JP2008032845A - Optical laminate, its manufacturing method, polarizing plate and image display apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical laminate which can simultaneously obtain two properties, black reproducibility such as glazed black feeling and antiglare property. <P>SOLUTION: The optical laminate having a rugged surface comprises an antiglare layer 12 which is provided on a light translucent base material 11 and which has rugged surface and a surface regulating layer 13 which is provided on the antiglare layer and which contains a resin binder and a fluidity regulating agent 14. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to an optical laminate, a method for producing the same, a polarizing plate, and an image display device.

In an image display device such as a cathode ray tube display device (CRT), a liquid crystal display (LCD), a plasma display (PDP), and an electroluminescence display (ELD), an optical laminate for preventing reflection is generally provided on the outermost surface. ing. Such an anti-reflection optical laminate suppresses image reflection or reduces reflectance by scattering or interference of light.

As one of such an antireflection optical laminate, an antiglare laminate in which an antiglare layer having an uneven shape is formed on the surface of a transparent substrate is known. Such an antiglare laminate can prevent external light from being scattered due to the uneven shape of the surface and prevent deterioration of visibility due to reflection of external light or image reflection. As an anti-glare laminated body, what formed the unevenness | corrugation with the particle | grains (patent document 1), and what made the uneven | corrugated shape by giving an emboss shaping process are known (patent document 2, 3).

However, with such a conventional antiglare laminate, it has been difficult to satisfy both the properties of “antiglare” and “contrast improvement”. For this reason, these anti-glare laminates may be inferior in black reproducibility, contrast, and the like including glossy blackness (glossy black as wet) in screen display. In other words, the black gradation expression in the bright room, especially in the low gradation, it is difficult to recognize the difference in black gradation, and the sensitivity may be low. Specifically, in black and gray color recognition, only blurring and black of the same color tone may be recognized. In particular, as the antiglare laminate having a good antiglare property (= scattering of external light), the visibility was remarkably lowered.

That is, in the antireflection laminate, it is an object to simultaneously obtain both properties of “antiglare” for achieving good visibility while realizing “contrast improvement”. There is a need to improve these problems and to obtain good properties in both luster and antiglare properties.

Patent Document 4 describes that a low refractive index layer is formed on a light diffusion layer having a concavo-convex structure, and also describes that colloidal silica is added to the low refractive index layer. However, it is not described that the surface adjustment layer is formed for the purpose of controlling the uneven structure.

JP-A-6-18706 Japanese Patent Laid-Open No. 6-16851 JP 2004-341070 A JP 2003-75605 A

The present invention has been made in view of the above-described situation, and an object of the present invention is to provide an optical laminate that can simultaneously obtain a plurality of properties such as black reproducibility such as glossiness and anti-glare properties.

The present invention relates to an optical laminate having irregularities on the surface, the antiglare layer having irregularities on the surface provided on the light-transmitting substrate, and the surface adjustment layer provided on the antiglare layer. And the surface adjustment layer is an optical laminate characterized by containing a resin binder and a fluidity control agent such as organic fine particles or inorganic fine particles.
The surface adjustment layer preferably has a thickness of 0.6 μm to 15 μm.
The surface adjustment layer preferably has a refractive index of 1.51 to 1.82.
The resin binder is preferably an ionizing radiation curable resin.
The oxide fine particles are preferably colloidal silica.
The optical layered body preferably further has a low refractive index layer on the surface adjustment layer.

This invention is a polarizing plate provided with a polarizing element, Comprising: The said polarizing plate is also a polarizing plate characterized by providing the optical laminated body mentioned above on the polarizing element surface.
The present invention is also a non-self-luminous image display device comprising the optical laminate or the polarizing plate on the outermost surface.
The present invention also provides a self-luminous image display device comprising the optical layered body on the outermost surface.

The present invention provides a fluidity modifier such as a resin binder and colloidal silica on the antiglare layer obtained by the step (1) and the antiglare layer obtained by the above step (1). It is also a method for producing the optical layered body, which comprises a step of forming a surface adjustment layer with the surface adjustment layer forming composition contained.
Hereinafter, the present invention will be described in detail.

The surface adjustment layer in the optical layered body of the present invention is a layer provided on the antiglare layer having irregularities on the surface, and the surface adjustment layer having a specific composition allows black reproducibility such as glossiness and antiglare. It is possible to obtain properties such as sex at the same time.

In the present invention, the surface conditioning layer formed for such purpose contains a fluidity modifier such as organic fine particles and inorganic fine particles and a binder resin, and a surface conditioning layer containing the fluidity modifier and the binder resin. It can form by apply | coating the composition for formation on a glare-proof layer, and producing a curing reaction as needed.

The glossiness of the image display device is the black reproducibility when the image display device is displayed in black in a bright room environment, and can be evaluated by visual observation. When the reflection angle of light incident on the optical laminate from outside is reflected over a wide range, the light reflects in all directions (diffuse reflection) according to the concave / convex angle of the optical laminate surface, and the observer's eyes Therefore, the original black color is not reproduced. (That is, only a part of the diffused light reaches the observer's eyes.) On the other hand, when the incident light is concentrated and reflected in the vicinity of the regular reflection angle (in the case of an antiglare layer having a gentle uneven shape), the light from the light source is hardly diffusely reflected and becomes regular reflected light. Since this specularly reflected light does not reach the observer's eyes, the original wet black color is reproduced. In the present specification, this original black color is described as glossy blackness.

Conventionally, in order to obtain a glossy blackness based on the above-described action, if an attempt is made to smooth the surface by forming fine surface irregularities by forming a surface adjustment layer, excessive smoothing has been applied. As a result, the glossy black feeling is excellent, but the performance of anti-glare property is remarkably lowered. However, when the film is formed with the composition containing the organic fine particles or the inorganic fine particles, both black reproducibility such as glossiness and antiglare performance can be achieved. The effect of obtaining such an effect is not clear, but the composition containing various fluidity modifiers as described above is capable of following the uneven shape of the surface by controlling the fluidity. In smoothing, it is possible to leave the convex shape without being completely crushed while giving moderate smoothness to the fine concavo-convex shape in the underlying concavo-convex layer that is completely crushed by the conventional surface adjustment layer. Presumed to be possible. As a result, the convex part which exists in the same area increases, and it is thought that anti-glare property can be improved without losing glossy blackness.

The shape of the organic fine particles or inorganic fine particles that can be used as the fluidity adjusting agent is not particularly limited, and may be any shape such as a spherical shape, a plate shape, a fiber shape, an amorphous shape, and a hollow shape.

As the organic fine particles, hard fine particles having an appropriate cross-linked structure inside the particles and less swelled by an active energy ray curable resin, a monomer, a solvent, or the like can be used. For example, styrene resin, styrene-acrylic copolymer resin, styrene-acrylic copolymer resin, acrylic resin, divinylbenzene resin, silicone resin, urethane resin, melamine resin, styrene-isoprene resin, benzoguanamine resin, etc. You can use what you want.

The type of the inorganic fine particles is not particularly limited, and examples thereof include silica, alkali metal oxide, alkaline earth oxide, titanium oxide, zinc oxide, aluminum oxide, boron oxide, tin oxide, Phosphorus oxide, indium tin oxide, zirconium oxide, metal, metal nitride, carbon isotope, fine silicate, calcium silicate, aluminum silicate, calcium carbonate, magnesium carbonate, fine talc, titanium oxide, diatomaceous earth, smectite, kaolin clay Etc. Specific examples of preferable metals include Al, Ni, Cu, Si, Sn, Au, and Ag. Specific examples of preferable metal nitrides include TiC, SiC, AlC, WC, and BC. Specific examples of preferable carbon isotopes. , Diamond, graphite, and carbon.

The inorganic fine particles may be conductive metal oxide fine particles. The conductive metal oxide fine particles are not particularly limited. For example, ZnO (refractive index 1.90, hereinafter, all values in parentheses indicate refractive index), Sb ₂ O ₂ (1.71). ), SnO ₂ (1.997), CeO ₂ (1.95), indium tin oxide (abbreviated as ITO; 1.95), In ₂ O ₃ (2.00), Al ₂ O ₃ (1.63), Antimony-doped tin oxide (abbreviation ATO; 2.0), aluminum-doped zinc oxide (abbreviation AZO; 2.0), and the like can be given. Two or more organic fine particles or inorganic fine particles may be used at the same time.

The organic fine particles or inorganic fine particles may have a core / shell structure. In this case, the shell portion may have a polymerizable functional group introduced on the surface. The shell portion has a structure in which a polymerizable functional group is directly or has a polymerizable functional group, a monomer, an oligomer, or a polymer in a graft form and bonded to the core by a chemical reaction; the polymerizable functional group on the surface of the particle portion (core) And a structure in which a monomer, an oligomer, and a polymer having a hydrogen atom are combined in a film form by a chemical reaction.

The particle part (core) of the ultrafine particles having the core / shell structure may be either an organic or inorganic component, and the shell part may be either an organic or inorganic component. Examples of ultrafine particles having a core / shell structure include those composed entirely of organic components (such as polymer latex), those composed entirely of inorganic components, and those composed entirely of organic-inorganic composite components. Furthermore, the graft fine particles in which one of the particle part (core) and the part having a polymerizable functional group attached to the surface (graft part or shell part) is an organic material and the other is an inorganic material; Core / shell particulates are also included.

When the core / shell fine particles having a polymerizable functional group on the surface thereof are used, a coating composition using a resin binder having a functional group (described later) is prepared, and the coating composition has the unevenness. It is preferable to apply and cure on the surface of the antiglare layer. As a result, the polymerizable functional group on the surface of the fine particles and the polymerizable functional group of the binder component react when the coating is cured, and a covalent bond is formed between the binder component and the core / shell fine particles. It is preferable in that the effect of improving the property is large and the effect of following the surface uneven shape is large. It is preferable to use a polyfunctional binder component having two or more polymerizable functional groups in one molecule as the resin binder because a crosslink can be formed. In particular, by adding a relatively small amount of a polyfunctional monomer or oligomer to the ultrafine particles having a polymerizable functional group, the binding force can be greatly improved at the contact point between the ultrafine particles, resulting in a surface uneven shape. This is very preferable because the following ability can be further improved.

As the organic fine particles or inorganic fine particles, those having a primary particle diameter in the range of 1 nm to 500 nm (number average particle diameter) are preferably used. If the primary particle diameter is less than 1 nm, it is difficult to impart sufficient hardness and strength to the coating film. On the other hand, if the primary particle diameter exceeds 500 nm, the transparency of the coating film is impaired and cannot be applied depending on the application. It may become. The particle diameters of the fine particles may be uniform or may have a distribution. Moreover, if it is a range which does not reduce the intensity | strength of a coating film, 2 or more types of microparticles | fine-particles from which a particle diameter differs can be mixed and used. The primary particle diameter of the fine particles may be visually measured from a secondary electron emission image photograph obtained by a scanning electron microscope (SEM) or the like, or a particle size using a dynamic light scattering method, a static light scattering method, or the like. Mechanical measurement may be performed by a distribution meter or the like.
The average particle diameter of the conductive metal oxide fine particles can be measured by a dynamic light scattering method or the like.

Among the above fine particles, colloidal silica, ATO, zirconia ultrafine particles, ultrafine antimony oxide and the like are preferable in the present invention, and colloidal silica is particularly preferable. The preferable size is about 1 to 70 nm.

In the present invention, “colloidal silica” means a colloidal solution in which colloidal silica particles are dispersed in water or an organic solvent. The particle size (diameter) of the colloidal silica is preferably that of ultrafine particles of 1 to 70 nm, for example. The particle diameter of the colloidal silica in the present invention is an average particle diameter according to the BET method (a surface area is measured by the BET method, and the average particle diameter is calculated by converting the particles to be true spheres).

The colloidal silica is a known one, and commercially available ones include, for example, “methanol silica sol”, “MA-ST-M”, “IPA-ST”, “EG-ST”, “EG-ST-ZL”. ”,“ NPC-ST ”,“ DMAC-ST ”,“ MEK ”,“ XBA-ST ”,“ MIBK-ST ”(all products of Nissan Chemical Industries, Ltd., all trade names),“ OSCAL1132, ” “OSCAL1232”, “OSCAL1332”, “OSCAL1432”, “OSCAL1532”, “OSCAL1632”, “OSCAL1132” (the above are products of Catalytic Chemical Industry Co., Ltd., all trade names) may be mentioned. it can.

The organic fine particles or inorganic fine particles are preferably contained in a fine particle mass of 5 to 300 with respect to the binder resin mass 100 of the surface adjustment layer (fine particle mass / binder resin mass = P / V ratio = 5 to 300 / 100). If it is less than 5, the followability to the uneven shape becomes insufficient, and it may be difficult to achieve both black reproducibility such as glossiness and antiglare property. If it exceeds 300, defects occur in physical properties such as adhesion and scratch resistance, so this range is preferable. The addition amount varies depending on the fine particles to be added, but in the case of colloidal silica, the addition amount is preferably 5 to 80. If it exceeds 80, it becomes a region where the antiglare property does not change even if it is added more, so the meaning of adding is lost, and if it exceeds this, poor adhesion with the lower layer occurs, so it should be within this range Is good.

The surface adjustment layer contains a resin binder. Although it does not specifically limit as said resin binder, A transparent thing is preferable, for example, ionizing radiation curable resin which is resin hardened | cured with an ultraviolet-ray or an electron beam, ionizing radiation curable resin, and solvent dry resin (thermoplastic resin etc.) And a resin obtained by curing a thermosetting resin, etc., by simply drying a solvent for adjusting the solid content during coating. More preferred is an ionizing radiation curable resin. In the present specification, “resin” is a concept including resin components such as monomers and oligomers.

Examples of the ionizing radiation curable resin include compounds having one or more unsaturated bonds such as compounds having an acrylate functional group. 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 polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri ( Reaction products such as (meth) allyllate and polyfunctional compounds such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate And poly (meth) acrylate esters of polyhydric alcohols). In the present specification, “(meth) acrylate” refers to methacrylate and acrylate.

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.

When the ionizing radiation curable resin is used as an ultraviolet curable resin, it is preferable to add a photopolymerization initiator or a photopolymerization accelerator to the surface adjustment layer forming composition. As the photopolymerization initiator, in the case of a resin system having a radical polymerizable unsaturated group, 1-hydroxy-cyclohexyl-phenyl marketed as acetophenones (for example, trade name Irgacure 184 (manufactured by Ciba Specialty Chemicals)) -Ketone), benzophenones, thioxanthones, benzoin, benzoin methyl ether and the like can be used alone or in combination. In the case of a resin system having a cationic polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, a benzoin sulfonic acid ester or the like is used alone or as a mixture as a photopolymerization initiator. be able to. The addition amount of the photopolymerization initiator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

The ionizing radiation curable resin can be used in combination with a solvent-drying resin. The solvent-drying resin that can be used in combination with the above-mentioned shadow radiation curable resin is not particularly limited, and generally, a thermoplastic resin can be used. By using the solvent-drying resin in combination, it is possible to effectively prevent coating defects on the coated surface, thereby obtaining a more excellent glossy blackness. 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.

When the material of the light-transmitting substrate is a cellulose resin such as TAC, the thermoplastic resin is preferably a cellulose resin such as nitrocellulose, acetyl cellulose, cellulose acetate propionate, ethyl hydroxyethyl cellulose, and the like.

Thermosetting resins that can be used as the binder resin include phenol resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine-urea cocondensation resin. , Silicon resin, polysiloxane resin, and the like. When a thermosetting resin is used, a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, and the like can be used in combination as necessary.

