KR101217964B1 - Optical layered product, polarizer, display device and method for producing optical layered product - Google Patents

Abstract

assignment
It aims at providing the optical laminated body which is excellent in anti-glare property and black part under clear light, and has the structure which can achieve high dark room contrast, and is excellent in manufacturing stability, and the manufacturing method of the said optical laminated body. Another object of the present invention is to provide a polarizing plate and a display device including the optical laminate.
Solution
An optical laminate comprising an optical functional layer laminated on a light-transmissive substrate, the optical functional layer having a first phase containing a relatively large amount of resin components and a second phase containing a relatively large amount of inorganic components and fine particles, A 2nd phase is unevenly distributed around microparticles | fine-particles, The optical laminated body characterized by the above-mentioned.

Description

Optical laminated body, polarizing plate, display device and manufacturing method of optical laminated body {OPTICAL LAYERED PRODUCT, POLARIZER, DISPLAY DEVICE AND METHOD FOR PRODUCING OPTICAL LAYERED PRODUCT}

This invention relates to the optical laminated body, polarizing plate, display apparatus, and the manufacturing method of an optical laminated body characterized by the 2nd image unevenly distributed around the microparticles | fine-particles of the optical functional layer which comprises an optical laminated body. The optical laminated body of this invention is installed in the display surface, such as a liquid crystal display (LCD), a plasma display (PDP), an organic electroluminescent element (OLED), is used as one component of a display, or an organic electroluminescent layer which comprises OLED In order to improve the efficiency of emitting light generated in the outside of the organic EL, it can be preferably used on the observation surface side. In particular, visibility such as anti-glare property, blackness under dark room, and dark room contrast are emphasized. For example, it is related with the optical laminated body which can be used suitably for the display etc. which are used for television.

Display devices such as a liquid crystal display (LCD) or a plasma display (PDP) may interfere with visibility of an image due to indoor lighting such as a fluorescent lamp, incident light from a window, projection of a shadow of an operator, or the like on the surface of the display device. . Therefore, in order to improve the visibility of the image on the display surface, such as an optical laminated body in which a fine uneven structure is formed to diffuse the surface reflected light to suppress specular reflection of external light and to prevent projection of the external environment (having anti-glare). The functional film is installed on the outermost surface.

Such a functional film is provided with an optical functional layer having a fine uneven structure formed on a light-transmissive substrate such as polyethylene terephthalate (hereinafter referred to as "PET") and triacetyl cellulose (hereinafter referred to as "TAC"), The lamination | stacking of the low refractive index layer on the light-diffusion layer is generally manufactured and sold, and the development of the functional film which provides a desired function by the combination of laminated constitution is progressing.

When the optical laminated body is used for the outermost surface of the display, when used in a bright space, there is a problem that the image of the black display becomes white due to light diffusion and the contrast decreases. For this reason, the optical laminated body which can achieve high contrast, even if anti-glare property is reduced (high contrast AG). As a method of improving the contrast of an optical laminated body, optimization of the uneven | corrugated shape of a surface is mentioned, for example.

As a method of forming an uneven shape on the surface of the optical functional layer, after coating the optical functional layer-forming paint containing fine particles on the light-transmissive substrate, the optical functional layer forming material is irradiated with ultraviolet rays to form an optical functional layer. It is common (for example, refer patent document 1).

Moreover, there also exists a method of making anti-glare property and contrast compatible by optimizing the particle diameter and surface uneven | corrugated shape (tilt angle) of microparticles | fine-particles contained in an optical function layer (for example, refer patent document 2).

In addition, there is also a method of forming surface irregularities without containing fine particles by using a plurality of resin components and forming a string structure using the phase separation characteristics of the resin component to achieve both anti-glare and contrast (for example, See Patent Document 3).

Japanese Patent Application Laid-Open No. 2002-196117 Japanese Patent Laid-Open No. 2008-158536 Japanese Patent Laid-Open No. 2008-225195

When using the optical function layer containing microparticles | fine-particles like patent document 1, it is effective for an anti-glare property and an anti-glare effect. However, since scattering of light occurs in the interface of the fine particles contained in the optical functional layer and the surface irregularities of the optical functional layer based on the shape of the fine particles, it is difficult to achieve high contrast.

As in Patent Document 2, there was a problem of insufficient contrast even when the particle diameter of the fine particles and the inclination angle of the surface irregularities were optimized.

As in Patent Literature 3, a method of forming a string-shaped convex portion on the surface using phase separation of a plurality of resin components has a problem in manufacturing stability.

Therefore, an object of the present invention is to provide an optical laminated body which is excellent in anti-glare property and blackness under bright room, and which can achieve high dark room contrast, and which is excellent in manufacturing stability and a method for producing the optical laminated body. do. It is also an object of the present invention to provide a polarizing plate and a display device comprising the optical laminate.

The present invention was able to solve the above problems by the following technical configuration.

(1) The optical laminated body in which the optical functional layer is laminated | stacked on the translucent base | substrate, The said optical functional layer is the 1st phase which contains a relatively large resin component, the 2nd phase which contains a relatively large inorganic component, and An optical laminated body containing fine particles, wherein a second phase is unevenly distributed around the fine particles.

(2) Said inorganic component is inorganic nanoparticle, The optical laminated body as described in said (1) characterized by the above-mentioned.

(3) Said 2nd phase is an aggregate of inorganic nanoparticles, The optical laminated body as described in said (1) characterized by the above-mentioned.

(4) The optical laminate according to (1), wherein the second phase contains 0.2% by weight or more of an inorganic component.

(5) The polarizing plate was laminated | stacked on the translucent base which comprises the optical laminated body in any one of said (1)-(4), The polarizing plate characterized by the above-mentioned.

(6) The display device characterized by including the optical laminate according to any one of (1) to (4).

(7) a drying step of applying a solution containing a resin component, an inorganic component, fine particles, a first solvent, and a second solvent onto the light-transmissive gas, and generating convection with volatilization of the first solvent and the second solvent, and A hardening process of hardening a dried coating film and forming an optical functional layer, The manufacturing method of the optical laminated body characterized by the above-mentioned.

