laminate according to claim 3, 4, 5, 6, or 7. The laminate according to claim 3, 4, 5, 6, 7 or 8, wherein the organic fine particles are not subjected to a surface hydrophilization treatment. A polarizing plate comprising a polarizing element,
The polarizing plate comprises the laminate according to claim 2, 3, 4, 5, 6, 7, 8, or 9 on the surface of a polarizing element. An image display device comprising the laminate according to claim 2, 3, 4, 5, 6, 7, 8 or 9 or the polarizing plate according to claim 10 on the outermost surface.