The film thickness (when cured) of the surface adjustment layer is preferably 0.6 μm or more and 15 μm or less (preferably 12 μm or less), more preferably the lower limit is 3 μm or more and the upper limit is 8 μm or less. In addition, after measuring the thickness A of the antiglare layer by a method described later, the thickness of the surface adjustment layer is measured by measuring the thickness B of the antiglare layer + the surface adjustment layer obtained by laminating the surface adjustment layer. It is a value calculated by subtracting the value. (If there is a difference in refractive index between the antiglare layer and the binder resin of the surface adjustment layer, it can be calculated by measuring A after measuring B of the finished product.) If it is less than 0.6 μm, the antiglare property is good, but the glossy blackness may not be improved. When the film thickness exceeds 15 μm, the glossy black feeling is very excellent, but there may be a problem that the antiglare property is not improved.

In the optical layered body of the present invention, the surface adjustment layer preferably has a refractive index of 1.49 to 1.86. That is, in the present invention, it is preferable that the surface adjustment layer has a hard property. However, when the refractive index is preferably about 1.38 to 1.46 for exhibiting the function as the low refractive index layer and the film thickness is in the above range, the low refractive index material can be any method ( For example, in the case of resin material alone, when inorganic / organic or organic-inorganic hybrid fine particles are added to the resin material, even when it is based on inorganic vapor deposition), it does not have enough hardness to be used on the outermost surface of the display. That is, a film having a low refractive index is soft and easily damaged, or is hard but brittle. In order to obtain the hard property by the surface adjustment layer having a low refractive index, the film thickness of the low refractive index layer needs to be extremely thin (for example, 0.1 to 0.5 μm). However, when the film thickness is about 0.1 to 0.5 μm, it is difficult to obtain the desired glossy blackness in the present invention. Therefore, a layer having a refractive index in the above range is preferable. The refractive index is more preferably an upper limit of 1.76, and more preferably a lower limit of 1.51.

The refractive index of the said surface adjustment layer can be made into the thing within a desired range by selecting the following preferable materials as the organic fine particle or inorganic fine particle to be used, and binder resin. For example, as the organic fine particles, in addition to the organic fine particles such as acrylic resin fine particles (1.50 to 1.53) and acrylic-styrene copolymer resin fine particles (1.54 to 1.60), the core / shell structure is used. Inorganic fine particles include colloidal silica (refractive index of 1.45 to 1.50), zirconia (2.19 to 2.40), ATO (2.0), ZnO ( 1.9), alumina (1.63), titania (2.52-2.76), antimony oxide (2.09) and the like can be used.

Examples of the resin binder that can be suitably used for obtaining the surface conditioning layer include compounds having a trifunctional or higher functional unsaturated bond in the above-described binder resin. Also, a compound having a high refractive index containing a bromine atom, a sulfur atom and a fluorene skeleton and having one or more unsaturated bonds may be used together with a compound having the above trifunctional or more unsaturated bonds, or alone. Can do.

Further, the difference between the refractive index of the surface adjustment layer and the refractive index of the resin binder forming the antiglare layer (the difference obtained by subtracting the refractive index of the resin binder forming the antiglare layer from the refractive index of the surface adjustment layer) is 0. It is preferably ˜0.25, and when the low refractive index layer is provided on the surface adjustment layer, it is preferably 0.1 to 0.25, and when the low refractive index layer is not provided, It is preferably 0 to less than 0.1. When the surface adjustment layer becomes the outermost surface without providing a low refractive index layer, if the difference in refractive index from the antiglare layer becomes too large, reflection at the interface between the antiglare layer and the surface adjustment layer occurs. Interference fringes are generated in the surface layer, causing a decrease in visibility, and if the outermost surface layer has a high refractive index, the reflectance is increased at the air layer interface, which is also preferable in that the visibility also decreases. Instead, the effects of the present invention may be impaired. The difference in refractive index between the binder of the antiglare layer and the surface adjustment layer is more preferably an upper limit of 0.1 and more preferably a lower limit of 0 when the surface adjustment layer is the outermost surface. The refractive index difference when the refractive index of the surface adjustment layer is subtracted from the refractive index of the resin binder forming the antiglare layer is more preferably 0 to 0.05.

In addition to the functions described above, the surface adjustment layer may have a function of imparting antistatic properties, refractive index adjustment, high hardness, antifouling properties, and the like. In this case, the said surface adjustment layer can be formed with the composition for surface adjustment layer formation containing another additive as needed.

The antistatic agent is not particularly limited, and examples thereof include cationic compounds such as quaternary ammonium salts, pyridinium salts, and primary to tertiary amino groups; sulfonate groups, sulfate ester bases, phosphate ester bases, and phosphonic acids. Anionic compounds such as bases; amphoteric compounds such as amino acids and aminosulfate esters; nonionic compounds such as amino alcohols, glycerin and polyethylene glycol; organometallic compounds such as tin and titanium alkoxides; Examples thereof include metal chelate compounds such as acetylacetonate salts of compounds. Compounds obtained by increasing the molecular weight of the compounds listed above can also be used. Also, polymerizability of organometallic compounds such as coupling agents having a tertiary amino group, a quaternary ammonium group or a metal chelate moiety and having a monomer, oligomer or functional group that can be polymerized by ionizing radiation. Compounds can also be used as antistatic agents.

Examples of the antistatic agent include conductive polymers. The conductive polymer is not particularly limited. For example, aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, heteroatom-containing polyaniline, mixed type Conjugated poly (phenylene vinylene), a double chain conjugated system that has a plurality of conjugated chains in the molecule, and a conductive polymer that is a polymer obtained by grafting or block-copolymerizing the conjugated polymer chain to a saturated polymer. And the like.

The antistatic agent is preferably added in an amount of 7 to 150% by mass based on the amount of the binder resin (excluding the solvent). More preferably, the upper limit of the addition amount is 100 or less, and the lower limit is 5 or more. By adjusting the addition amount within the above numerical range, it is possible to maintain the transparency as an optical laminate, and to impart antistatic performance without adversely affecting properties such as glossiness and antiglare properties. Is preferable.

Although the formation method of the said surface adjustment layer is not specifically limited, For example, the surface obtained by mixing said organic fine particle or inorganic fine particle, binder resin (including resin components, such as a monomer and an oligomer), a solvent, and arbitrary components It can form by apply | coating the composition for adjustment layer formation on a glare-proof layer. Solvents include alcohols such as isopropyl alcohol, methanol and ethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as methyl acetate, ethyl acetate and butyl acetate; halogenated hydrocarbons; toluene, xylene and the like Aromatic hydrocarbons; or a mixture thereof, preferably ketones and esters.

The composition for forming a surface adjustment layer may further contain a leveling agent such as fluorine or silicone. The composition for forming a surface adjustment layer to which a leveling agent is added has a function of improving the coated surface and imparting an effect of scratch resistance.

The composition for forming a surface adjustment layer can be applied by a known coating method such as a Miya bar coating method, a roll coating method, or a gravure coating method. After application of the composition for forming a surface adjustment layer, drying and curing are performed as necessary. In the formation of the surface adjustment layer, it is preferable to use an ultraviolet curable resin as the resin binder and perform curing with ultraviolet rays. When curing by ultraviolet rays, it is preferable to use ultraviolet rays having a wavelength range of 190 to 380 nm. Curing with ultraviolet rays can be performed, for example, with a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or the like. 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 insulating core transformer type, a linear type, a dynamitron type, and a high frequency type.

The antiglare layer of the optical layered body of the present invention is a layer provided on the surface of the light-transmitting substrate and has irregularities on the surface. The method for forming the unevenness is not particularly limited, and a known method can be used. The total thickness of the two layers of the antiglare layer and the surface conditioning layer and other layers provided as necessary is preferably 0.5 μm or more and 27 μm or less (preferably 20 μm or less), more preferably the lower limit. 1 μm, and the upper limit is 23 μm (more preferably 15 μm). The total thickness of the antiglare layer and the surface conditioning layer and the other layers provided as necessary is the antiglare uneven outermost surface in contact with air from the interface between the base material and the first layer laminated thereon. Thickness up to. From the substrate interface to the outermost surface, not only the anti-glare layer and the surface adjustment layer, but also other optical functional layers may be laminated to form a multilayer. The thickness can be measured by the following method.

(Layer thickness: Total thickness measurement method)
Using a confocal laser microscope (LeicaTCS-NT: manufactured by Leica Co., Ltd .: magnification “500 to 1000 times”), the cross section of the optical laminate was observed through transmission, the presence or absence of an interface was judged, and the following evaluation criteria were used. Specifically, in order to obtain a clear image without halation, a wet objective lens is used for the confocal laser microscope, and about 2 ml of oil having a refractive index of 1.518 is placed on the optical laminate. Judged. The use of oil was used to eliminate the air layer between the objective lens and the optical stack. For each screen obtained by measurement, measure the film thickness from the maximum convex part of the unevenness on the outermost surface and the base material of the minimum concave part, one point at a time, and measure it for five screens, a total of 10 points, the average value Was calculated. The film thickness of the surface adjustment layer was measured at two points for each film thickness from the base material of the maximum and minimum protrusions of the anti-glare layer per screen, for a total of 10 points for 5 screens. It can be determined by measuring, calculating the average value, and subtracting from the total layer thickness previously determined.
The laser microscope can observe a non-destructive cross section when there is a difference in refractive index between layers. Therefore, if the difference in refractive index is unclear or the difference is close to 0, the thickness of the antiglare layer and the surface adjustment layer is SEM and TEM cross-sectional photographs in which the layer can be observed by the difference in composition of each layer The same can be obtained by observation.

The method for forming the antiglare layer is not particularly limited. For example, a method for forming an antiglare layer having an uneven shape using a composition for forming an antiglare layer containing a resin and fine particles (Method 1); A method of forming an antiglare layer having an uneven shape using a composition for forming an antiglare layer containing only a resin or the like (Method 2); a process of embossing the uneven shape using any shaping material The method (method 3) etc. which form an anti-glare layer using can be mentioned. Hereinafter, these methods 1 to 3 will be described in detail.

(Method 1) Method of forming an antiglare layer having a concavo-convex shape using a composition for forming an antiglare layer containing a resin and fine particles The fine particles used in the above method (1) are spherical, For example, it may be a true sphere or an ellipse, and more preferably a true sphere. The average particle diameter R (μm) of the fine particles is preferably 1.0 μm or more and 20 μm or less, more preferably an upper limit of 15.0 μm and a lower limit of 3.5 μm. The average particle diameter (R) of the fine particles is a value measured by a laser diffraction method, a Coulter method (electric resistance method), or the like. The fine particles may be aggregated particles. In the case of aggregated particles, the secondary particle diameter is preferably within the above range.

In the fine particles, 80% or more (preferably 90% or more) of the whole fine particles are preferably in the range of R ± 1.0 (preferably 0.3) μm. Thereby, the uniformity of the uneven shape of the antiglare laminate can be improved.

The fine particles are not particularly limited, and inorganic and organic particles can be used. Preferably, the particles are transparent. Specific examples of the fine particles formed of an organic material include plastic beads. Plastic beads include styrene beads (refractive index 1.60), melamine beads (refractive index 1.57), acrylic beads (refractive index 1.50 to 1.53), acrylic-styrene beads (refractive index 1.54 to 1.58), benzoguanamine beads, polycarbonate beads, polyethylene beads, and the like. The plastic beads preferably have a hydrophobic group on the surface, and examples thereof include styrene beads. Examples of the inorganic fine particles include amorphous silica.

The amorphous silica has a particle size of 0. It is preferred to use 5-5 μm silica beads. It is preferable that content of the said amorphous silica is 1-30 mass parts with respect to binder resin. In order to improve the dispersibility of the amorphous silica without causing an increase in the viscosity of the composition for forming an antiglare layer, which will be described in detail below, the average particle diameter and the addition amount are changed, and the particle surface is changed. The presence or absence of organic matter treatment can be changed and used. When the organic substance treatment is performed on the particle surface, a hydrophobic treatment is preferable.

The organic matter treatment includes a method of chemically bonding a compound to the bead surface and a physical method of penetrating into a void in a composition forming the bead without chemically bonding to the bead surface. Yes, you can use either one. In general, a chemical treatment method using an active group on a silica surface such as a hydroxyl group or a silanol group is preferably used from the viewpoint of treatment efficiency. As the compound used for the treatment, a silane-based, siloxane-based, or silazane-based material having high reactivity with the above-described active group is used. For example, linear alkyl single group substituted silicone materials such as methyltrichlorosilane, branched alkyl monosubstituted silicone materials, or polysubstituted linear alkyl silicone compounds such as di-n-butyldichlorosilane and ethyldimethylchlorosilane, and polysubstituted branched A chain alkyl silicone compound. Similarly, mono-substituted, poly-substituted siloxane materials and silazane materials having a linear alkyl group or a branched alkyl group can also be used effectively.

Depending on the required function, those having a hetero atom, an unsaturated bond group, a cyclic bond group, an aromatic functional group or the like may be used at the terminal or intermediate part of the alkyl chain. In these compounds, the alkyl group contained is hydrophobic, so that the surface of the material to be treated can be easily converted from hydrophilic to hydrophobic, and both the high-molecular material with poor affinity when untreated is high. Affinity can be obtained.

In addition to the fine particles, a plurality of types of fine particles such as second fine particles and third fine particles having different average particle diameters may be included. More preferably, the fine particles further include first fine particles having the particle size and second fine particles having an average particle size different from the first fine particles. The second fine particles and the third fine particles may be fine particles composed of components different from the first fine particles.

In the present invention, when the average particle diameter of the fine particles is R (μm) and the average particle diameter of the second fine particles is r (μm), the following formula (I):
0.25R (preferably 0.50) ≦ r ≦ 1.0R (preferably 0.70) (I)
Those satisfying these conditions are preferred.
When r is 0.25R or more, the dispersion of the coating liquid is facilitated and the particles are not aggregated. Moreover, a uniform uneven | corrugated shape can be formed, without receiving to the influence of the wind at the time of floating in the drying process after application | coating.

According to another aspect of the present invention, the total mass ratio per unit area of the resin, the (first) fine particles, and the second fine particles is (M). _{1. When} the total mass per unit area of the second fine particles is M ₂ and the total mass per unit area of the resin is M, the following formulas (II) and (III):
0.08 ≦ (M ₁ + M ₂ ) /M≦0.36 (II)
0 ≦ M ₂ ≦ 4.0M ₁ (III)
Those satisfying these conditions are preferred.

The second fine particles are not particularly limited, and inorganic and organic particles similar to the first fine particles can be used. The content of the second fine particles is preferably 3 to 100% by mass with respect to the content of the first fine particles. The third fine particles may have the same blending amount as the second fine particles.

The antiglare layer can be formed of a composition for forming an antiglare layer containing the fine particles and a curable resin. The curable resin is preferably transparent, for example, an ionizing radiation curable resin that is a resin curable by ultraviolet rays or an electron beam, a mixture of an ionizing radiation curable resin and a solvent-drying resin, or a thermosetting resin. Can be mentioned. More preferred is an ionizing radiation curable resin. As these resins, the resins exemplified as the resins that can be used as the resin binder in the surface adjustment layer can be used.

The antiglare layer comprises fine particles and a resin in a suitable solvent, for example, alcohols such as isopropyl alcohol, methanol, and ethanol; ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone; methyl acetate, acetic acid Esters such as ethyl and butyl acetate; halogenated hydrocarbons; aromatic hydrocarbons such as toluene and xylene; or a composition for forming an antiglare layer obtained by mixing them with a mixture thereof is applied to a light-transmitting substrate. Can be formed.

According to a preferred embodiment of the present invention, it is preferable to add a leveling agent such as fluorine or silicone to the composition for forming an antiglare layer. The composition for forming an antiglare layer to which a leveling agent is added can improve the coating suitability and can impart the effect of scratch resistance. The leveling agent is preferably used for a film-like light-transmitting substrate (for example, triacetyl cellulose or polyethylene terephthalate) that requires heat resistance.