According to the present invention, it is possible to provide an optical laminate and a method for producing the optical laminate, which have a structure having excellent antiglare property and blackness under bright room and at the same time achieving high dark room contrast. Moreover, the polarizing plate and display apparatus which comprise the said optical laminated body can be provided.

Furthermore, according to this invention, the optical laminated body which can be used suitably for the television application which requires high contrast can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS The schematic diagram which shows the structure of an optical function layer, Comprising: (a) top view of sea island structure, (b) top view of random aggregation structure, (c) cross section side view of sea island structure, (d) cross section of random aggregation structure Side view.
2 is a SEM photograph of the structure of the surface of the optical functional layer according to Example 1 after carbon deposition.
3 is a SEM photograph of a cross section of the laminate according to Example 1 after carbon deposition.
4 is a photograph of mapping the structure of the surface of the optical functional layer according to Example 1 by EDS to the inorganic component (Si).
5 is a SEM photograph of the structure of the surface of the optical functional layer according to Comparative Example 3 after carbon deposition.
6 is a photograph in which the structure of the surface of the optical functional layer according to Comparative Example 3 is mapped by EDS to the inorganic component (Si).
FIG. 7 is a SEM photograph of the island-in-sea structure of the surface of the optical functional layer according to Comparative Example 5 after carbon deposition.

The present invention will be described below. The optical functional layer which comprises this invention has a random aggregation structure. 1 is a diagram schematically illustrating the structure of an optical functional layer. (a) and (b) is a top view which shows the surface structure of an optical function layer, (c) and (d) is a side sectional view which shows the cross-sectional structure of the optical laminated body side surface. (a) and (c) are optical functional layers of a conventional sea island structure, and (b) and (d) are optical functional layers having a random aggregation structure.

Since the optical functional layer which comprises this invention should just have a 1st phase and a 2nd phase, an optical functional layer may have a 3rd phase and a 4th phase, and the number of phases which comprise an optical functional layer is not restrict | limited. . For example, the optical functional layer may have a lamer structure. Specifically, the other phase (for example, 3rd phase) is formed on the unevenness | corrugation of the optical function layer 16 in FIG.1 (d).

As shown to Fig.1 (b) and (d), the optical function layer which comprises this invention contains the 1st phase 1 containing relatively many resin components at least, and the said resin component relatively few (inorganic) Relatively high content of components) and second phase (2). These second phases 2 are each present in various sizes and shapes. The first phase 1 and the second phase 2 constituting the optical functional layer are intertwined in three dimensions.

Moreover, the microparticles | fine-particles 3 exist in the optical function layer 16 which comprises this invention. In the circumference | surroundings of this microparticles | fine-particles 3, the 1st phase 1 which comprises the optical function layer 16 hardly exists, and the 2nd phase 2 exists. That is, the 2nd phase 2 exists ubiquitous around the microparticles | fine-particles 3 which comprise the optical function layer 16. FIG. The uneven distribution of the second phase 2 around the fine particles 3 can be confirmed using a laser microscope, a scanning electron microscope (SEM), an energy dispersive X-ray spectrometer (EDS), or the like.

In this invention, it is judged based on the SEM result seen from the optical functional layer surface of an optical laminated body whether "the 2nd phase is unevenly distributed around a particle." First, ten fine particles are arbitrarily selected from the SEM results. Next, the ratio of the second phase among the first phase and the second phase existing in the concentric circles 10 times the long diameter of the fine particles is determined from the respective fine particle centers. Next, an average value of the proportion of the second phase in any of ten concentric circles is calculated. If the average value is relatively high compared to the comparative control, the second phase is ubiquitous around the fine particles, and if the average value is relatively low compared to the comparative control, the second phase is ubiquitous around the fine particles. It is not applicable.

Comparative controls are obtained from the SEM results. The comparative control centers on the ten points present in the first phase and corresponds to concentric circles 10 times the size of each of the particulate long diameters. However, 10 points here are all provided in the part which does not contain microparticles | fine-particles in the said concentric circles. In this way, the average value of the ratio which the 2nd phase occupies in the concentric circle centering on 10 points is computed.

In the present invention, the optical functional layer includes a first phase and a second phase, and the first phase and the second phase are intertwined in three dimensions, and the random structure comprises a random structure in which the second phase is unevenly distributed around the fine particles. It is called.

As shown in Fig. 1 (c), the optical functional layer 15 has formed surface irregularities on the light-transmitting substrate 20 by using the shapes of the fine particles 30 and 31. That is, since the resin 40 present on the fine particles 30 and 31 rises along the shape of the fine particles, and the resin 40 does not rise in the portion where the fine particles 30 and 31 do not exist, the convex portion As the concave portions were alternately formed, the surface irregularities of the optical functional layer 15 had a large inclination. 1 (a) and (c), even when a plurality of fine particles are present together to form surface irregularities, such surface irregularities have a large inclination.

On the other hand, since the second phase 2 is unevenly distributed around the fine particles 3 in the optical functional layer 16 of the present invention, as compared with the conventional optical functional layer shown in Figs. 1 (a) and (c), It can reduce fine irregularities and improve blackness under high anti-glare and bright room. This improves the degree of blackness under the bright room with the first phase by forming the relatively flat surface of the optical functional layer constituting the first phase, and at the same time achieves high darkroom contrast and is convex by the fine particles received in the second phase. Since a part is formed, an anti-glare effect is achieved by the microparticles | fine-particles accommodated in the said 2nd phase.

In addition, when microparticles | fine-particles exist in a 1st phase and a 2nd phase, and a 2nd phase is not unevenly distributed around microparticles | fine-particles, since an unevenness | corrugation is formed in various parts of an optical function layer (the number of unevenness | corrugation increases), an optical functional layer becomes white, and it is unpreferable. not. Moreover, since it is difficult to control the number, height, etc. of surface asperity, it is difficult for the optical function layer which does not contain microparticles | fine-particles, and manufacturing is not preferable.