Examples of the method for applying the antiglare layer forming composition to the light-transmitting substrate include application methods such as a roll coating method, a Miya bar coating method, and a gravure coating method. After application of the composition for forming an antiglare layer, drying and ultraviolet curing are performed as necessary. Specific examples of the ultraviolet light source include ultrahigh pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black light fluorescent lamps, and metal halide lamp lamps. As an ultraviolet wavelength, a wavelength range of 190 to 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. The resin is cured, fine particles in the resin are fixed, and a desired uneven shape is formed on the outermost surface of the antiglare layer.

(Method 2) A method for forming an antiglare layer having a concavo-convex shape using a composition for forming an antiglare layer containing only a polymer and the like without adding fine particles . In this method, at least two components from the group consisting of a resin precursor are combined, and a composition for forming an antiglare layer mixed with an appropriate solvent is applied to a light-transmitting substrate.

The concavo-convex shape by the method 2 is, for example, an antiglare layer composition containing at least two components from the group consisting of a polymer and a curable resin precursor (hereinafter referred to as a “phase-separated antiglare layer composition”). It can be formed using In such a method, by using a composition for phase-separation type antiglare layer in which at least two components from a group consisting of a polymer and a curable resin precursor are mixed together with an appropriate solvent, A film having a phase separation structure can be formed by spinodal decomposition.

The phase-separation-type antiglare layer composition is at least two kinds from the group consisting of a polymer and a curable resin precursor in the process of evaporating or removing the solvent by drying or the like after coating on the light-transmitting substrate. A phase separation due to spinodal decomposition occurs between the components, and a phase separation structure having a relatively regular interphase distance can be formed.

The spinodal decomposition forms a co-continuous phase structure with the progress of phase separation that occurs as the solvent is removed, and when the phase separation further proceeds, the continuous phase becomes discontinuous by its surface tension, and the droplet phase structure ( Independent phase sea-island structure such as spherical, true spherical, disk-like or ellipsoidal. Therefore, an intermediate structure between the co-continuous phase structure and the droplet phase structure (phase structure in the process of transition from the co-continuous phase to the droplet phase) can be formed depending on the degree of phase separation. In the above method 2, the sea-island structure (droplet phase structure or phase structure in which one phase is independent or isolated), bicontinuous phase structure (or network structure), or bicontinuous phase structure by spinodal decomposition is used. Due to the intermediate structure mixed with the droplet phase structure, fine unevenness is formed on the surface of the antiglare layer after the solvent is dried.

In such spinodal decomposition accompanied by evaporation of the solvent, since the average distance between the domains of the phase separation structure has regularity or periodicity, the uneven shape finally formed also has regularity or periodicity. It is preferable in that it can be made. The phase separation structure formed by spinodal decomposition can be fixed by curing a curable functional group or a curable resin precursor in the polymer. Curing of the curable functional group or the curable resin precursor can be performed by heating, light irradiation, or a combination of these methods depending on the type of the curable resin precursor. The heating temperature is not particularly limited as long as it is a condition that can maintain the phase separation structure formed by the spinodal decomposition, and is preferably 50 to 150 ° C., for example. Curing by light irradiation can be performed by the same method as that for the surface adjustment layer. In the composition for layer separation type | mold glare-proof layer which has photocurability, it is preferable to contain a photoinitiator. The curable component may be a polymer having a curable functional group or a curable resin precursor.

It is preferable to use at least two components from the group consisting of the polymer and the curable resin precursor by selecting a combination that undergoes phase separation by spinodal decomposition in a liquid phase. Examples of combinations for phase separation include (a) a combination in which a plurality of polymers are incompatible with each other, (b) a combination in which a polymer and a curable resin precursor are incompatible and phase separated, (c ) A combination in which a plurality of curable resin precursors are incompatible with each other and phase-separated. Among these combinations, (a) a combination of a plurality of polymers and (b) a combination of a polymer and a curable resin precursor are preferable, and (a) a combination of a plurality of polymers is particularly preferable.

In the phase separation structure, a droplet phase structure having at least island-like domains is advantageous from the viewpoint that irregularities are formed on the surface of the antiglare layer and the surface hardness is increased. When the phase separation structure composed of the polymer and the curable resin precursor is a sea-island structure, the polymer component may form a sea phase, but from the viewpoint of surface hardness, the polymer component is an island-like domain. Is preferably formed. Due to the formation of island-like domains, an uneven shape exhibiting desired optical characteristics is formed on the surface of the antiglare layer after drying.

The average distance between the domains of the phase separation structure usually has regularity or periodicity, and corresponds to the surface roughness Sm. The average interphase distance between domains is, for example, about 10 to 500 μm (for example, 10 to 400 μm), preferably 20 to 350 μm (for example, 20 to 300 μm), and more preferably about 30 to 250 μm (for example, 30 to 200 μm). Also good. The average distance between the domains of the phase separation structure can be adjusted by selecting a combination of resins (particularly, selecting a resin based on solubility parameters). By adjusting the average distance between the domains in this way, the distance between the irregularities on the finally obtained film surface can be set to a desired value.

Examples of the polymer include cellulose derivatives (for example, cellulose esters, cellulose carbamates, cellulose ethers), styrene resins, (meth) acrylic resins, organic acid vinyl ester resins, vinyl ether resins, halogen-containing resins, and olefins. Resins (including alicyclic olefin resins), polyester resins, polyamide resins, polycarbonate resins, thermoplastic polyurethane resins, polysulfone resins (for example, polyethersulfone, polysulfone), polyphenylene ether resins (for example, 2,6-xylenol polymer), silicone resin (for example, polydimethylsiloxane, polymethylphenylsiloxane), rubber or elastomer (for example, diene rubber such as polybutadiene and polyisoprene, styrene) - butadiene copolymer, acrylonitrile - butadiene copolymer, acrylic rubber, urethane rubber, silicone rubber) and the like, can be used in combination of these alone or two or more. Among the plurality of polymers, at least one polymer may have a functional group involved in the curing reaction of the curable resin precursor, for example, a polymerizable group such as a (meth) acryloyl group. The polymer component may be thermosetting or thermoplastic, but is more preferably a thermoplastic resin.

The polymer is preferably non-crystalline and soluble in an organic solvent (particularly a common solvent capable of dissolving a plurality of polymers and curable compounds). In particular, resins with high moldability or film formability, transparency and weather resistance, such as styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (cellulose esters, etc.) Etc. are preferred.

Among the cellulose derivatives, specific examples of cellulose esters include, for example, aliphatic organic acid esters such as cellulose acetates such as cellulose diacetate and cellulose triacetate; cellulose propionate, cellulose butyrate, and cellulose acetate propionate. C _1-6 organic acid esters such as cellulose acetate butyrate; Aromatic organic acid esters such as C _7-12 aromatic carboxylic acid esters such as cellulose phthalate and cellulose benzoate; Inorganic acid esters such as cellulose phosphate and cellulose sulfate Mixed acid esters such as acetic acid and cellulose nitrate ester; cellulose carbamates such as cellulose phenyl carbamate; cellulose ethers such as cyanoethyl cellulose; hydroxyethyl cellulose; Methylcellulose, C _1-6 alkyl cellulose such as ethyl cellulose; mud propyl hydroxy C _2-4 alkyl cellulose such as cellulose carboxymethyl cellulose or a salt thereof, benzyl cellulose, acetyl alkyl cellulose.

Examples of the styrene resin include styrene monomers alone or copolymers (for example, polystyrene, styrene-α-methylstyrene copolymer, styrene-vinyltoluene copolymer), styrene monomers and other copolymers. Copolymers with polymerizable monomers [for example, (meth) acrylic monomers, maleic anhydride, maleimide monomers, dienes] and the like are included. Examples of the styrene-based copolymer include a styrene-acrylonitrile copolymer (AS resin), a copolymer of styrene and a (meth) acrylic monomer [for example, a styrene-methyl methacrylate copolymer, a styrene- Methyl methacrylate- (meth) acrylic acid ester copolymer, styrene-methyl methacrylate- (meth) acrylic acid copolymer, etc.], styrene-maleic anhydride copolymer, and the like. Preferred styrenic resins include polystyrene, copolymers of styrene and (meth) acrylic monomers [for example, copolymers based on styrene and methyl methacrylate such as styrene-methyl methacrylate copolymer. ], AS resin, styrene-butadiene copolymer and the like.

As said (meth) acrylic-type resin, the homopolymer or copolymer of a (meth) acrylic-type monomer, the copolymer of a (meth) acrylic-type monomer and a copolymerizable monomer, etc. can be used. Specific examples of the (meth) acrylic monomer include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, (Meth) acrylic acid isobutyl, (meth) acrylic acid hexyl, (meth) acrylic acid octyl, (meth) acrylic acid 2-ethylhexyl (meth) acrylic acid C _1-10 alkyl; (meth) acrylic acid phenyl, etc. (Meth) acrylic acid aryl; hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; glycidyl (meth) acrylate; N, N-dialkylaminoalkyl (meth) acrylate; Acrylonitrile; has an alicyclic hydrocarbon group such as tricyclodecane (Meth) acrylate etc. can be illustrated. Specific examples of the copolymerizable monomer include the styrene monomer, vinyl ester monomer, maleic anhydride, maleic acid, fumaric acid and the like. These monomers may be used alone or in combination. Can be used in combination with more than one species.

Examples of the (meth) acrylic resin include poly (meth) acrylic esters such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymers, and methyl methacrylate- (meth) acrylic acid ester copolymers. , Methyl methacrylate-acrylic acid ester- (meth) acrylic acid copolymer, (meth) acrylic acid ester-styrene copolymer (MS resin and the like), and the like. Specific examples of preferable (meth) acrylic resins include poly (meth) acrylic acid C _1-6 alkyl such as poly (meth) acrylic acid methyl, particularly methyl methacrylate as a main component (50 to 100% by mass, preferably And a methyl methacrylate-based resin, which is about 70 to 100% by mass).

Specific examples of the above organic acid vinyl ester resins include vinyl ester monomers alone or copolymers (polyvinyl acetate, polyvinyl propionate, etc.), vinyl ester monomers and copolymerizable monomers. (Ethylene-vinyl acetate copolymer, vinyl acetate-vinyl chloride copolymer, vinyl acetate- (meth) acrylic acid ester copolymer, etc.) or derivatives thereof. Specific examples of the vinyl ester resin derivatives include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl acetal resin, and the like.

Specific examples of the vinyl ether resins include homopolymers or copolymers of vinyl C _1-10 alkyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl t-butyl ether; and vinyl C _1-10 alkyl ether Examples thereof include a copolymer with a copolymerizable monomer (such as vinyl alkyl ether-maleic anhydride copolymer).

Specific examples of the halogen-containing resin include polyvinyl chloride, polyvinylidene fluoride, vinyl chloride-vinyl acetate copolymer, vinyl chloride- (meth) acrylate ester copolymer, vinylidene chloride- (meth) acrylate ester copolymer. A polymer etc. are mentioned.

Examples of the olefin resin include olefin homopolymers such as polyethylene and polypropylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- ( Examples thereof include copolymers such as (meth) acrylic acid ester copolymers. Specific examples of alicyclic olefin-based resins include cyclic olefins (for example, norbornene, dicyclopentadiene) homopolymers or copolymers (for example, alicyclic hydrocarbon groups such as sterically rigid tricyclodecane). Polymer), a copolymer of the above cyclic olefin and a copolymerizable monomer (for example, ethylene-norbornene copolymer, propylene-norbornene copolymer), and the like. Specific examples of the alicyclic olefin-based resin are available under the trade name “ARTON” and the trade name “ZEONEX”.

Examples of the polyester resin include aromatic polyesters using aromatic dicarboxylic acids such as terephthalic acid, such as poly C _2-4 alkylene terephthalate such as polyethylene terephthalate and polybutylene terephthalate, and poly C _2-4 alkylene naphthalate. Mention may be made of homopolyesters, copolyesters containing C _2-4 alkylene arylate units (C _2-4 alkylene terephthalate and / or C _2-4 alkylene naphthalate units) as main components (for example, 50% by mass or more). it can. As specific examples of the copolyester, among the structural units of poly _C2-4 alkylene arylate, a part of _C2-4 alkylene glycol is substituted with polyoxy _C2-4 alkylene glycol, _C6-10 alkylene glycol, alicyclic. Diol (cyclohexanedimethanol, hydrogenated bisphenol A, etc.), diol having an aromatic ring (9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene having a fluorenone side chain, bisphenol A, bisphenol A-alkylene oxide Copolyesters substituted with adducts, etc., and aromatic dicarboxylic acids partially substituted with asymmetric aromatic dicarboxylic acids such as phthalic acid and isophthalic acid, and aliphatic C _6-12 dicarboxylic acids such as adipic acid Polyester is included. Specific examples of the polyester resins include polyarylate resins, aliphatic polyesters using aliphatic dicarboxylic acids such as adipic acid, and homopolymers or copolymers of lactones such as ε-caprolactone. A preferred polyester resin is usually amorphous such as an amorphous copolyester (for example, C _2-4 alkylene arylate copolyester).

Examples of the polyamide resins include aliphatic polyamides such as nylon 46, nylon 6, nylon 66, nylon 610, nylon 612, nylon 11 and nylon 12, dicarboxylic acids (eg, terephthalic acid, isophthalic acid, adipic acid, etc.) and diamines. And polyamides obtained from (for example, hexamethylenediamine, metaxylylenediamine). A specific example of the polyamide-based resin may be a homopolymer or a copolymer of lactam such as ε-caprolactam, and is not limited to homopolyamide but may be copolyamide.

Examples of the polycarbonate resin include aromatic polycarbonates based on bisphenols (such as bisphenol A) and aliphatic polycarbonates such as diethylene glycol bisallyl carbonate.

As the polymer, a polymer having a curable functional group can also be used. The curable functional group may be present in the polymer main chain or may be present in the side chain, but more preferably in the side chain. Examples of the curable functional group include condensable groups and reactive groups (for example, hydroxyl group, acid anhydride group, carboxyl group, amino group or imino group, epoxy group, glycidyl group, isocyanate group), polymerizable group (for example, C _2-6 alkenyl group such as vinyl, propenyl, isopropenyl group, butenyl, allyl, etc., C _2-6 alkynyl group such as ethynyl, propynyl, butynyl, etc., C _2-6 alkenylidene group such as vinylidene, or their polymerizability And a group having a group (for example, a (meth) acryloyl group), etc. Among these functional groups, a polymerizable group is preferable.

As a method for introducing the curable functional group into the side chain, for example, a thermoplastic resin having a functional group such as a reactive group or a condensable group and a polymerizable compound having a reactive group with the functional group are used. The method of making it react can be mentioned.

Examples of the thermoplastic resin having a functional group such as a reactive group or a condensable group include a thermoplastic resin having a carboxyl group or its acid anhydride group (for example, (meth) acrylic resin, polyester resin, polyamide resin). ), A thermoplastic resin having a hydroxyl group (for example, a (meth) acrylic resin having a hydroxyl group, a polyurethane resin, a cellulose derivative, a polyamide resin), a thermoplastic resin having an amino group (for example, a polyamide resin), Examples thereof include thermoplastic resins having an epoxy group (for example, (meth) acrylic resins and polyester resins having an epoxy group). Moreover, the resin which introduce | transduced the said functional group into copolymerization or graft polymerization to thermoplastic resins, such as a styrene resin, an olefin resin, and an alicyclic olefin resin, may be sufficient.

When the polymerizable compound is reacted with a thermoplastic resin having a carboxyl group or an acid anhydride group thereof, a polymerizable compound having an epoxy group, a hydroxyl group, an amino group, an isocyanate group, or the like can be used. When making it react with the thermoplastic resin which has a hydroxyl group, the polymeric compound etc. which have a carboxyl group or its acid anhydride group, an isocyanate group, etc. are mentioned. When making it react with the thermoplastic resin which has an amino group, the polymeric compound etc. which have carboxyl or its acid anhydride group, an epoxy group, an isocyanate group, etc. are mentioned. When making it react with the thermoplastic resin which has an epoxy group, the polymeric compound etc. which have a carboxyl group or its acid anhydride group, an amino group, etc. are mentioned.