The optical functional layer which comprises this invention should just have a random aggregation structure as a main structure, for example, another structure (for example, sea island structure) may exist in a part.

After depositing gold on the random aggregation structure formed by the present invention and observing with an electron microscope, it can be seen that the fine particles contained in the optical functional layer form convex portions of the surface irregularities.

In addition, after the carbon deposition is performed on the random agglomerated structure formed by the present invention, the element distribution in terms of carbon deposition can be roughly confirmed by observing with an electron microscope. This is because a plurality of elements exist on the surface of carbon deposition, but for example, the larger the atomic number is classified into white, the smaller the atomic number is displayed in black, and the like, so that the element distribution can be distinguished by light and shade of color.

Furthermore, in the optical functional layer and the random aggregation structure formed by the present invention, mapping by EDS can be performed to identify the elements present on the surface of the coating film (optical functional layer) or on the cross section of the coating film (optical functional layer). The mapping by this EDS can color display the part in which many specific elements (for example, a carbon atom, an oxygen atom, a silicon atom, etc.) are distributed.

The electron microscope observation and the mapping by EDS can confirm the uneven structure and the distribution of a specific element of a random aggregation structure. Thereby, for example, in the convex part of surface asperity, it can confirm which specific element is distributed a lot.

2 and 4 will be described in more detail. 2 and 4 are photographed at the same time in the surface state of the optical functional layer manufactured by Example 1 described later, and the optical functional layer is composed of a resin component, an inorganic component and fine particles.

2 is an SEM photograph of carbon deposition on the surface of the optical functional layer. The image displayed by the reflective electron detector represents the reflected electrons resulting from the component contained in the surface of the optical functional layer as an image.

The reflected electrons depend on the atomic number, and can be classified and displayed, for example, in which a large atomic number is displayed in white, in which a small atomic amount is displayed in black, and the like. As shown in FIG. 2, the optical functional layer is not comprised uniformly in each element inside in a surface horizontal direction, but is comprised from the part with relatively large content of an element with a large atomic number, and the part with relatively small content.

4 shows the result of mapping the inorganic component (Si) by EDS on the surface of the optical functional layer, and shows the amount of the Si component contained in shades of color. As shown in FIG. 4, the Si component is composed of a portion having a relatively high content and a portion having a relatively small content. In addition, although FIG. 4 shows the mapping result of a silica (Si) for the specific example, it is also possible to show the mapping result of another inorganic component element or resin (organic) component. In the mapping result shown in FIG. 4, it can detect that inorganic components, such as a silica, are concentration of 0.2 weight% according to detection conditions. That is, in the optical functional layer consisting of two phases of the first phase and the second phase, the first phase is composed of at least 90% by weight of the resin component and the inorganic component, and the second phase is less than 99.8% by weight of the resin component and 0.2% by weight. It is comprised from the above inorganic component. It is preferable that it is 95 weight% or more, and, as for the resin component contained in a 1st phase, it is more preferable that it is 99 weight% or more. It is preferable that the inorganic component contained in a 2nd phase is 1% or more, It is more preferable that it is 5% or more, It is especially preferable that it is 10% or more. It is preferable that the resin component contained in a 2nd phase is less than 99%, It is more preferable that it is less than 95%, It is especially preferable that it is less than 90%. The amount of the inorganic component included in the optical functional layer is included in much of the second phase compared to the first phase.

The content of the components other than the resin component is relatively small in the portion where the content of the resin component is relatively large (part where the color is dark in FIG. 2) (first phase).

On the other hand, the content of the components other than the resin component is relatively high in the portion where the content of the resin component is relatively small (the non-dark colored portion in FIG. 2) (second phase).

That is, the optical functional layer which concerns on this invention exists in which the 1st phase and the 2nd phase are intertwined, and when one component becomes small, it has a complementary relationship that the other component increases.

In addition, although FIG.2 and FIG.4 shows content of each component in the surface horizontal direction of an optical function layer, it is the same complement also when showing content of each component in the vertical direction (thickness direction) of an optical function layer. A result showing the relation can be obtained (FIG. 3).

<Method of forming a random aggregation structure>

The random agglomerated structure of the present invention can be produced using a phenomenon in which aggregates of inorganic components are randomly localized along with convection during volatilization of a solvent around the fine particles. Specifically, a solution containing a resin component, an inorganic component, fine particles, and a solvent (a first solvent and a second solvent) is applied onto the light transmitting gas, and convection is carried out with the volatilization of the solvent (the first solvent and the second solvent). It can manufacture through the drying process to generate | occur | produce, and the hardening process which hardens a dried coating film and forms an optical functional layer. More specifically, it can be normally carried out by coating the solution on a light-transmissive gas and evaporating the solvent from the coating layer.

Although the detailed mechanism in the combination of aggregation and convection is not known, it can be estimated as follows.

(1) By condensation accompanying convection at the time of solvent volatilization, a convection domain arises first in the coating layer after application | coating.

(2) Next, aggregation of the inorganic material occurs in each convective domain, and the aggregate becomes large with time, but the growth of the aggregation at the convective domain wall stops. With the occurrence and time of aggregation, the inorganic component aggregates with the fine particles as the nucleus.

(3) As a result, the size of the aggregate is properly maintained and these are scattered in the optical functional layer to form a random aggregated structure.

According to the surface unevenness accompanying the random aggregation structure in the present invention, it is possible to achieve both the anti-glare property, the clear and dark contrast, which are difficult in the surface unevenness of the conventional islands-in-the-sea structure.

Below, the material which can be preferably used for each layer which comprises this invention is demonstrated.

<Transparent gas>

The light-transmissive gas according to the best mode according to the present invention is not particularly limited as long as it has light transmittance, and glass such as quartz glass or soda glass may be used, but PET, TAC, polyethylene naphthalate (PEN), and polymethyl meta Acrylate (PMMA), polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cycloolefin copolymer Various resin films, such as (COC), norbornene containing resin, an acrylic resin, a polyether sulfone, a cellophane, and an aromatic polyamide, can be used suitably. Moreover, when using for PDP and LCD, it is more preferable to use 1 type chosen from PET film, TAC film, and norbornene containing resin film.