Among the polymerizable compounds, examples of the polymerizable compound having an epoxy group include epoxycyclo C _5-8 alkenyl (meth) acrylates such as epoxycyclohexenyl (meth) acrylate, glycidyl (meth) acrylate, allyl glycidyl ether and the like. Can be illustrated. Examples of the compound having a hydroxyl group include hydroxy C _1-4 alkyl (meth) acrylate such as hydroxypropyl (meth) acrylate, C _2-6 alkylene glycol (meth) acrylate such as ethylene glycol mono (meth) acrylate, and the like. It can be illustrated. Examples of the polymerizable compound having an amino group include amino _C1-4 alkyl (meth) acrylate such as aminoethyl (meth) acrylate, C _3-6 alkenylamine such as allylamine, 4-aminostyrene, diaminostyrene, and the like. Examples include aminostyrenes. Examples of the polymerizable compound having an isocyanate group include (poly) urethane (meth) acrylate and vinyl isocyanate. Examples of the polymerizable compound having a carboxyl group or an acid anhydride group thereof include unsaturated carboxylic acids such as (meth) acrylic acid and maleic anhydride, or anhydrides thereof.

As a typical example, a thermoplastic resin having a carboxyl group or its acid anhydride group and an epoxy group-containing compound, particularly a (meth) acrylic resin ((meth) acrylic acid- (meth) acrylic acid ester copolymer, etc.) ) And an epoxy group-containing (meth) acrylate (such as epoxycycloalkenyl (meth) acrylate and glycidyl (meth) acrylate). Specifically, a polymer in which a polymerizable unsaturated group is introduced into a part of the carboxyl group of the (meth) acrylic resin, for example, one of the carboxyl groups of the (meth) acrylic acid- (meth) acrylic acid ester copolymer. The (meth) acrylic polymer (Cyclomer P, manufactured by Daicel Chemical Industries, Ltd.) in which the epoxy group of 3,4-epoxycyclohexenylmethyl acrylate was reacted to the part to introduce a photopolymerizable unsaturated group into the side chain ) Etc. can be used.

The amount of the functional group (particularly polymerizable group) involved in the curing reaction for the thermoplastic resin is preferably 0.001 to 10 mol, more preferably 0.01 to 5 with respect to 1 kg of the thermoplastic resin. Mol, more preferably about 0.02 to 3 mol.

The curable resin precursor is a compound having a functional group that reacts with heat or active energy rays (such as ultraviolet rays or electron beams), and is cured or crosslinked with heat or active energy rays or the like (particularly cured or crosslinked). Resin). Examples of the resin precursor include a thermosetting compound or a resin [low molecular weight compound having an epoxy group, a polymerizable group, an isocyanate group, an alkoxysilyl group, a silanol group, etc. (for example, an epoxy resin or an unsaturated polyester resin). , Urethane-based resins, silicone-based resins)], photocurable compounds that can be cured by actinic rays (such as ultraviolet rays) (for example, photocurable monomers, oligomeric ultraviolet curable compounds), and the like. , An EB (electron beam) curable compound or the like. In addition, a photocurable compound such as a photocurable monomer, an oligomer, or a photocurable resin that may have a low molecular weight may be simply referred to as a “photocurable resin”.

The photocurable compound may be, for example, a monomer or an oligomer (or a resin, particularly a low molecular weight resin). Examples of the monomer include a monofunctional monomer [(meth) acrylic acid ester, etc. (Meth) acrylic monomers, vinyl monomers such as vinylpyrrolidone, (meth) acrylates having a bridged cyclic hydrocarbon group such as isobornyl (meth) acrylate, adamantyl (meth) acrylate, etc.], at least 2 Polyfunctional monomer having two polymerizable unsaturated bonds [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol Alkylene glycol di (meth) acrylate such as di (meth) acrylate; (Poly) oxyalkylene glycol di (meth) acrylate such as glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyoxytetramethylene glycol di (meth) acrylate; tricyclodecane dimethanol di (meth) acrylate , Di (meth) acrylates having bridged cyclic hydrocarbon groups such as adamantane di (meth) acrylate; trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta And polyfunctional monomers having about 3 to 6 polymerizable unsaturated bonds such as erythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate].

Examples of oligomers or resins include (meth) acrylates of bisphenol A-alkylene oxide adducts, epoxy (meth) acrylates (bisphenol A type epoxy (meth) acrylates, novolac type epoxy (meth) acrylates, etc.), polyester (meth) acrylates ( For example, aliphatic polyester type (meth) acrylate, aromatic polyester type (meth) acrylate, etc.), (poly) urethane (meth) acrylate (for example, polyester type urethane (meth) acrylate, polyether type urethane (meth) acrylate) And silicone (meth) acrylate. These photocurable compounds can be used alone or in combination of two or more.

The curable resin precursor is preferably a photocurable compound that can be cured in a short time, for example, an ultraviolet curable compound (such as a monomer, an oligomer, or a resin that may have a low molecular weight) or an EB curable compound. In particular, a practically advantageous resin precursor is an ultraviolet curable resin. Further, in order to improve resistance such as scratch resistance, the photocurable resin is a compound having 2 or more (preferably about 2 to 6, more preferably about 2 to 4) polymerizable unsaturated bonds in the molecule. Is preferred. The molecular weight of the curable resin precursor is about 5000 or less, preferably about 2000 or less, more preferably about 1000 or less in consideration of compatibility with the polymer.

The polymer and the curable resin precursor have a glass transition temperature of, for example, −100 ° C. to 250 ° C., preferably −50 ° C. to 230 ° C., more preferably about 0 to 200 ° C. (for example, about 50 to 180 ° C. ) Is preferable. From the viewpoint of surface hardness, the glass transition temperature is advantageously 50 ° C. or higher (for example, about 70 to 200 ° C.), preferably 100 ° C. or higher (for example, about 100 to 170 ° C.). The mass average molecular weight of the polymer can be selected, for example, from 1,000,000 or less, preferably from about 1,000 to 500,000.

The curable resin precursor may be used in combination with a curing agent as necessary. For example, in the thermosetting resin precursor, a curing agent such as amines or polyvalent carboxylic acids may be used in combination. Content of a hardening | curing agent is 0.1-20 mass parts with respect to 100 mass parts of curable resin precursor, Preferably it is 0.5-10 mass parts, More preferably, it is 1-8 mass parts (especially 1-5 mass). Part), and may be about 3 to 8 parts by mass. The photocurable resin precursor may be used in combination with a photopolymerization initiator. As said photoinitiator, the compound illustrated as what can be used in the said surface adjustment layer can be used.

The curable resin precursor may be used in combination with a curing accelerator. For example, the photocurable resin may contain a photocuring accelerator such as a tertiary amine (for example, dialkylaminobenzoic acid ester), a phosphine photopolymerization accelerator, and the like.

In the method 2, at least two kinds of components are selected from the group consisting of the polymer and the curable resin precursor as described above. In the case of the combination (a) in which a plurality of polymers are incompatible with each other and phase-separated, the above-described polymers can be used in appropriate combination. For example, when the first resin is a styrene resin (polystyrene, styrene-acrylonitrile copolymer, etc.), the second resin is a cellulose derivative (for example, cellulose esters such as cellulose acetate propionate), (meta ) Acrylic resins (polymethyl methacrylate, etc.), alicyclic olefin resins (polymers containing norbornene as a monomer), polycarbonate resins, polyester resins (the above poly C _2-4 alkylene arylate copolyesters) Etc.) can be used. For example, when the first polymer is a cellulose derivative (for example, cellulose esters such as cellulose acetate propionate), the second polymer is a styrene resin (polystyrene, styrene-acrylonitrile copolymer, etc.), Uses (meth) acrylic resins, alicyclic olefin resins (polymers containing norbornene as monomers), polycarbonate resins, polyester resins (poly C _2-4 alkylene arylate copolyesters, etc.) can do. In a combination of a plurality of resins, at least cellulose esters (for example, cellulose C _2-4 alkyl carboxylic acid esters such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate) may be used.

The ratio (mass ratio) between the first polymer and the second polymer is, for example, 1/99 to 99/1, preferably 5/95 to 95/5 for the first polymer / second polymer, Preferably, it can be selected from the range of about 10/90 to 90/10, and is usually about 20/80 to 80/20, particularly about 30/70 to 70/30.

Further, the curable resin precursor (particularly, a monomer or oligomer having a plurality of curable functional groups) can be used in combination with the combination of the plurality of polymers. In this case, from the viewpoint of scratch resistance after curing, one of the plurality of polymers (especially both polymers) is involved in the curing reaction (functional group involved in the curing of the curable resin precursor). May be a thermoplastic resin. The thermoplastic resin and the curable resin precursor are preferably incompatible with each other. In this case, at least one polymer may be incompatible with the resin precursor, and the other polymer may be compatible with the resin precursor.

The ratio (mass ratio) between the polymer and the curable resin precursor is not particularly limited, and for example, the polymer / curable resin precursor can be selected from a range of about 5/95 to 95/5, and the viewpoint of surface hardness. Therefore, it is preferably about 5/95 to 60/40, more preferably about 10/90 to 50/50, particularly about 10/90 to 40/60.

When the polymer is composed of a plurality of incompatible polymers and phase-separated, the curable resin precursor is a combination in which at least one of the incompatible polymers is compatible with each other near the processing temperature. Is preferably used. That is, when a plurality of incompatible polymers are constituted by, for example, a first resin and a second resin, the curable resin precursor is compatible with at least either the first resin or the second resin. And preferably compatible with both polymer components. When compatible with both polymer components, at least two phases of a mixture mainly composed of the first resin and the curable resin precursor and a mixture mainly composed of the second resin and the curable resin precursor Phase separate.

When the compatibility of the plurality of selected polymers is low, the polymers are effectively phase separated in the drying process for evaporating the solvent, and the function as an antiglare layer is improved. Multiple polymer phase separation is easy by preparing a homogeneous solution using good solvents for both components and visually checking whether the remaining solids become cloudy in the process of gradually evaporating the solvent. Can be determined.

In the composition for phase-separation type antiglare layer, the solvent can be selected and used according to the type and solubility of the polymer and curable resin precursor, and at least solids (a plurality of polymers and curable resin precursors are used). Body, reaction initiator, and other additives) may be used as long as they can be uniformly dissolved, and can be used in wet spinodal decomposition. Examples of such a solvent include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons ( Cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (ethanol, isopropanol, Butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethylsulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.), etc. It may be a mixed solvent.

The concentration of the solute (polymer and curable resin precursor, reaction initiator, other additives) in the composition for phase separation type antiglare layer is within a range where phase separation occurs and does not impair castability and coating properties. For example, it is 1-80 mass%, Preferably it is 5-60 mass%, More preferably, it is about 15-40 mass% (especially 20-40 mass%) grade.

(Method 3) Method of forming an antiglare layer using a process for embossing the concavo-convex shape Method 3 is a method of forming a resin coating layer and imparting the concavo-convex shape to the surface of the coating layer. This is a method for forming an antiglare layer having an uneven shape by performing mold processing. Such a method can be suitably performed by a forming process using a mold having an uneven shape opposite to the uneven shape of the antiglare layer. Examples of the mold having the reverse uneven shape include an embossed plate and an embossed roll.

In Method 3, the composition for forming an antiglare layer may be applied after being provided with a concavo-convex shape, or the composition for forming an antiglare layer may be supplied to the interface between the light-transmitting substrate and the concavo-convex type, The composition for forming an antiglare layer may be interposed between the concavo-convex mold and the light-transmitting substrate to form the concavo-convex shape and form the antiglare layer at the same time. In the present invention, a flat embossed plate can be used instead of the embossed roller.

The concavo-convex surface formed on the embossing roller or the flat embossing plate can be formed by various known methods such as a sandblasting method or a bead shot method. The antiglare layer formed using an embossing plate (embossing roller) by the sandblasting method has a shape in which a large number of concave shapes are distributed on the upper side. An antiglare layer formed using an embossed plate (embossing roller) by a bead shot method has a shape in which a number of convex shapes are distributed on the upper side.

When the average roughness of the uneven shape formed on the surface of the antiglare layer is the same, the antiglare layer having a shape in which a large number of convex portions are distributed on the upper side has a shape in which a large number of concave portions are distributed on the upper side. It is said that there are few reflections, such as an indoor lighting device, compared with what is. For this reason, according to a preferred embodiment of the present invention, it is preferable to form the concavo-convex shape of the antiglare layer using a concavo-convex mold formed in the same shape as the concavo-convex shape of the antiglare layer by the bead shot method.

As a mold material for forming the concavo-convex mold surface, plastic, metal, wood or the like can be used, and a composite of these may be used. As the mold material for forming the concavo-convex mold surface, metal chromium is preferable from the viewpoint of strength and wear resistance due to repeated use. From the viewpoint of economy and the like, chromium is applied to the surface of the iron embossing plate (embossing roller). Plating is preferred.

Specific examples of the particles (beads) to be sprayed when forming the concavo-convex mold by the sand blast method or the bead shot method include inorganic particles such as metal particles, silica, alumina, or glass. The particle diameter (diameter) of these particles is preferably about 100 μm to 300 μm. When spraying these particles onto the mold material, a method of spraying these particles together with a high-speed gas can be used. At this time, an appropriate liquid such as water may be used in combination. Further, in the present invention, it is preferable to use a concavo-convex mold formed with a concavo-convex shape after chromium plating or the like for the purpose of improving durability during use. Is preferable.

The optical layered body of the present invention may further have a low refractive index layer on the surface of the surface adjustment layer. Thereby, the antireflection function can be improved.

The low refractive index layer is formed on the surface of the surface adjustment layer, and has a refractive index lower than that of the surface adjustment layer. According to a preferred aspect of the present invention, the refractive index of the surface adjustment layer is 1.5 or more, and the refractive index of the low refractive index layer is less than 1.5, preferably 1.45 or less. Is preferred.

The low refractive index layer consists of 1) a resin containing silica or magnesium fluoride, 2) a fluororesin that is a low refractive index resin, 3) a fluororesin containing silica or magnesium fluoride, 4) silica or fluoride You may be comprised with either of the thin films of magnesium.

The fluororesin is a polymerizable compound containing at least a fluorine atom in the molecule or a polymer thereof. The polymerizable compound is not particularly limited, but, for example, those having a curing reactive group such as a functional group that is cured by ionizing radiation (ionizing radiation curable group) and a polar group that is cured by heat (thermosetting polar group). preferable. Moreover, the compound which has these reactive groups simultaneously may be sufficient.

As the polymerizable compound having an ionizing radiation curable group containing a fluorine atom, 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 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-trifluoromethacryl (Meth) acrylate compounds having fluorine atoms in the molecule, such as methyl acrylate and ethyl α-trifluoromethacrylate; C 1-14 fluoroalkyl groups having at least 3 fluorine atoms in the molecule, fluorocyclo An alkyl group or a fluoroalkylene group and at least two (meta And fluorine-containing polyfunctional (meth) acrylic acid ester compounds having an acryloyloxy group.

Examples of the polymerizable compound having a thermosetting polar group containing a fluorine atom include 4-fluoroethylene-perfluoroalkyl vinyl ether copolymer; fluoroethylene-hydrocarbon vinyl ether copolymer; epoxy, polyurethane, cellulose, Examples include fluorine-modified products of resins such as phenol and polyimide. As said thermosetting polar group, hydrogen bond forming groups, such as a hydroxyl group, a carboxyl group, an amino group, an epoxy group, are mentioned preferably, for example. These are excellent not only in adhesion to the coating film but also in affinity with inorganic ultrafine particles such as silica.

Polymerizable compounds having both ionizing radiation curable groups and thermosetting polar groups (fluorinated resins) include acrylic or methacrylic acid moieties and fully fluorinated alkyl, alkenyl, aryl esters, fully or partially fluorinated vinyl ethers. Examples thereof include fully or partially fluorinated vinyl esters, fully or partially fluorinated vinyl ketones, and the like.