The transparency of these light-transmissive substrates is preferably high, but the total light transmittance (JIS K7105) is preferably 80% or more, more preferably 90% or more. The thickness of the light-transmissive substrate is preferably thin from the viewpoint of weight reduction, but considering the productivity and operability, it is very preferable to use one in the range of 1 to 700 µm, preferably in the range of 25 to 250 µm. .

Translucent substrates are treated with alkali treatments, corona treatments, plasma treatments, spatter treatments, primer coatings such as surfactants and silane coupling agents, and thin film dry coatings such as Si deposition. The adhesion between the base and the optical functional layer can be improved, and the physical strength and chemical resistance of the optical functional layer can be improved. Moreover, also when forming another layer between a translucent base and an optical function layer, the interface adhesiveness of each layer can be improved and the physical strength and chemical-resistance of the said optical function layer can be improved by the same method as the above.

<Optical functional layer>

The optical functional layer contains a resin component and an inorganic component and is formed by curing the resin component. The optical functional layer contains fine particles (inorganic fine particles or organic fine particles).

(Resin ingredient)

As a resin component which comprises an optical function layer, if it has sufficient intensity | strength and transparency as a film after hardening, it can use without a restriction | limiting in particular. Examples of the resin component include a thermosetting resin, a thermoplastic resin, an ionizing radiation curable resin, a two-liquid mixed resin, and the like, and among these, by a simple and easy processing operation in accordance with the curing treatment by electron beam or ultraviolet irradiation. The ionizing radiation curable resin that can be cured is very suitable.

As an ionizing radiation curable resin, it has radically polymerizable functional groups, such as acryloyl group, methacryloyl group, acryloyloxy group, and methacryloyloxy group, and cationically polymerizable functional groups, such as an epoxy group, a vinyl ether group, and an oxetane group. Compositions in which the monomers, oligomers, prepolymers, and polymers are singly or appropriately mixed are used. Examples of monomers include methyl acrylate, methyl methacrylate, methoxy polyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, ethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, trimethylolpropane tri Methacrylate, pentaerythritol triacrylate, and the like. As oligomers and prepolymers, acrylate compounds such as polyester acrylate, polyurethane acrylate, polyfunctional urethane acrylate, epoxy acrylate, polyether acrylate, alkyd acrylate, melamine acrylate, silicone acrylate, unsaturated polyester Epoxy compounds such as tetramethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether, and various alicyclic epoxy, 3-ethyl-3 Hydroxymethyl oxetane, jade such as 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl benzene, di [1-ethyl (3-oxetanyl)] methyl ether Cetane compound is mentioned. Examples of the polymer include polyacrylates, polyurethane acrylates, polyester acrylates, and the like. These can be used individually or in mixture of multiple.

Among such ionizing radiation curable resins, the polyfunctional monomer having three or more functional groups can speed up the curing rate or improve the hardness of the cured product. Moreover, hardness, flexibility, etc. of hardened | cured material can be provided by using polyfunctional urethane acrylate.

An ionizing radiation curable fluorinated acrylate can be used as the ionizing radiation curable resin. The ionizing radiation curable fluorinated acrylate is an ionizing radiation curable type compared to other fluorinated acrylates. Since crosslinking occurs between molecules, the effect of expressing sufficient antifouling property even after saponification treatment is achieved. As an ionizing radiation hardening type fluorinated acrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 3- (perfluoro-7-) Methyloctyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-9-methyldecyl) ethyl methacrylate, 3- (perfluoro-8-methyldecyl) -2-hydroxypropylmethacryl Late, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (perfluoro-9-methyldecyl) ethyl acrylate, pentadecafluorooctyl (Meth) acrylate, undecafluorohexyl (meth) acrylate, nonafluoropentyl (meth) acrylate, heptafluorobutyl (meth) acrylate, octafluoropentyl (meth) acrylate, pentafluoropropyl (Meth) acrylate, trifluoro (meth) acrylate, triisofluoroiso Propyl (meth) acrylate, trifluoroethyl (meth) acrylate, the following compound (i)-(xxxi), etc. can be used. In addition, all the following compounds show the case of an acrylate, and all the acryloyl group in a formula can be changed into a methacryloyl group.

[Formula 1]

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

    These can also be used individually or in mixture of multiple types. The fluorinated alkyl group-containing urethane acrylate having a urethane bond in the fluorinated acrylate is more preferable in view of wear resistance, elasticity and flexibility of the cured product. Moreover, polyfunctional fluorinated acrylate is very preferable among fluorinated acrylate. Furthermore, the polyfunctional fluorinated acrylate here means having two or more (preferably three or more, more preferably four or more) (meth) acryloyloxy groups.

Although the ionizing radiation curable resin can be cured by electron beam irradiation itself, a photopolymerization initiator can be added when curing is performed by ultraviolet irradiation. In addition, any of ultraviolet rays, visible rays, infrared rays, and electron beams may be used as the radiation used. Moreover, such radiation may be polarized or unpolarized.

As a photoinitiator, Cation, such as an acetphenone series, benzophenone series, a thioxanthone series, benzoin, radical polymerization initiators, such as a benzoin methyl ether, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, etc. The polymerization initiator can be used alone or in combination as appropriate.

Moreover, additives, such as a smoothing agent (leveling agent) and an antistatic agent, can be contained in ionizing radiation hardening type resin. The smoothing agent aims at equalizing the tension of the coating film surface and has a function of healing defects before the coating film is formed.

Examples of the smoothing agent include a silicone leveling agent, a fluorine leveling agent, and an acrylic leveling agent. The said smoothing agent may be used independently and may use 2 or more types together. Among the above leveling agents, a silicone leveling agent and a fluorine leveling agent are preferable, and a silicon leveling agent is particularly preferable from the viewpoint of forming an uneven structure on the optical functional layer.