Examples of the polymer of the polymerizable compound containing a fluorine atom include a polymer of a monomer or a monomer mixture containing at least one fluorine-containing (meth) acrylate compound of the polymerizable compound having the ionizing radiation curable group; At least one fluorine (meth) acrylate compound and a fluorine atom in a molecule such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Copolymers with (meth) acrylate compounds not containing; fluoroethylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, 3,3,3-trifluoropropylene, 1,1,2-trichloro-3, 3,3-trifluoropropylene, hex Homopolymers and copolymers of fluorine-containing monomers such as hexafluoropropylene; and the like.

Moreover, the silicone containing vinylidene fluoride copolymer which made these copolymers contain a silicone component can also be used as a polymer of the said polymeric compound. Examples of 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 Corn, fluorine-modified silicones, polyether-modified silicone can be exemplified. Among them, those having a dimethylsiloxane structure are preferable.

In addition to the above, a fluorine-containing compound having at least one isocyanato group in the molecule, and 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 A compound obtained by reacting a fluorine-containing polyether polyol, a fluorine-containing alkyl polyol, a fluorine-containing polyester polyol, a fluorine-containing polyol such as a fluorine-containing ε-caprolactone-modified polyol, and a compound having an isocyanato group. Compounds; etc. can also be used as the fluororesin.

In forming the low refractive index layer, for example, it can be formed using a composition containing a raw material component (a composition for forming a refractive index layer). More specifically, a raw material component (resin, etc.) and, if necessary, an additive (for example, “fine particles having voids”, a polymerization initiator, an antistatic agent, an antiglare agent, etc., described later) are dissolved or dispersed in a solvent. A low refractive index layer can be obtained by using the resulting solution or dispersion as a composition for forming a low refractive index layer, forming a coating film of the composition, and curing the coating film. Examples of the additive such as a polymerization initiator, an antistatic agent and an antiglare agent include those described above for the antiglare layer.

Examples of the solvent include those described above for the antiglare layer, preferably methyl isobutyl ketone, cyclohexanone, isopropyl alcohol (IPA), n-butanol, t-butanol, diethyl ketone, and PGME.

The preparation method of the said composition should just be implemented according to a well-known method, if a component can be mixed uniformly. For example, it can mix using the well-known apparatus mentioned above in formation of a hard-coat layer.

The formation method of a coating film should just follow a well-known method. For example, the various methods described above for forming the hard coat layer can be used.

What is necessary is just to select the hardening method of the obtained coating film suitably according to the content etc. of the composition. For example, in the case of an ultraviolet curing type, the coating film may be cured by irradiating with ultraviolet rays.

In the low refractive index layer, it is preferable to use “fine particles having voids” as the low refractive index agent. The “fine particles having voids” can reduce the refractive index while maintaining the layer strength of the surface adjustment layer. In the present invention, the term “fine particles having voids” refers to a structure in which a gas is filled with gas and / or a porous structure containing gas, and the gas in the fine particle is compared with the original refractive index of the fine particle. It means fine particles whose refractive index decreases in inverse proportion to the occupation ratio. The present invention also includes fine particles capable of forming a nanoporous structure inside and / or at least part of the surface depending on the form, structure, aggregated state, and dispersed state of the fine particles inside the coating. . The low refractive index layer using these fine particles can adjust the refractive index to 1.30 to 1.45.

Examples of the inorganic fine particles having voids include silica fine particles prepared by the method described in JP-A-2001-233611. Silica fine particles obtained by the production methods described in JP-A-7-133105, JP-A-2002-79616, JP-A-2006-106714 and the like may be used. Since silica fine particles having voids are easy to manufacture and have high hardness, when a low refractive index layer is formed by mixing with a binder, the layer strength is improved and the refractive index is 1.20-1. It is possible to prepare within the range of about 45. In particular, as specific examples of the organic fine particles having voids, hollow polymer fine particles prepared by using the technique disclosed in JP-A-2002-80503 are preferably exemplified.

The fine particles capable of forming a nanoporous structure inside and / or at least a part of the surface of the coating are manufactured for the purpose of increasing the specific surface area in addition to the silica fine particles, and the packing column and the porous surface Examples include a release material that adsorbs various chemical substances on the part, a porous fine particle used for catalyst fixation, a dispersion or aggregate of hollow fine particles intended to be incorporated into a heat insulating material or a low dielectric material. As such a specific example, an aggregate of porous silica fine particles and a silica fine particle manufactured by Nissan Chemical Industries, Ltd. were linked in a chain form from the product names Nippon and Nippon manufactured by Nippon Silica Kogyo Co., Ltd. as commercial products. From the colloidal silica UP series (trade name) having a structure, those within the range of the preferable particle diameter of the present invention can be used.

The average particle diameter of the “fine particles having voids” is 5 nm or more and 300 nm or less, preferably the lower limit is 8 nm or more and the upper limit is 100 nm or less, more preferably the lower limit is 10 nm or more and the upper limit is 80 nm or less. When the average particle diameter of the fine particles is within this range, excellent transparency can be imparted to the surface adjustment layer. The average particle diameter is a value measured by a method such as a dynamic light scattering method. The “fine particles having voids” are usually about 0.1 to 500 parts by mass, preferably about 10 to 200 parts by mass with respect to 100 parts by mass of the matrix resin in the low refractive index layer.

In the formation of the low refractive index layer, the viscosity of the composition for forming a low refractive index layer is in the range of 0.5 to 5 cps (25 ° C.), preferably 0.7 to 3 cps (25 ° C.) at which preferable coatability is obtained. It is preferable to make it. An antireflection film 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 to a substrate can be formed.

The resin curing means may be the same as described in the section of the antiglare layer. 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 film thickness (nm) d _A of the low refractive index layer is expressed by the following formula (V):
d _A = mλ / (4n _A ) (V)
(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 has the following formula (VI):
_{120 <n A d A <145} (VI)
It is preferable from the viewpoint of low reflectivity.

The light-transmitting substrate preferably has smoothness and heat resistance and is excellent in mechanical strength. Examples of materials for forming the light-transmitting substrate include polyester (polyethylene terephthalate, polyethylene naphthalate), cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, polyamide, polyimide, polyethersulfone, polysulfone, polypropylene, poly Examples thereof include thermoplastic resins such as methyl pentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polymethyl methacrylate, polycarbonate, and polyurethane, preferably polyester (polyethylene terephthalate, polyethylene naphthalate) and cellulose triacetate.

In addition, an amorphous olefin polymer (Cyclo-Olefin-Polymer: COP) film having an alicyclic structure can also be used. This is a base material on which a norbornene polymer, a monocyclic olefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer resin, etc. are used. For example, manufactured by Nippon Zeon Co., Ltd. ZEONEX, ZEONOR (norbornene resin), Sumitomo Bakelite Co., Ltd. Sumilite FS-1700, JSR Co., Ltd. Arton (modified norbornene resin), Mitsui Chemicals, Inc. Appel (cyclic olefin copolymer), Ticona Examples include Topas (cyclic olefin copolymer) manufactured by the company, 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 Corporation is also preferable as an alternative base material for triacetylcellulose.

In the present invention, it is preferable to use these thermoplastic resins as a film-like body rich in thin film flexibility. However, depending on the use mode in which curability is required, these thermoplastic resin plates or It is also possible to use a glass plate.

The thickness of the light transmissive substrate is preferably 20 μm or more and 300 μm or less, more preferably the upper limit is 200 μm or less, and the lower limit is 30 μm or more. When the light-transmitting substrate is a plate-like body, the thickness may exceed these thicknesses. When forming an antiglare layer on the base material, in order to improve adhesion, in addition to physical treatment such as corona discharge treatment and oxidation treatment, a coating called an anchor agent or primer is applied in advance. May be.

In the optical layered body of the present invention, the surface haze value on the surface of the optical layered body is preferably 0.1% to 5.0%. When the surface haze value is within the above range, it is preferable in that a preferable surface shape having an antiglare property can be obtained while maintaining a glossy blackness. The said surface haze value can be suitably adjusted by adjusting the uneven | corrugated shape etc. of the film surface mentioned above.

The surface haze value is a value measured by the following method.
A resin such as pentaerythritol triacrylate (including a resin component such as a monomer or an oligomer) is diluted with toluene or the like on the irregularities of the antiglare layer to obtain a solid content of 60%, and the dry film thickness is 8 μm with a wire bar. Apply as follows. As a result, the surface unevenness of the antiglare layer is crushed and a flat layer is formed. However, if the leveling agent is contained in the composition for forming the antiglare layer and the recoat agent is easily repelled and difficult to wet, the antiglare film is preliminarily saponified (2 mol / l NaOH ( Or KOH) solution 55 ° C. for 3 minutes, washed with water, completely removed with Kimwipe, and then dried in a 50 ° oven for 1 minute). The film having a flat surface has no internal haze and no haze due to surface irregularities. This haze can be determined as an internal haze. And the value which deducted the internal haze from the haze (overall haze) of the original film is calculated | required as a haze (surface haze) resulting from only surface asperity.

The optical laminate of the present invention can be used for each application such as a cathode ray tube display (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), etc. It is preferable to use a film having physical properties required depending on the application. In particular, the required optical characteristics are slightly different between when used in a non-self-emitting image display device and when used in a spontaneous light-emitting image display device. Is preferred.

For example, when the optical layered body of the present invention is used in a non-self-luminous image display device for LCD or the like, the internal haze value of the optical layered body is preferably 0% or more and 70% or less. When the internal haze value is in the above range, an effect of improving “glare” (described later) when the optical layered body of the present invention is used for an LCD can be obtained. The internal haze value is a value measured by the method described in the method for measuring the surface haze value described above.

When an antiglare layer having an uneven shape is formed by the above method 1 to obtain an optical laminate having the above internal haze value, the difference n between the refractive index of the resin used and the fine particles is 0.03 or more and 0.20 or less. By doing so, an optical layered body having the above internal haze value can be obtained. N is more preferably a lower limit of 0.05 or more, further preferably 0.07 or more, more preferably an upper limit of 0.18 or less, still more preferably 0.12 or less. In this way, by setting the difference n between the refractive index of the resin and the fine particles within the above range, it is possible to impart internal haze to the optical laminate, and from image unevenness such as an LCD and the back side such as a backlight. When the transmitted light passes through an optical laminate having a concavo-convex shape, the surface unevenness acts as a fine lens and disturbs the displayed pixel (glare to the eyes) It is possible to effectively prevent flickering due to a difference in luminance).

In the case of forming an antiglare layer having a concavo-convex shape by the above method 2, a method of adjusting the refractive index difference of two or more components to be used, and in the case of the above method 3, the fine particles and the resin Internal haze can be adjusted by a method such as embossing a material in which the refractive index difference is adjusted or a material in which the refractive index difference between two or more resin components is adjusted in the same manner as in Method 2.

Furthermore, for example, when the optical laminate of the present invention is used in a self-luminous image display device such as PDP, FED, ELD (organic EL, inorganic EL), CRT, the internal haze value is 0% or more and 3% or less. Preferably there is. By setting it as such a low haze value, it is preferable at the point from which the outstanding effect is acquired in the property of both glossiness and anti-glare property.

As an example of a method for forming an antiglare layer having a concavo-convex shape by the above method 1 and obtaining an optical laminate having a low internal haze value (0 to 3%), the difference between the resin used and the refractive index of the fine particles By setting n to 0 or more and 0.05 or less, a method of obtaining an optical laminate having the above internal haze value can be exemplified. N is more preferably a lower limit of 0.001 or more, further preferably 0.005 or more, more preferably an upper limit of 0.03 or less, and still more preferably 0.01 or less. In other words, it is better to adjust the refractive index difference between the resin and the fine particles as much as possible. When the difference n between the refractive indexes of the resin and the fine particles is within the above range, a high contrast and a low internal haze value can be realized. When the optical laminate is intended to realize such characteristics, the difference n between the refractive index of the resin and the fine particles is preferably within the above range. In order to set the internal haze value to a value higher than 3% and prevent glare, the refractive index difference may be made larger than 0.05. However, since the internal haze value can be changed not only by the refractive index difference between materials but also by the film thickness and the amount of material added, the refractive index difference range of the material is not limited to the above.

When forming an antiglare layer having a concavo-convex shape by the above method 2 or when forming by the above method 3, the internal haze is adjusted by adjusting the refractive index difference between the materials used in each method as in the method 1. Can be adjusted.

By providing the optical laminate according to the present invention on the surface of the polarizing element on the surface opposite to the surface on which the antiglare layer is present in the optical laminate, a polarizing plate can be obtained. 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 optical laminate of the present invention, it is preferable to saponify the light-transmitting substrate (preferably a triacetyl cellulose film). By the saponification treatment, the adhesiveness is improved and an antistatic effect can be obtained.

The present invention is also an image display device including the optical laminate or the polarizing plate on the outermost surface. The image display device may be a non-self-luminous image display device such as an LCD, or a self-luminous image display device such as a PDP, FED, ELD (organic EL, inorganic EL), or CRT.

An LCD as a typical example of the non-spontaneous light emission type 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 optical laminate of the present invention or the polarizing plate of the present invention is formed on the surface of this transmissive display.

In the case where the present invention is a liquid crystal display device having the optical laminate, the light source of the light source device is irradiated from the lower side of the optical laminate. Note that in the STN liquid crystal display device, 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 spontaneous emission type image display device includes a front glass substrate and a rear glass substrate disposed with a discharge gas sealed between the front glass substrate and the front glass substrate. When the image display device of the present invention is a PDP, the above-mentioned optical laminate is provided on the surface of the surface glass substrate or the front plate (glass substrate or film substrate).

The self-luminous image display device is an ELD device that emits light when a voltage is applied, such as zinc sulfide and a diamine substance: a phosphor is deposited on a glass substrate, and the voltage applied to the substrate is controlled. It may be an image display device such as a CRT that converts light into light and generates an image visible to the human eye. In this case, the optical laminated body described above 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 apparatus of the present invention can be used for display display of a television, a computer, a word processor, or the like. In particular, it can be suitably used for the surface of high-definition image displays such as CRTs, liquid crystal panels, PDPs, and ELDs.

With the optical layered body of the present invention, properties such as black reproducibility such as glossiness and anti-glare property in an image display device can be obtained simultaneously.

Hereinafter, the present invention will be described in more detail based on examples.
The composition of each layer which comprises an optical laminated body was prepared according to the following composition.

Antiglare layer composition (A) (used in Examples 1, 2 and Comparative Examples 1, 2, and 3)
Amorphous silica matte agent dispersed ink: Resin dispersion of amorphous silica (PETA) with an average particle size of 2.5 μm, solid content 60%, silica component is 15% of total solids, solvent is toluene), UV curable resin Pentaerythritol triacrylate (PET) (Nippon Kayaku Co., Ltd., refractive index 1.51), monodisperse acrylic beads (particle size 7.0 μm, refractive index 1.535) as translucent fine particles, Using dispersed styrene beads (particle size 3.5 μm, refractive index 1.60), when the total amount of PETA in the total solid amount is 100 parts by mass, the monodisperse acrylic beads are 20 parts by mass, and the monodisperse styrene beads are Was 2.5 parts by mass, and the amorphous silica was adjusted to 2.0 parts by mass. Furthermore, 0.04% of a silicon-based leveling agent is added to 100 parts by mass of the total amount of the resin, so that the solid content of the final composition is 40.5% by mass and toluene / cyclohexanone = 8/2. Toluene and cyclohexanone were appropriately added and mixed well. This composition was filtered through a polypropylene filter having a pore diameter of 30 μm to obtain an antiglare layer composition (A).
In addition, the refractive index of the composition binder for anti-glare layers is 1.51.