As said silicone type smoothing agent, polyether modified silicone, polyester modified silicone, perfluoro modified silicone, reactive silicone, polydimethylsiloxane, polymethyl alkylsiloxane, etc. are mentioned, for example.

As such silicone-based smoothing agent, "SILWET series", "SUPERSILWET series", "ABNSILWET series" made by Nippon Unicar, "KF series" made by Shin-Etsu Chemical Co., Ltd., "X-22 series", Big Chemi Japan Co., Ltd. BYK-300 series made by Kyoeisha Chemical, "Glanol Series", manufactured by Toray Dow Corning Corporation, "SH Series", "ST Series", "FZ Series" ) "FM series", "TSF series" by GE TOSHIBA Silicone Co., Ltd. (above brand name), etc. are marketed.

As a fluorine-type smoother, the compound which has a fluoro alkyl group is preferable. Such a fluoroalkyl group may have a linear or branched structure having 1 to 20 carbon atoms, an alicyclic structure (preferably a 5- or 6-membered ring), or may have an ether bond. The fluorine-based smoothing agent may be a polymer or oligomer.

Moreover, as a fluorine-type smoothing agent, the smoothing agent which hydrophobic group has a perfluoro carbon chain is mentioned. Specifically, fluoroalkyl carboxylic acid, N-perfluorooctanesulfonyl glutamate, sodium 3- (fluoroalkyloxy) -1-alkylsulfonate, 3- (ω-fluoroalkanoyl-N-ethylamino) -1-sodium propanesulfonic acid, N- (3-perfluorooctanesulfonamide) propyl-N, N-dimethyl-N-carboxymethylene ammonium betaine, perfluoroalkylcarboxylic acid, perfluorooctane sulfonic acid diethanolamide, Perfluoroalkylsulfonate, N-propyl-N- (2-hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkylsulfonamidepropyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, Phosphate bis (N-perfluorooctylsulfonyl N-ethylaminoethyl) etc. are mentioned.

As such a fluorine-type smoothing agent, for example, "poly flow 600" by Kyoeisha Chemical Co., Ltd., "R-2020, M-2020, R-3833, M-3833" by Daikin Chemical Co., Ltd. `` Megafax F-171, F-172D, F-179A, F-470, F-475, R-08, Defense Corporation MCF-300 '' (manufactured by Dainippon Ink, Inc.) Brand name), etc. are mentioned.

As the fluorine-based smoothing agent, each material represented by Chemical Formulas 1 to 5 may also be used.

As the acrylic smoothing agent, "ARUFON-UP1000 series", "UH2000 series", "UC3000 series" made by Toa synthetic chemicals, "Polyflow 77" (above a brand name) made by Kyoeisha Chemical Co., Ltd. are commercially available. It is becoming.

When there is too little content of the smoothing agent in an optical function layer, it will become difficult to obtain the smoothing (leveling) effect of a coating film. When there is too much content of a smoothing agent, aggregate formation of an inorganic component will become impossible.

From this point of view, the content of the leveling agent in the optical functional layer is preferably in the range of 0.05 to 3% by weight, and preferably 0.1 to 2% by weight, based on 100% by weight of all components (excluding the organic solvent) of the optically functional layer. The range is more preferable, and the range of 0.2-1 weight% is especially preferable.

The compounding quantity of resin components, such as an ionizing radiation curable resin, is contained 50 weight% or more with respect to the total weight of a solid component in the resin composition which comprises an optical functional layer, and 60 weight% or more is very suitable. Although an upper limit is not specifically limited, For example, it is 99.8 weight%. If it is less than 50 weight%, there exists a problem that sufficient hardness cannot be obtained.

In addition, the solid content of resin components, such as an ionizing radiation curable resin, contains the solids other than the inorganic component mentioned later and microparticles | fine-particles, and includes not only solid content of resin components, such as ionizing radiation curable resin, but also solid content of other arbitrary components.

(Inorganic ingredient)

The inorganic component used in the present invention may be contained in the optical functional layer to aggregate during film formation to form a second phase and a random aggregated structure. As the inorganic component, inorganic nanoparticles can be used. Examples of the inorganic nanoparticles include metal oxides and metals such as silica, tin oxide, indium oxide, antimony oxide, alumina, titanium dioxide and zirconium oxide or silica colloidal solution, zirconium oxide colloidal solution, titanium dioxide colloidal solution and alumina colloidal solution. Metal oxide colloidal solutions, AEROSIL, swellable clays, layered organic clays, and the like. One type may be used for the said inorganic nanoparticles, and multiple types may be used for it.

In addition, microparticles | fine-particles and an inorganic component (inorganic nanoparticles) are separate, and can be distinguished by particle size.

Layered organic clay is preferable in that it can stably form a random aggregated structure among such inorganic nanoparticles. The reason why the layered organic clay can stably form a random agglomerated structure is that the layered organic clay is highly compatible with the resin component (organic component) and has a cohesive nature, making it easy to form a structure in which the first and second phases are intertwined. It is mentioned that it is easy to form a random aggregation structure at the time of film forming. In the present invention, the layered organic clay refers to the introduction of organic onium ions between the layers of swellable clay. Layered organic clay has low dispersibility to a specific solvent, and when a layered organic clay and a solvent having specific properties are used as the coating material for forming an optical functional layer, an optical layer having surface irregularities is formed by forming a random aggregation structure according to the selection of the solvent. The functional layer will be formed.

Swellable clay

The swellable clay has a cation exchange performance and may be water that swells between layers of the swellable clay, and may be natural or may be a composite (including a substituent and a derivative). Moreover, the mixture of a natural product and a synthetic material may be sufficient.

Swellable clays include, for example, mica, synthetic mica, vermiculite, montmorillonite, iron montmorillonite, Weidelite, saponite, hectorite, stevensite, nontronite, margadiite, illite, canneite, lamellar titanic acid, Smectite, synthetic smectite and the like. 1 type may be used for such swellable clay, and it may mix and use plurality.

Organic onium ions

The organic onium ions are not limited as long as they can be organicized using cation exchangeability of the swellable clay.

As the onium ion, for example, a quaternary ammonium salt such as dimethyl distearyl ammonium salt or trimethyl stearyl ammonium salt, an ammonium salt having a benzyl group or a polyoxyethylene group is used, or a phosphonium salt, a pyridinium salt or an imidazolium salt. Ions can be used. Salts include, for ^{example, Cl -, Br -, NO} 3 -, OH -, CH 3 COO - may be an anion such as a salt. It is preferable to use quaternary ammonium salt as a salt.

Although the functional group of organic onium ion is not restrict | limited, When using the material containing any of an alkyl group, a benzyl group, a polyoxypropylene group, or a phenyl group, since anti-glare property is easy to exhibit, it is preferable.

The preferred range of the alkyl group is 1 to 30 carbon atoms, for example methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, penta Decyl, octadecyl, etc. are mentioned.

In the polyoxypropylene group (CH ₂ CH (CH ₃ ) O) _n H or (CH ₂ CH ₂ CH ₂ O) _n H], the preferred range of n is 1 to 50, and more preferably 5 to 50, The more the number of moles added, the better the dispersibility with respect to the organic solvent. However, if the excess molar excess is excessive, the product becomes tacky. Therefore, the number of n is more preferably 20-50 when the emphasis is on dispersibility with respect to the solvent. Moreover, when the number of n is 5-20, a product is non-tacky and is excellent in grindability. In addition, from the viewpoint of dispersibility and handling, the total number of n in the entire quaternary ammonium is preferably 5 to 50.

Specific examples of the quaternary ammonium salt include tetraalkyl ammonium chloride, tetraalkyl ammonium bromide, polyoxypropylene trialkyl ammonium chloride, polyoxypropylene trialkyl ammonium bromide, di (polyoxypropylene)? Dialkyl ammonium chloride, Di (polyoxypropylene) dialkyl ammonium bromide, tri (polyoxypropylene) alkyl ammonium chloride, tri (polyoxypropylene) alkyl ammonium bromide, etc. are mentioned.

With respect to the quaternary ammonium ion of general formula (I), what is preferable as R <^1> is methyl group or benzyl group. R ² is preferably an alkyl group having 1 to 12 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. Preferred as R ³ is an alkyl group having 1 to 25 carbon atoms. Preferred as R ⁴ are an alkyl group having 1 to 25 carbon atoms, a (CH ₂ CH (CH ₃ ) O) _n H group or a (CH ₂ CH ₂ CH ₂ O) _n H group. It is preferable that n is 5-50.

[Formula 6]

In addition, when the alumina colloidal solution is used as the inorganic nanoparticles, the surface hardness of the optical functional layer is improved and the scratch resistance is also improved.

The inorganic nanoparticles may be modified. A silane coupling agent can be used for modification of an inorganic nanoparticle. As a silane coupling agent, vinyltrimethoxysilane, 3-glycidoxy propyl trimethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, (gamma) -methacryl Royloxypropyl trimethoxysilane, (gamma) -acryloyloxypropyl trimethoxysilane, (gamma) -methacryloyloxypropyl triethoxysilane, (gamma) -acryloyloxypropyl triethoxysilane, etc. are used. The silane coupling agent may have a functional group copolymerizable with the polymerizable double bond of the radiation curable resin constituting the resin component.

It is preferable that the average particle diameter of an inorganic nanoparticle is 100 nm or less, It is more preferable that it is 50 nm or less, Most preferably, it is 20 nm or less. The lower limit of the average particle diameter is not limited as long as the inorganic nanoparticles have cohesion, but is, for example, 1 nm. When the average particle diameter of inorganic nanoparticles exceeds 100 nm, the haze value of an optical laminated body tends to become high, and phenomena, such as whitening, tend to occur, and contrast also falls.

The compounding quantity of an inorganic component contains 0.1-10 weight% with respect to the total weight of the solid component in a resin composition, and 0.2-5 weight% is especially suitable. If the blending amount of the inorganic component is less than 0.1% by weight, a sufficient number of surface irregularities will not be formed, resulting in insufficient antiglare properties. When the compounding quantity of an inorganic component exceeds 10 weight%, there exists a problem that surface unevenness increases and visibility is impaired.

(menstruum)

It is preferable to contain a 1st solvent and a 2nd solvent as a solvent which forms the surface asperity for obtaining anti-glare property.

By adding a 1st solvent and a 2nd solvent to the resin composition of the said invention, it can be set as the coating material for optical function layer formation of this invention. Since the coating material for optical function layer formation of this invention contains the said 1st solvent and a 2nd solvent, it is an optical function, without adding the microparticles | fine-particles which were considered essential for creating the surface asperity shape of the optical function layer conventionally. The surface uneven | corrugated shape of a layer can be created.

A 1st solvent means what can be disperse | distributed in the state which has transparency, without causing substantially turbidity to an inorganic component. Substantially no haze includes things that can be regarded as the same as no haze and no haze at all. Specifically as a 1st solvent, the haze value of the mixed liquid which added and mixed 1000 weight part of 1st solvent with respect to 100 weight part of inorganic components says 10% or less. It is preferable that haze value of the mixed liquid which added and mixed the 1st solvent is 8% or less, and it is more preferable that it is 6% or less. In addition, although the lower limit of the mixed liquid haze value is not specifically limited, For example, it is 0.1%. As a 1st solvent, what is called a low polarity solvent (nonpolar solvent) can be used, for example.

A 2nd solvent means what can be disperse | distributed in the state which made turbidity to the inorganic component. As a 2nd solvent, the haze value of the mixed liquid which specifically added and mixed 1000 weight part of 2nd solvent with respect to 100 weight part of inorganic components says that it is 30% or more. It is preferable that it is 40% or more, and, as for the haze value of the mixed liquid which added and mixed the 2nd solvent, it is more preferable that it is 50% or more. In addition, although the upper limit of the mixed liquid haze value is not specifically limited, For example, it is 99%.