Antiglare layer composition (B) (used in Examples 3, 4, 5, 6 Comparative Examples 4, 5, 6)
UV curable resin pentaerythritol triacrylate (PETA) (Nippon Kayaku Co., Ltd.) 28.4 parts by mass Dipentaerythritol hexaacrylate (DPHA) (Nippon Kayaku Co., Ltd.) 1.50 parts by mass acrylic polymer (Molecular weight 75,000) 3.18 parts by mass photocuring initiator Irgacure 184 (manufactured by Ciba Specialty Chemicals) 1.96 parts by mass photocuring initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) 0.33 parts by mass Translucent fine particles Monodisperse styrene beads (particle size 3.5 μm, refractive index 1.60) 4.55 parts by mass Silicon-based leveling agent 0.0105 parts by mass The above materials and toluene: cyclohexanone 7: The solvent of No. 3 was added so that the total solid content would be 38% and mixed well to prepare a composition. This composition was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a composition for antiglare layer (B). In addition, the refractive index of the composition binder for anti-glare layers is 1.51.

Surface adjustment layer composition (A) (used in Comparative Examples 2 and 3)
UV curable resin UV1700B (Nippon Gosei Kagaku Co., Ltd. dipentaerythrole hexaacrylate, refractive index 1.51) 31.1 parts by mass Aronix M315 (trade name, ethylene oxide of isocyanuric acid manufactured by Toagosei Co., Ltd.) 3 mol adduct triacrylate) 10.4 parts by mass photocuring initiator Irgacure 184 (manufactured by Ciba Specialty Chemicals) 1.49 parts by mass photocuring initiator Irgacure 907 (Ciba Specialty Chemicals) Manufactured) 0.41 parts by mass antifouling agent UT-3971 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 2.07 parts by mass toluene 525.18 parts by mass cyclohexanone 60.28 parts by mass It was adjusted.
This composition was filtered through a polypropylene filter having a pore diameter of 10 μm to prepare a composition for surface adjustment layer (A) having a solid content of 40.5%.
The refractive index of the surface adjustment layer formed by the surface adjustment layer composition (A) is 1.51.

Composition for surface adjustment layer (B) (used in Examples 1 and 4) (P / V = 33.6)
Colloidal silica slurry (MIBK dispersion); solid content 40%, average particle size 20 nm
2.86 parts by mass UV curable resin UV-1700B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., dipentaerythrole hexaacrylate, refractive index 1.51 solid content MIBK: diluted with methyl isobutyl ketone) 5.34 parts by mass Aronix M315 (trade name, triacrylate of ethylene oxide 3 mol adduct of isocyanuric acid manufactured by Toagosei Co., Ltd. 60% MIBK diluted) 1.34 parts by mass Irgacure 184 (photocuring initiator; Ciba Specialty Chemicals) Made)
0.024 parts by mass Irgacure 907 (photocuring initiator; manufactured by Ciba Specialty Chemicals)
0.004 parts by mass UT-3971 (antifouling agent; solid content 30% MIBK solution; manufactured by Nippon Synthetic Chemical Industry)
0.007 parts by mass Toluene 2.85 parts by mass Cyclohexanone 0.60 parts by mass The above components were sufficiently mixed to prepare a composition. This composition was filtered through a polypropylene filter having a pore size of 30 μm to prepare a composition for surface adjustment layer (B) having a solid content of 40.5%. The refractive index of the surface adjustment layer formed by the surface adjustment layer composition (B) is 1.51.

Composition for surface adjustment layer (C) (used in Example 2) (P / V = 75)
Colloidal silica slurry (MIBK dispersion); solid content 40%, average particle size 20 nm
4.87 parts by mass UV-1700B (ultraviolet curable resin; manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content 60% MIBK) 4.08 mass parts Aronics M315 (ultraviolet curable resin; manufactured by Toa Gosei Co., Ltd., solid content 60% MIBK) 1.02 Mass parts Irgacure 184 (photocuring initiator; manufactured by Ciba Specialty Chemicals)
0.018 parts by mass Irgacure 907 (photocuring initiator; manufactured by Ciba Specialty Chemicals)
0.003 parts by mass UT-3971 (antifouling agent; solid content 30% MIBK solution; manufactured by Nippon Synthetic Chemical Industry)
0.006 parts by mass Toluene 2.50 parts by mass Cyclohexanone 0.53 parts by mass The above components were sufficiently mixed to prepare a composition. This composition was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a composition for surface adjustment layer (C) having a solid content of about 40%. The refractive index of the surface adjustment layer formed by the surface adjustment layer composition (C) is 1.51.

Composition for surface adjustment layer (D) (used in Example 3) P / V = 7
ATO ultrafine particle dispersion (ASD006, manufactured by Dainichi Seika) solid content 50%, solvent ethanol, methanol, isopropyl alcohol, polyethylene glycol monoethyl ether
80 parts by mass Isopropyl alcohol 20 parts by mass The above composition was filtered through a polypropylene filter having a pore size of 30 μm to prepare a composition for surface adjustment layer (C) having a solid content of 40%. The refractive index of the surface adjustment layer formed by the surface adjustment layer composition (C) is 1.52.

Composition for surface adjustment layer (E) (used in Example 5) P / V = 200
TiO ₂ ultrafine particles 18.68 parts by mass pentaerythritol triacrylate 9.34 parts by mass Dispersant Irgacure 184 (photocuring initiator; manufactured by Ciba Specialty Chemicals)
0.37 parts by mass Methyl isobutyl ketone 69.73 parts by mass The above components were sufficiently dispersed and mixed to prepare a composition. The composition was filtered through a polypropylene filter having a pore size of 30 μm to prepare a composition for surface adjustment layer (D) having a solid content of about 31.5%. The refractive index of the surface adjustment layer formed by the surface adjustment layer composition (D) is 1.80.

Composition for surface adjustment layer (F) (used in Example 6)
Zirconia ultrafine particle-containing coating composition (manufactured by JSR, trade name: “KZ7973”, refractive index: 1.69 resin matrix, solid content 50%) 80 parts by mass methyl isobutyl ketone 20 parts by mass It filtered with the filter made from a polypropylene, and prepared the composition for surface adjustment layers (C) of 40% of solid content. In addition, the refractive index of the surface adjustment layer formed with the composition (C) for surface adjustment layers is 1.69.

Composition for surface adjustment layer (G) (used in Comparative Example 6)
UV curable resin UV1700B (Nippon Gosei Kagaku Co., Ltd. dipentaerythrole hexaacrylate, refractive index 1.51) 31.1 parts by mass Aronix M315 (trade name, ethylene oxide of isocyanuric acid manufactured by Toagosei Co., Ltd.) Triacrylate of 3 mol adduct) 10.4 parts by mass photocuring initiator Irgacure 184 (manufactured by Ciba Specialty Chemicals)
1.49 parts by mass photocuring initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals)
0.41 parts by mass Antifouling agent UT-3971 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 2.07 parts by mass Toluene 739.58 parts by mass Cyclohexanone 84.88 parts by mass The above components were sufficiently mixed to prepare a composition. .
The composition was filtered through a polypropylene filter having a pore size of 10 μm to prepare a surface adjustment layer composition (G) having a solid content of about 5%.
The refractive index of the surface adjustment layer formed by the surface adjustment layer composition (A) is 1.51.

Surface adjustment layer composition (H) (used in Example 7)
Antimony oxide ultrafine particle dispersion composition (XJC-0173 made by Nippon Pernox, solid content 45%, P / V150, solvent polyethylene glycol monomethyl ether) 100 parts by mass UV1700B (made by Nippon Synthetic Chemical Industry Co., Ltd.) , Refractive index 1.51) 0.149 parts by mass photocuring initiator Irgacure 184 (manufactured by Ciba Specialty Chemicals)
0.027 parts by mass photocuring initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals)
0.0045 parts by mass Methyl isobutyl ketone 175.7 parts by mass Polyethylene glycol monomethyl ether 175.7 parts by mass The above components were sufficiently dispersed and mixed to prepare a composition. The composition was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a composition for surface adjustment layer (H) having a solid content of about 10%. The refractive index of the surface adjustment layer formed by the surface adjustment layer composition (H) is 1.59.

Low refractive index composition (A) (used in Examples 5 and 6)
Through rear 12SW (hollow silica slurry (IPA, MIBK dispersion) solid content 20%, particle size 50 nm; catalyst chemical industry) 9.57 parts by mass pentaerythritol triacrylate PET30 (UV curable resin; manufactured by Nippon Kayaku Co., Ltd.) 0.981 mass Part AR110 (fluoropolymer; solid content 15% MIBK solution; manufactured by Daikin Industries)
6.53 parts by mass Irgacure 369 (photocuring initiator; manufactured by Ciba Specialty Chemicals)
0.069 parts by mass X-22-164E (silicone leveling agent; manufactured by Shin-Etsu Chemical Co., Ltd.)
0.157 parts by mass Propylene glycol monomethyl ether (PGME) 28.8 parts by mass Methyl isobutyl ketone 53.9 parts by mass The above components were stirred and then filtered through a polypropylene filter having a pore size of 10 μm to obtain a composition for a low refractive index layer. (A) was prepared. This has a refractive index of 1.40.

Low refractive index layer composition (B) (used in Comparative Example 4)
AR110 (fluoropolymer; solid content 15% MIBK solution; manufactured by Daikin Industries)
10 parts by weight Irgacure 369 (photocuring initiator; manufactured by Ciba Specialty Chemicals)
0.06 parts by mass Methyl isobutyl ketone 20 parts by mass The above components were stirred and then filtered through a polypropylene filter having a pore size of 10 μm to prepare a composition for low refractive index layer (B) having a solid content of 5%. This has a refractive index of 1.38.

Composition for low refractive index layer (C) (used in Comparative Example 5)
Fluorine-based resin composition (manufactured by JSR, trade name: “TM086”) 34.14 parts by mass photopolymerization initiator (manufactured by JSR, trade name: “JUA701”) 0.85 parts by mass MIBK 65 parts by mass After stirring, the mixture was filtered through a polypropylene filter having a pore size of 10 μm to prepare a composition for low refractive index layer (C). This has a refractive index of 1.42.

Example 1
Formation of Antiglare Layer Using a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm as a transparent substrate, the above antiglare layer composition is coated on a film with a winding rod ( (Meyer's Bar) # 8, applied and dried in an oven at 70 ° C for 1 minute to evaporate the solvent, and then irradiate with ultraviolet rays to a dose of 30 mJ to cure the coating and prevent glare A layer was formed. In the antiglare layer, fine particles having a maximum refractive index difference of 0.09 from the binder resin are used as the fine particles. The antiglare layer thus formed has an internal diffusion effect and can more effectively prevent mengilla.

Formation of surface adjustment layer Furthermore, the composition for surface adjustment layer (B) was applied on the antiglare layer using a winding rod for coating (Meyer's bar) # 12, and was then heated in an oven at 70C. After heating and drying for 1 minute to evaporate the solvent, the coating film is cured by irradiating with ultraviolet rays to an irradiation dose of 100 mJ under a nitrogen purge (oxygen concentration of 200 ppm or less), and the surface adjustment layer is formed into a dry film thickness. An antiglare optical laminate was obtained by laminating 6.6 μm. (Total thickness of the antiglare layer on the substrate: about 11 μm)

Example 2
Formation of Antiglare Layer Using a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm as a transparent substrate, the above antiglare layer composition (A) is coated on a film. Apply using wire rod (Meyer's bar) # 8, heat-dry in an oven at 70 ° C for 1 minute, evaporate the solvent, and then irradiate with UV rays to a dose of 30 mJ to cure the coating An antiglare layer was formed. In the antiglare layer, fine particles having a maximum refractive index difference of 0.09 from the binder resin are used as the fine particles. The antiglare layer thus formed has an internal diffusion effect and can more effectively prevent mengilla.

Formation of surface adjustment layer Further, the composition (C) for the surface adjustment layer was applied onto the antiglare layer using a winding rod (Meyer's bar) # 28 for coating, and then in an oven at 70C. After heating and drying for 1 minute to evaporate the solvent, the coating film is cured by irradiating with ultraviolet rays to an irradiation dose of 100 mJ under a nitrogen purge (oxygen concentration of 200 ppm or less), and the surface adjustment layer is formed into a dry film thickness. 15.0 μm was laminated to obtain an antiglare optical laminate. (Total thickness of the antiglare layer on the substrate: about 19 μm)

Example 3
Formation of Antiglare Layer Using a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm as a transparent substrate, the above antiglare layer composition (B) is coated on a film. Apply using wire rod (Meyer's bar) # 8, heat-dry in an oven at 70 ° C for 1 minute, evaporate the solvent, and then irradiate with UV rays to a dose of 30 mJ to cure the coating An antiglare layer was formed. In the antiglare layer, fine particles having a maximum refractive index difference of 0.09 from the binder resin are used as the fine particles. The antiglare layer thus formed has an internal diffusion effect and can more effectively prevent mengilla.

Formation of surface adjustment layer Furthermore, the composition for surface adjustment layer (D) was applied on the antiglare layer using a winding rod for coating (Meyer's bar) # 28, and was heated in an oven at 70C. After heating and drying for 1 minute to evaporate the solvent, the coating film is cured by irradiating with ultraviolet rays to an irradiation dose of 100 mJ under a nitrogen purge (oxygen concentration of 200 ppm or less), and the surface adjustment layer is formed into a dry film thickness. 3.0 μm was laminated to obtain an antiglare optical laminate. (Total thickness of the antiglare layer on the substrate: about 7.5 μm)

Example 4
Formation of Antiglare Layer Using a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm as a transparent substrate, the above antiglare layer composition (B) is coated on a film. Apply using wire rod (Meyer's bar) # 8, heat-dry in an oven at 70 ° C for 1 minute, evaporate the solvent, and then irradiate with UV rays to a dose of 30 mJ to cure the coating An antiglare layer was formed. In the antiglare layer, fine particles having a maximum refractive index difference of 0.09 from the binder resin are used as the fine particles. The antiglare layer thus formed has an internal diffusion effect and can more effectively prevent mengilla.

Formation of surface adjustment layer Furthermore, the composition for surface adjustment layer (B) was applied onto the antiglare layer using a winding rod for coating (Meyer's bar) # 28 in an oven at 70C. After heating and drying for 1 minute to evaporate the solvent, the coating film is cured by irradiating with ultraviolet rays to an irradiation dose of 100 mJ under a nitrogen purge (oxygen concentration of 200 ppm or less), and the surface adjustment layer is formed into a dry film thickness. 0.7 μm was laminated to obtain an antiglare optical laminate. (Total thickness of the antiglare layer on the substrate: about 5 μm)

Example 5
Formation of Antiglare Layer Using a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm as a transparent substrate, the above antiglare layer composition (B) is coated on a film. Apply using wire rod (Meyer's bar) # 8, heat-dry in an oven at 70 ° C for 1 minute, evaporate the solvent, and then irradiate with UV rays to a dose of 30 mJ to cure the coating An antiglare layer was formed. In the antiglare layer, fine particles having a maximum refractive index difference of 0.09 from the binder resin are used as the fine particles. The antiglare layer thus formed has an internal diffusion effect and can more effectively prevent mengilla.

Formation of surface adjustment layer Furthermore, the composition for surface adjustment layer (E) was applied onto the antiglare layer using a winding rod for coating (Meyer's bar) # 28, and then in an oven at 70C. After heating and drying for 1 minute to evaporate the solvent, the coating film is cured by irradiating with ultraviolet rays to an irradiation dose of 100 mJ under a nitrogen purge (oxygen concentration of 200 ppm or less), and the surface adjustment layer is formed into a dry film thickness. 0.9 μm was laminated to obtain an antiglare optical laminate. (Total thickness of the antiglare layer on the substrate: about 5.5 μm)

Formation of Low Refractive Index Layer Further, the composition (A) for the low refractive index layer is applied onto the surface preparation layer using a winding rod for coating (Meyer's bar) # 4, and it is kept in an oven at 50 ° C. for 1 minute. After drying by heating and evaporating the solvent, the coating film is cured by irradiating ultraviolet rays with an irradiation dose of 150 mJ under a nitrogen purge (oxygen concentration of 200 ppm or less), and a low refractive index with a film thickness of about 100 nm. A layer was formed to obtain an antiglare low reflection optical laminate.