As the second solvent, for example, a so-called polar solvent can be used.

In addition, the haze value calculated | required when determining a 1st solvent and a 2nd solvent was measured by JISK7105.

The 1st solvent and 2nd solvent which can be used depend on the kind of inorganic component. As a solvent which can be used as a 1st solvent and a 2nd solvent, Alcohol, such as methanol, ethanol, 1-propanol, 2-propanol, butanol, isopropyl alcohol (IPA), isobutanol; Acetone, methyl ethyl ketone (MEK) Ketones such as cyclohexanone and methyl isobutyl ketone (MIBK); ketone alcohols such as diacetone alcohol; aromatic hydrocarbons such as benzene, toluene and xylene; glycols such as ethylene glycol, propylene glycol and hexylene glycol; Glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, diethyl carbitol, and propylene glycol monomethyl ether; N-methylpyrrolidone and dimethylformamide Esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, amyl acetate; ethers such as dimethyl ether and diethyl ether, and water can be used. One kind of such solvents may be used as the first solvent or the second solvent, or a plurality of solvents may be mixed to form the first solvent or the second solvent.

Here, mixing and using a 1st solvent and a 2nd solvent is preferable because it becomes easy to form the surface asperity for obtaining anti-glare property. The mixing ratio of the first solvent and the second solvent is preferable in the weight ratio in the range of 10:90 to 90:10 because it easily forms surface irregularities for obtaining anti-glare properties. As a mixing ratio of a 1st solvent and a 2nd solvent, it is preferable that it is the range of 15: 85-85: 15 by weight ratio, and it is preferable that it is the range of 20: 80-80: 20. If the first solvent is less than 10 parts by weight, there is a problem that an appearance defect due to the undispersed product occurs. If the first solvent is more than 90 parts by weight, there is a problem that surface irregularities for obtaining sufficient anti-glare property cannot be obtained.

Moreover, the compounding quantity of a resin composition and a solvent (the thing which combined the 1st solvent and the 2nd solvent) should just be the range of 70: 30-30: 70 by weight ratio.

If the resin composition is less than 30 parts by weight, dry stains or the like may occur, and the appearance may deteriorate, and the number of surface irregularities may increase, thereby impairing visibility.

If the resin composition is more than 70 parts by weight, the solubility (dispersibility) of the solid content tends to be impaired, so there is a problem in that the film cannot be formed.

(Fine particles)

The said resin composition contains translucent microparticles | fine-particles. After apply | coating the coating material for optical function layer formation which added the solvent to the said resin composition on a translucent base, the coating material for optical function layer formation can be hardened and an optical function layer can be formed. By adding translucent microparticles | fine-particles to a resin composition, it becomes easy to adjust the shape and number of the surface asperity of the said optical function layer.

As light-transmitting microparticles | fine-particles, organic light-transmitting microparticles | fine-particles which consist of an acrylic resin, a polystyrene resin, a styrene-acryl copolymer, a polyethylene resin, an epoxy resin, a silicone resin, polyvinylidene fluoride, a poly ethylene fluorine-type resin, silica, alumina, titanium dioxide, Inorganic light transmitting fine particles such as zirconium oxide, calcium oxide, tin oxide, indium oxide, and antimony oxide can be used. The refractive index of the light-transmitting fine particles is preferably 1.40 to 1.75. When the refractive index is less than 1.40 or larger than 1.75, the difference in refractive index with the light-transmissive substrate or the resin matrix becomes too large, and the total light transmittance decreases. In addition, the refractive index difference between the transparent particles and the resin is preferably 0.2 or less. It is preferable that it is the range of 0.3-10 micrometers, as for the average particle diameter of translucent microparticles | fine-particles, 1-7 micrometers is more preferable, and its 2-6 micrometers are further more preferable.

If the particle size is smaller than 0.3 mu m, the anti-glare property is lowered. If the particle diameter is larger than 10 mu m, it is not preferable because the glare occurs and the degree of the surface irregularities becomes too large and the surface becomes white. Moreover, although the ratio of the translucent microparticles | fine-particles contained in the said resin is not specifically limited, It is preferable to set it as 0.1-20 weight part with respect to 100 weight part of resin compositions, in order to satisfy characteristics, such as an anti-glare function and glare, and the surface of an optical function layer It is easy to control the fine concave-convex shape and the haze value. Here, "refractive index" points out the measured value according to JISK-7142. In addition, an "average particle diameter" points out the average value of 100 particle diameters measured with the electron microscope.

The compounding quantity of microparticles | fine-particles is contained 0.1 weight% or more with respect to the total weight of a solid component in the resin composition which comprises an optical function layer, and 1.0 weight% or more is very suitable. Although an upper limit is not specifically limited, For example, it is 5.0 weight%. If it is less than 0.1 weight%, there exists a problem of not being able to acquire sufficient anti-glare property.

Antistatic agent (conductive agent)

The optical function layer of this invention can contain an antistatic agent (conductive agent). By addition of a electrically conductive agent, dust adhesion on the surface of an optical laminated body can be prevented effectively. Specific examples of the antistatic agent (conductive agent) include various cationic compounds having cationic groups such as quaternary ammonium salts, pyridinium salts, and first to third amino groups, sulfonate groups, sulfate ester bases, phosphate ester bases, and phosphonate groups Anionic compounds having anionic groups, such as amino acids, amphoteric compounds such as aminosulfate esters, nonionic compounds such as amino alcohols, glycerin and polyethylene glycol, organic metal compounds such as alkoxides of tin and titanium, and And metal chelate compounds such as acetylacetonate salts, and the like, and compounds obtained by high molecular weight of the above-mentioned compounds. Moreover, polymeric compounds, such as organometallic compounds, such as a coupling agent which has a tertiary amino group, a quaternary ammonium group, or a metal chelate part, and has a monomer or oligomer or functional group which can be polymerized by ionizing radiation, can also be used as an antistatic agent. have.