Example 6
Formation of Antiglare Layer Using a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm as a transparent substrate, the above antiglare layer composition (B) is coated on a film. Apply using wire rod (Meyer's bar) # 8, heat-dry in an oven at 70 ° C for 1 minute, evaporate the solvent, and then irradiate with UV rays to a dose of 30 mJ to cure the coating An antiglare layer was formed. In the antiglare layer, fine particles having a maximum refractive index difference of 0.09 from the binder resin are used as the fine particles. The antiglare layer thus formed has an internal diffusion effect and can more effectively prevent mengilla.

Formation of surface adjustment layer Furthermore, the composition for surface adjustment layer (F) was applied onto the antiglare layer using a winding rod for coating (Meyer's bar) # 28, and then in an oven at 70C. After heating and drying for 1 minute to evaporate the solvent, the coating film is cured by irradiating with ultraviolet rays to an irradiation dose of 100 mJ under a nitrogen purge (oxygen concentration of 200 ppm or less), and the surface adjustment layer is formed into a dry film thickness. 2.0 μm was laminated to obtain an antiglare optical laminate. (Total thickness of the antiglare layer on the substrate: about 6.5 μm)

Formation of Low Refractive Index Layer Further, the composition (A) for the low refractive index layer is applied onto the surface preparation layer using a winding rod for coating (Meyer's bar) # 4, and it is kept in an oven at 50 ° C. for 1 minute. After drying by heating and evaporating the solvent, the coating film is cured by irradiating ultraviolet rays with an irradiation dose of 150 mJ under a nitrogen purge (oxygen concentration of 200 ppm or less), and a low refractive index with a film thickness of about 100 nm. A layer was formed to obtain an antiglare low reflection optical laminate.

Example 7
Formation of Antiglare Layer Using a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm as a transparent substrate, the above antiglare layer composition (B) is coated on a film. Apply using wire rod (Meyer's bar) # 8, heat-dry in an oven at 70 ° C for 1 minute, evaporate the solvent, and then irradiate with UV rays to a dose of 30 mJ to cure the coating An antiglare layer was formed. In the antiglare layer, fine particles having a maximum refractive index difference of 0.09 from the binder resin are used as the fine particles. The antiglare layer thus formed has an internal diffusion effect and can more effectively prevent mengilla.

Formation of surface adjustment layer Furthermore, the composition for surface adjustment layer (H) was applied onto the antiglare layer using a winding rod for coating (Meyer's bar) # 28, and was then heated in an oven at 70C. After heating and drying for 1 minute to evaporate the solvent, the coating film is cured by irradiating with ultraviolet rays to an irradiation dose of 100 mJ under a nitrogen purge (oxygen concentration of 200 ppm or less), and the surface adjustment layer is formed into a dry film thickness. 0.6 μm was laminated to obtain an antiglare optical laminate. (Total thickness of the antiglare layer on the substrate: about 5 μm)

Comparative Example 1
Formation of an antiglare layer A triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm was used as a transparent substrate, and the antiglare layer composition was coated on a film winding rod (Meyers). Bar) # 8 was applied, dried by heating in an oven at 70 ° C. for 1 minute to evaporate the solvent, and then irradiated with ultraviolet rays to give an irradiation dose of 60 mJ to cure the coating film and to produce an antiglare layer. The surface adjustment layer was not provided.

Comparative Example 2
Formation of an antiglare layer A triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm was used as a transparent substrate, and the antiglare layer composition was coated on a film winding rod (Meyers). Bar) Apply using # 8, heat-dry in oven at 70 ° C. for 1 minute, evaporate the solvent, and then irradiate with ultraviolet rays so that the irradiation dose becomes 30 mJ to cure the coating film and antiglare layer Formed.

Formation of surface adjustment layer Further, the composition for surface adjustment layer (A) was applied on the antiglare layer using a winding rod for coating (Meyer's bar), and 1 in an oven at 70C. After heating and drying for 5 minutes to evaporate the solvent, the coating film is cured by irradiating with ultraviolet rays to an irradiation dose of 100 mJ under a nitrogen purge (oxygen concentration of 200 ppm or less). 5 μm was laminated to obtain an antiglare optical laminate. (Total thickness of the antiglare layer on the substrate: about 11 μm)

Comparative Example 3
Formation of Antiglare Layer Using a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm as a transparent substrate, the above antiglare layer composition (A) is coated on a film. Apply using wire rod (Meyer's bar) # 8, heat-dry in an oven at 70 ° C for 1 minute, evaporate the solvent, and then irradiate with UV rays to a dose of 30 mJ to cure the coating An antiglare layer was formed. In the antiglare layer, fine particles having a maximum refractive index difference of 0.09 from the binder resin are used as the fine particles. The antiglare layer thus formed has an internal diffusion effect and can more effectively prevent mengilla.

Formation of surface adjustment layer Furthermore, the composition (A) for the surface adjustment layer was applied onto the antiglare layer using a winding rod for coating (Meyer's bar) # 28, and in an oven at 70C. After heating and drying for 1 minute to evaporate the solvent, the coating film is cured by irradiating with ultraviolet rays to an irradiation dose of 100 mJ under a nitrogen purge (oxygen concentration of 200 ppm or less), and the surface adjustment layer is formed into a dry film thickness. 20 μm was laminated to obtain an antiglare optical laminate. (Total thickness of the antiglare layer on the substrate: 25 μm)

Comparative Example 4
Formation of Antiglare Layer Using a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm as a transparent substrate, the above antiglare layer composition (B) is coated on a film. Apply using wire rod (Meyer's bar) # 8, heat-dry in an oven at 70 ° C for 1 minute, evaporate the solvent, and then irradiate with UV rays to a dose of 30 mJ to cure the coating An antiglare layer was formed. In the antiglare layer, fine particles having a maximum refractive index difference of 0.09 from the binder resin are used as the fine particles. The antiglare layer thus formed has an internal diffusion effect and can more effectively prevent mengilla.

Formation of surface adjustment layer Further, the composition for low refractive index layer (B) was applied on the antiglare layer using a winding rod for coating (Meyer's bar) # 4 as the surface adjustment layer, and 70 After heating and drying in an oven at ℃ for 1 minute to evaporate the solvent, the coating is cured by irradiating with ultraviolet rays to an irradiation dose of 100 mJ under a nitrogen purge (oxygen concentration of 200 ppm or less) to adjust the surface. The layers were laminated with a dry film thickness of 0.1 μm to obtain an antiglare optical laminate. (Total thickness of the antiglare layer on the substrate: 4.3 μm)

Comparative Example 5
Formation of Antiglare Layer Using a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm as a transparent substrate, the above antiglare layer composition (B) is coated on a film. Apply using wire rod (Meyer's bar) # 8, heat-dry in an oven at 70 ° C for 1 minute, evaporate the solvent, and then irradiate with UV rays to a dose of 30 mJ to cure the coating An antiglare layer was formed. In the antiglare layer, fine particles having a maximum refractive index difference of 0.09 from the binder resin are used as the fine particles. The antiglare layer thus formed has an internal diffusion effect and can more effectively prevent mengilla.

Formation of surface adjustment layer Further, the composition (C) for the low refractive index layer was applied on the antiglare layer using a winding rod (Meyer's bar) # 8 for coating, and in an oven at 70C. After heating and drying for 1 minute to evaporate the solvent, the coating film is cured by irradiating with ultraviolet rays to an irradiation dose of 100 mJ under a nitrogen purge (oxygen concentration of 200 ppm or less), and the surface adjustment layer is dried. A thickness of 0.2 μm was laminated to obtain an antiglare optical laminate. (Total thickness of the antiglare layer on the substrate: 4.5 μm)

Comparative Example 6
Formation of Antiglare Layer Using a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm as a transparent substrate, the above antiglare layer composition (B) is coated on a film. Apply using wire rod (Meyer's bar) # 8, heat-dry in an oven at 70 ° C for 1 minute, evaporate the solvent, and then irradiate with UV rays to a dose of 30 mJ to cure the coating An antiglare layer was formed. In the antiglare layer, fine particles having a maximum refractive index difference of 0.09 from the binder resin are used as the fine particles. The antiglare layer thus formed has an internal diffusion effect and can more effectively prevent mengilla.

Formation of surface adjustment layer Furthermore, the composition (G) for the surface adjustment layer was applied on the antiglare layer using a winding rod (Meyer's bar) # 28 for coating, and was heated in an oven at 70C. After heating and drying for 1 minute to evaporate the solvent, the coating film is cured by irradiating with ultraviolet rays to an irradiation dose of 100 mJ under a nitrogen purge (oxygen concentration of 200 ppm or less), and the surface adjustment layer is formed into a dry film thickness. 0.5 μm was laminated to obtain an antiglare optical laminate. (Total thickness of the antiglare layer on the substrate: about 5 μm)

The obtained optical laminated bodies of Example 1 and Comparative Examples 1 and 2 were evaluated based on the following evaluation methods.

Surface haze and surface adjustment layer thickness For the optical laminates of Example 1 and Comparative Examples 1 and 2, the haze value (%) and surface adjustment layer thickness (μm) were measured according to the definitions in this specification. The results are shown in Table 1.

Refractive index of surface adjustment layer The refractive index of the surface adjustment layer was measured with an Abbe refractometer according to JIS K7142.

Measurement of refractive index and film thickness 2
The refractive index and the film thickness can be obtained as follows in addition to the above-described method. The spectral reflectance of the film on which the film to be measured is laminated is measured with a Shimadzu MPC3100 spectrophotometer, and the 5 ° regular reflectance spectrum is measured in the wavelength range from 380 to 780 nm. (Note that the 5 ° regular reflectance is measured. In order to prevent back reflection of the film which is an optical laminate, the thickness of the optical film is determined from the λ / 4 value of the spectrum. And the refractive index was calculated based on this. The film thickness was calculated from the result of the reflection spectrum. Here, a refractive index of 550 nm is adopted as a representative value.

Glossiness test After pasting a crossed Nicol polarizing plate on the opposite side of the film surface of the optical laminates of Example 1 and Comparative Examples 1 and 2, sensory evaluation was performed under three-wavelength fluorescence. The black feeling was evaluated in detail according to the following criteria.

Evaluation criteria Evaluation ○: Glossy black color could be reproduced.
Evaluation x: A glossy black color could not be reproduced.

Anti-glare sensory test method The back surface of a surface-treated film is subjected to an adhesive treatment and attached to a black acrylic plate as a sample for evaluation. A black and white stripe plate having a width of 20 mm is prepared, and the stripe is reflected on the sample at an angle of 20 degrees from the normal line and observed. At this time, the illuminance of the sample surface was 250 lx, and the luminance (white) of the stripe was 65 cd / m ² . The distance between the stripe plate and the sample was 1.5 m, and the distance between the sample and the observer was 1 m. This is defined as follows according to the appearance of the stripe when viewed by the observer: ○: The stripe cannot be recognized ×: The stripe can be recognized

Results In the examples, both the glossy blackness and the antiglare properties were good at the same time, whereas in the comparative examples, none of the physical properties could be satisfied.

Example 8 Production of non-self-luminous image display device
Preparation of polarizer A polyvinyl alcohol film having a thickness of 75 μm, a polymerization degree of 2,400, and a saponification degree of 99.9% or more was uniaxially stretched at a draw ratio of 5 times by a dry method, and while maintaining a tension state, It was immersed for 60 seconds in an aqueous solution at 28 ° C. containing 0.03 parts by mass of iodine and 5 parts by mass of potassium iodide per 100 parts by mass. Next, while maintaining the tension state, it was immersed for 300 seconds in a boric acid aqueous solution at a temperature of 71 ° C. containing 8.0 parts by mass of boric acid and 6.8 parts by mass of potassium iodide per 100 parts by mass of water. Thereafter, it was washed with pure water at 28 ° C. for 10 seconds. The film washed with water was dried at 50 ° C. for 600 seconds to prepare a polarizer.

Production of polarizing plate and non-self-luminous image display device 1) The surface was immersed in a saponification treatment (2 mol / l NaOH (or KOH) solution: 55 ° C.) for 3 minutes, washed with water, and completely wiped with Kimwipe After removal, the film is dried at 50 ° C. for 1 minute) on an 80 μm-thick triacetylcellulose (TAC) film (first light-transmitting substrate), and 5% by weight polyvinyl alcohol aqueous solution as an adhesive is applied to a dry film thickness of 100 nm. It was bonded to the prepared and adjusted polarizer, dried at 60 ° C. for 5 minutes to remove the solvent, and a TAC protective film was laminated on one side of the polarizer.
2) An antiglare layer and a surface adjustment layer were formed on a triacetylcellulose (TAC) film (second light-transmitting substrate) having a thickness of 80 μm in the same manner as in Example 1 to prepare an optical laminate.
3) This optical layered product was saponified, and a 5% by weight polyvinyl alcohol aqueous solution as an adhesive was applied to the surface opposite to the surface coated with the hard coat so that the film thickness after drying was 100 nm. The polarizer with a single-side protective film produced in step 1) was bonded to the side without the protective film, dried at 60 ° C. for 5 minutes to remove the solvent, and further aged at 40 ° C. for 72 hours to produce a polarizing plate.
This polarizing plate was laminated with a transparent optical adhesive on the polarizing plate portion of the LCD panel as shown in FIG. 2 to obtain a non-self-luminous image display device.

Example 9 Manufacture of self-luminous image display device
Preparation of composite filter for PDP front plate (1) Preparation of electromagnetic wave shielding filter layer:
First, as the transparent base film 11, a biaxially stretched polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name “A4300”) having a continuous strip shape and a non-colored transparent thickness of 100 μm was prepared.
A polyester resin primer layer is formed on one surface of the transparent substrate film, and then a nickel-chromium alloy layer having a thickness of 0.1 μm and a copper layer having a thickness of 0.2 μm are sequentially formed by sputtering. Part) was provided to form a conductive treatment layer. Next, a copper metal plating layer having a thickness of 2.0 μm was provided on the conductive treatment layer surface by an electrolytic plating method using a copper sulfate bath.

Next, a blackening layer was formed on the conductor layer (metal plating layer). Specifically, a nickel plate is used for the anode, and the conductor layer is formed on a transparent substrate film in a blackening treatment plating bath made of a mixed aqueous solution of nickel ammonium sulfate aqueous solution, zinc sulfate aqueous solution and sodium thiocyanate aqueous solution. The laminated film is immersed and subjected to electrolytic plating to blacken, and a blackened layer made of a nickel-zinc alloy is formed on the entire surface of the exposed metal plated layer to form a transparent substrate film. A continuous belt-like laminate in which a conductor layer (a conductive treatment layer, a metal plating layer, and a blackening layer) was laminated on one side was obtained.

Next, the conductive layer of the continuous band-shaped laminate is etched by using a photolithographic method, and the mesh region including the opening portion and the line portion for each display unit to be applied and four rounds of the mesh region are formed. A frame-shaped grounding area was formed on the surrounding outer edge.

In addition, the said etching performed the process from masking to etching consistently with respect to the said continuous strip | belt-shaped laminated body using the manufacturing line for color TV shadow masks. That is, after a photosensitive etching resist is applied to the entire surface of the conductor layer of the laminate, it is closely exposed using a mask having a negative pattern of a desired mesh pattern, developed, hardened, and baked. After the resist layer is processed into a pattern in which the resist layer remains in the portion corresponding to the line portion and the resist layer does not exist in the portion corresponding to the opening portion, the conductor layer (conductive treatment layer is formed by using ferric chloride aqueous solution. And the metal plating layer) and the blackened layer were removed by etching to form a mesh-shaped opening, followed by sequential washing with water, stripping of the resist, washing and drying.

Further, in the above pattern, the mesh shape of the mesh region has a square opening, the line width of the life part which is a non-opening part is 10 μm, the line interval (pitch) is 300 μm, and the height of the line part is 2. When the sheet is cut into rectangular sheets at 3 μm, the bias angle defined as the minor angle with respect to the long side of the rectangle is 49 degrees. In addition, when the continuous band-shaped composite filter is cut into a rectangular sheet for each display unit to be applied (one unit), the mesh area is determined when the composite filter is bonded to the front surface of the PDP. There is a portion that faces the image display region, and a pattern that leaves a frame portion having a width of 15 mm with no opening as a grounding region on the outer periphery of the four sides of the peripheral portion of the mesh-like region is designed.
In this way, a continuous belt-shaped laminate (laminated film in which a conductive mesh layer was laminated on a transparent substrate film) constituting [electromagnetic wave shielding filter layer] was obtained.

(2) Formation of pressure-sensitive adhesive layer (also serves as Ne light absorption and toning filter layer):
Next, the Ne light absorption layer and the pressure-sensitive adhesive layer to which the toning dye is added are formed on the surface opposite to the conductor mesh layer (surface on the transparent substrate film side) of the above-described continuous band-shaped laminate. did. As the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer, an acrylic pressure-sensitive adhesive (Kuraray Co., Ltd., trade name LA2140) is solid in a solvent {methyl ethyl ketone / toluene (solvent blending ratio = 1: 1 by mass)}. The thing melt | dissolved so that it might become 20% (mass basis) of minutes was used.
In the acrylic adhesive solution, 0.009 parts by mass of a porphyrin-based Ne light-absorbing dye (trade name: TAP-2, manufactured by Yamada Chemical Co., Ltd.) and a toning dye (trade name: Plast red 8320, manufactured by Arimoto Chemical Co., Ltd.) ) 0.005 parts by mass were added and dispersed sufficiently to prepare a coating solution.

And it apply | coated with the die coater so that it may become the application amount of 20 g / m < ² > with respect to the surface at the side of the transparent base film used as the back surface of a laminated body, and 100 degreeC in the oven which the dry air with a wind speed of 5 m / sec hits And dried for 1 minute to form a pressure-sensitive adhesive layer. Further, a releasable release film was attached to the surface of the pressure-sensitive adhesive layer for protection.

(3) Formation of NIR absorption filter layer A biaxially stretched polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name “A4300”) having a continuous belt-like and non-colored transparent thickness of 38 μm was prepared.
Next, a polyester resin primer layer was formed on one side of the transparent substrate film.
Next, a near infrared absorbing paint was prepared. That is, an acrylic resin binder is dissolved in a solvent {methyl ethyl ketone / toluene (solvent blending ratio = 1: 1 on a mass basis)} so as to have a solid content of 20% (mass basis), resulting in a phthalocyanine NIR absorption. 0.04 parts by mass of the trade name Excolor IR-10A, 0.02 parts by mass of Excolor 906B, and 0.04 parts by mass of Excolor 910B (all three types manufactured by Nippon Shokubai Co., Ltd.) are added. And sufficiently dispersed to prepare a coating solution.

And it apply | coated with the die coater so that it may become application amount 20g / m < ² > with respect to this primer layer by the side of this transparent base film, and it is 100 degreeC at 1 degreeC in the oven which hits dry air with a wind speed of 5 m / sec. It was dried for a minute to form a near-infrared absorbing layer.

Next, a non-colored transparent pressure-sensitive adhesive layer was formed on the surface of the transparent base film opposite to the near-infrared absorbing layer. As an adhesive, an acrylic adhesive (trade name LA2140, manufactured by Kuraray Co., Ltd.) in a solvent {methyl ethyl ketone / toluene (solvent blending ratio = 1: 1 on a mass basis)} with a solid content of 20% (mass basis) What was melt | dissolved was used.
The pressure-sensitive adhesive coating solution is applied to the coating surface on the film side by a die coater so that the coating amount is 20 g / m ² , and is applied at 100 ° C. for 1 minute in an oven to which dry air with a wind speed of 5 m / sec is applied. After drying, a pressure-sensitive adhesive layer was formed. Further, a releasable release film was bonded to the surface of the pressure-sensitive adhesive layer for protection. Thus, it was set as the NIR absorption filter layer.

(4) Formation of an adhesive layer and UV absorbing filter layer on the back surface of the antiglare filter layer:
The antiglare optical laminate and the antiglare filter layer were the same as in Example 1 except that the transparent substrate film TAC of Example 1 was changed to a polyethylene terephthalate film (film thickness 100 μm, A4300 manufactured by Toyobo Co., Ltd.). Got.
An uncolored transparent pressure-sensitive adhesive layer was formed on the transparent substrate film surface side of the antiglare filter layer. The pressure-sensitive adhesive coating solution is an acrylic pressure-sensitive adhesive (manufactured by Kuraray Co., Ltd., trade name LA2140) as a solvent {methyl ethyl ketone / toluene (solvent blending ratio = 1: 1 on a mass basis)} solid content 20% (mass basis). In addition, a product to which 1% by mass of a benzotriazole ultraviolet absorber was added was used.

The pressure-sensitive adhesive coating solution is applied to the coating surface of the anti-glare filter layer on the transparent substrate film side by a die coater so that the coating amount is 20 g / m ^2. A pressure-sensitive adhesive layer / ultraviolet absorption filter layer was formed by drying at 100 ° C. for 1 minute in a corresponding oven. Further, a releasable release film was bonded to the surface of the pressure-sensitive adhesive layer for protection.

(5) Lamination and compounding of each filter layer Each filter layer produced as described above was laminated and compounded.
First, the release film on the back surface is peeled and removed from the antiglare filter layer prepared in (4), and the NIR absorption filter layer prepared in (3) is exposed to near-infrared absorption on the exposed adhesive layer / ultraviolet absorption filter layer side. The laminated body which consists of [Anti-glare filter layer / adhesive layer and UV absorption filter layer / NIR absorption filter layer] was formed by contacting the layer side and applying pressure between a pair of rollers. A schematic diagram of the composite filter thus formed is shown in FIG.

Next, the release film is peeled and removed from the back surface of the NIR absorption filter layer of the obtained laminate, and the exposed adhesive layer is brought into contact with the conductor layer of the electromagnetic wave shielding filter layer prepared in (1). A laminate comprising [antiglare filter layer / adhesive layer / UV absorbing filter layer / NIR absorption filter layer / electromagnetic wave shielding filter layer / Ne light absorption and toning filter layer / adhesive layer] And a composite filter for a PDP front plate was obtained.
The composite filter produced as described above is laminated on the front plate of the PDP glass substrate as shown in FIG. 4 by applying the adhesive as implemented in (3), and a self-luminous image display device is obtained. Produced.

Example 10 Self-luminous image display device PDP front plate composite filter 2
(1) Creation of electromagnetic wave shielding filter layer:
First, as a conductor layer, a continuous strip-shaped electrolytic copper foil having a thickness of 10 μm in which a blackening layer made of copper-cobalt alloy particles was formed on one surface by electrolytic plating was prepared. After galvanizing on both surfaces of the copper foil, a known chromate treatment was performed by a dipping method to form rust prevention layers on both the front and back surfaces.

In addition, as a transparent resin base film, a continuous strip-shaped non-colored transparent biaxially stretched polyethylene terephthalate film (manufactured by Teijin DuPont Films, trade name “HBPF8W”) having a thickness of 100 μm was prepared. In addition, this base film is formed by mixing an ultraviolet absorber and also has an ultraviolet absorption filter layer.
Next, a polyester resin primer layer was formed on both sides of the base film.

Next, the copper foil is coated on the primer layer of the base film on the blackened layer side from 12 parts by mass of a polyester polyurethane polyol having an average molecular weight of 30,000, and the curing agent is 1 part by mass of a xylene diisocyanate prepolymer. After dry laminating with a transparent two-component curable urethane resin adhesive consisting of the following, it is cured at 50 ° C. for 3 days, and a transparent adhesive layer having a thickness of 7 μm is formed between the copper foil (rust preventive layer) and the transparent base film. A continuous belt-like laminate having the following was obtained.

Next, the conductive layer and the blackened layer are etched on the continuous band-shaped laminate by using a photolithographic method, and the mesh-shaped region including the opening portion and the line portion, and four rounds of the mesh-shaped region are formed. A conductive mesh layer having a frame-shaped mesh-free grounding region was formed on the surrounding outer edge.

Specifically, using a production line for a color TV shadow mask, the etching was performed consistently from masking to etching on the continuous belt-like laminated sheet. That is, after applying a photosensitive etching resist to the entire surface of the conductor layer of the laminated sheet, a desired mesh pattern is closely exposed, developed, hardened, and baked on the area corresponding to the line portion of the mesh. After processing the resist layer into a pattern in which the resist layer remains and there is no resist layer on the area corresponding to the opening, the conductor layer and the blackened layer are etched away with an aqueous ferric chloride solution. A mesh-shaped opening was formed, and then water washing, resist peeling, washing, and drying were sequentially performed.

Next, on the exposed conductive mesh layer, a resin composed of PMMA (Tg around 130 ° C.) is made into a composition having a solid content of 20% with a solvent (methyl ethyl ketone / toluene = 1/1) and dried by a die coater. Coating was carried out so that the coating amount was 20 g / m ^2, and a transparent layer was laminated to form a mesh protective layer.
In this way, a laminate composed of [ultraviolet absorption filter layer / electromagnetic wave shielding filter layer] was obtained.

(2) Formation of Ne light absorption, NIR absorption, and toning filter layer:
A resin binder of an acrylic resin (glass transition temperature 130 ° C., hydroxyl value = 0) in a solvent {methyl ethyl ketone / toluene (solvent blending ratio = 1: 1 on a mass basis)} has a solid content of 20% (mass basis). In the thus-dissolved acrylic resin solution, 0.04 parts by mass of the trade name Excolor IR-10A, 0.02 parts by mass of Excolor 906B, 0.02 parts by mass of Excolor 906B, and Excolor 910B (both of the above three types) are phthalocyanine NIR absorbing dyes. 0.04 parts by mass of Nippon Shokubai Co., Ltd., 0.009 parts by mass of porphyrin-based Ne light-absorbing dye (trade name: TAP-2, Yamada Chemical Co., Ltd.), and toning dye (trade name: Plast red 8320 Arimoto) Chemical Co., Ltd.) 0.005 parts by mass were added and dispersed sufficiently to prepare a coating solution.

And it apply | coated so that it might become application amount 20g / m < ² > with the die coater on the conductor layer of this laminated body, and it dried at 100 degreeC for 1 minute in the oven which hits dry air with a wind speed of 5 m / sec, A non-adhesive solid was formed, and a layer serving as both Ne light absorption, NIR absorption, and a toning filter layer was formed.
In this way, a laminate composed of [UV absorption filter layer (also transparent substrate film) / electromagnetic wave shielding filter layer / Ne light absorption, NIR absorption, and toning filter layer] was obtained.

(3) Formation of anti-glare filter layer:
An antiglare filter layer formed by forming an adhesive layer on the back surface was obtained in the same manner as in Example 3 except that no ultraviolet absorber was added to the adhesive layer.

(4) Lamination and compounding of each filter layer Each filter layer produced as described above was laminated and compounded.
First, an uncolored transparent glass plate having a thickness of 5 mm was prepared.
Next, the release film on the back surface is peeled and removed from the antiglare filter layer prepared in (3), and the exposed adhesive layer side is brought into contact with one surface of the glass plate and pressed between a pair of rollers. And laminated.
Next, the obtained laminate is prepared in (1) and (2) via an adhesive layer having a coating amount of 20 g / m ² on the other side of the glass plate (side without the antiglare filter layer). The laminated body of the electromagnetic wave shielding filter layer and the Ne light absorption, NIR absorption, and toning filter was laminated by pressing between a pair of rollers so that the transparent base film side faces the glass plate side.
In this way, a laminate composed of [antiglare filter layer / adhesive layer / glass plate / electromagnetic wave shielding filter layer / Ne light absorption, NIR absorption, and toning filter layer] was formed, and before the PDP of Example 7 A composite filter for the face plate was obtained.

As shown in FIG. 5, this composite filter was incorporated into the front surface of the PDP front plate via a spacer and a metal fitting to form a self-luminous image display device.

Each of the image display devices of Examples 8 to 10 had properties excellent in antiglare property and black reproducibility (glossy blackness).

The optical laminate of the present invention can be used as an antireflection film for cathode ray tube display (CRT), liquid crystal display (LCD), plasma display (PDP), electroluminescence display (ELD) and the like.

It is a schematic diagram which shows an example of the optical laminated body of this invention. FIG. 10 is a schematic diagram illustrating a stacked structure of a non-spontaneous light emission type image display device of Example 8. 10 is a schematic diagram showing a laminated structure of a composite filter of Example 9. FIG. It is a schematic diagram which shows the structure of a PDP glass substrate. It is sectional drawing of the spontaneous issue type image display apparatus of Example 10. FIG.

Explanation of symbols

11. Light transmissive substrate 12. Antiglare layer 13. Surface adjustment layer 14. Organic fine particles or inorganic fine particles 21. Glass substrate inside display 22. Pixel unit 23. Black matrix layer 24. Color filters 25, 27. Transparent electrode layer 26. Back side glass substrate 28. Sealing material 29. Alignment film 210. Polarizing film 211. Backlight unit 31. Surface adjustment layer 32. Antiglare layer 33. Polyethylene terephthalate layer 34. Adhesive layer 35. NIR layer 36. Conductor mesh layer 41. Glass substrate (front plate)
42. Display electrode (transparent electrode + pass electrode)
43. Transparent dielectric layer 44. MgO
45. Dielectric layer 46. Glass substrate (back plate)
47. Address electrode 48. Phosphor 51. Plasma display panel (PDP)
52. Front filter
53. Spacer 54. Enclosure 55. Screw 56. Front (display surface)

Claims (12)

An optical laminate having irregularities on the surface,
An antiglare layer having irregularities on the surface provided on the light-transmitting substrate, and a surface adjustment layer provided on the antiglare layer,
The surface adjusting layer contains a resin binder and a fluidity adjusting agent. The optical laminate according to claim 1, wherein the surface adjustment layer has a thickness of 0.6 μm to 15 μm. The optical laminate according to claim 1, wherein the surface adjustment layer has a refractive index of 1.49 to 1.82. 4. The optical laminate according to claim 1, wherein the resin binder is an ionizing radiation curable resin. The optical laminate according to claim 1, 2, 3, or 4, wherein the fluidity controlling agent is colloidal silica. 6. The optical laminate according to claim 1, further comprising a low refractive index layer on the surface adjustment layer. By the step (1) of providing an antiglare layer having irregularities on a light-transmitting substrate and the composition for forming a surface adjustment layer containing a resin binder and colloidal silica on the antiglare layer obtained by the step (1). The optical layered body according to claim 1, comprising a step of forming a surface adjustment layer. A polarizing plate comprising a polarizing element,
The polarizing plate comprises the optical layered body according to claim 1, 2, 3, 4, 5, or 6 on the surface of a polarizing element. An image display device comprising the optical laminate according to claim 1, 2, 3, 4, 5, or 6 or the polarizing plate according to claim 8 on an outermost surface. A non-self-luminous image display device comprising the optical laminate according to claim 1, 2, 3, 4, 5, or 6 or the polarizing plate according to claim 8 on an outermost surface. A self-luminous image display device comprising the optical laminate according to claim 1, 2, 3, 4, 5, or 6 on an outermost surface. By the step (1) of providing an antiglare layer having irregularities on a light-transmitting substrate and the composition for forming a surface adjustment layer containing a resin binder and colloidal silica on the antiglare layer obtained by the step (1). The method for producing an optical laminated body according to claim 1, comprising a step of forming a surface adjustment layer.

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