Moreover, electroconductive fine particles are mentioned as an antistatic agent. Specific examples of the conductive fine particles include those made of metal oxides. Such metal oxides are indium tin oxide, In ₂ O ₃ , Al ₂ O ₃ , antimony-doped tin oxide (abbreviated; ATO), often abbreviated as ZnO, CeO ₂ , Sb ₂ O ₂ , SnO ₂ , ITO, Aluminum dope zinc oxide (abbreviation; Azo) etc. are mentioned. Electroconductive fine particles refer to what is called submicron size of 1 micron or less, Preferably an average particle diameter is 0.1 nm-0.1 micrometer.

Moreover, a conductive polymer is mentioned as another specific example of an antistatic agent (conductive agent). The material is not particularly limited, and examples thereof include aliphatic conjugated polyacetylene, polyacene, polyazene, aromatic conjugated polyphenylene, heterocyclic conjugated polypyrrole, polythiophene, polyisothianaphthene and hetero atom. Conjugated polyaniline, polythienylenevinylene, mixed conjugated poly (phenylenevinylene), conjugated system having a plurality of conjugated chains in a molecule, a double-chain conjugated system, derivatives of such conductive polymers, and conjugated polymer chains to saturated polymers And at least one selected from the group consisting of conductive composites that are graft or block copolymerized polymers. Especially, it is more preferable to use organic type antistatic agents, such as a polythiophene, polyaniline, and a polypyrrole. By using the said organic type antistatic agent, it becomes possible to exhibit the outstanding antistatic performance, to raise the total light transmittance of an optical laminated body, and to reduce haze value. In addition, an anion such as organic sulfonic acid or iron chloride may be added as a dopant (electron donor) for the purpose of improving conductivity and antistatic performance. In consideration of the dopant addition effect, in particular, polythiophene is preferable because of its high transparency and antistatic properties. Oligothiophene can also be used suitably as said polythiophene. It does not specifically limit as said derivative, For example, the alkyl group substituent of polyphenyl acetylene, polydiacetylene, etc. are mentioned.

<Optical laminated body>

After coating the optical functional layer-forming paint containing the constituent components on the light-transmissive substrate, the optical functional layer-forming coating is cured by irradiating heat or ionizing radiation (e.g., electron beam or ultraviolet radiation). By forming a functional layer, the optical laminated body of this invention can be obtained.

The optical functional layer may be formed on one surface of the light-transmissive substrate or may be formed on both surfaces.

Moreover, you may have another layer on the opposite surface of an optical function layer between an optical function layer and a translucent base, and may have another layer on an optical function layer. As another layer here, a polarizing layer, a light-diffusion layer, a low reflection layer, an antifouling layer, an antistatic layer, an ultraviolet-ray-infrared (NIR) absorption layer, a neon cut layer, an electromagnetic shield layer, etc. are mentioned, for example.

It is preferable that it is the range of 1.0-12.0 micrometers, More preferably, the thickness of an optical function layer is the range of 2.0-11.0 micrometers, More preferably, it is the range of 3.0-10.0 micrometers. When the optical functional layer is thinner than 1.0 µm, curing failure due to oxygen inhibition at the time of ultraviolet curing is likely to occur, and the wear resistance of the optical functional layer is easily deteriorated. When the optical functional layer is thicker than 12.0 µm, curling may occur due to curing shrinkage of the optical functional layer, and microcracks may be generated, the adhesion to the light-transmitting substrate, or the light transmittance may be reduced. And with the increase of a film thickness, it becomes a cause of the cost increase by the increase of required paint amount.

It is preferable that the optical laminated body of this invention is the range of 5.0-85.0 (value measured using the 0.5 mm optical comb according to JIS K7105), and, as for the optical laminated body, 20.0-75.0 are more preferable. Contrast deteriorates when image clarity is less than 5.0, and antiglare property deteriorates when it exceeds 85.0, and it is not suitable for the optical laminated body used for a display surface.

The optical laminated body of this invention has a fine uneven | corrugated shape on the surface of an optical function layer. Here, the fine concavo-convex shape is very suitably in the range of 0.2 to 1.4, the average inclination angle calculated from the average inclination required in accordance with ASME95, more preferably 0.25 to 1.2, more preferably 0.30 to 1.0. If the average inclination angle is less than 0.2, anti-glare property is deteriorated, and if the average inclination angle is more than 1.4, the contrast is deteriorated, so that it is not suitable for the optical laminated body used for the display surface.

Moreover, it is preferable that surface roughness Ra is 0.03-0.2 micrometer, It is more preferable that it is 0.03-0.15 micrometer, and, as for the optical laminated body of this invention as the fine uneven | corrugated shape of an optical function layer, it is especially preferable that it is 0.03-0.10 micrometer. If surface roughness Ra is less than 0.03 micrometer, the anti-glare property of an optical laminated body will become inadequate. When surface roughness Ra exceeds 0.2 micrometer, the contrast of an optical laminated body deteriorates.

Uneven | corrugated average space | interval Sm exists in the range of 30-300 micrometers, More preferably, it is 50-250 micrometers, More preferably, it is 100-250 micrometers. If the thickness is less than 30 µm, the surface scattering becomes large, resulting in a deterioration of the contrast of the optical laminate. If it exceeds 300 µm, there is a disadvantage in that anti-glare property is deteriorated.

Ten-point average surface roughness Rz exists in the range of 0.3-1.2 micrometers, More preferably, it is 0.4-1.0 micrometer, More preferably, it is 0.5-0.9 micrometer. If it is less than 0.3 µm, there is a disadvantage that antiglare property is deteriorated. If it is more than 1.2 µm, there is a disadvantage that the contrast of the optical laminate is deteriorated.

<Polarization gas>

In this invention, you may laminate | stack a polarizing base on the translucent base of the surface opposite to an optical function layer. Here, the polarizing gas may be a light absorbing polarizing gas that transmits only specific polarized light and absorbs other light, or a light reflecting polarizing gas that transmits only specific polarized light and reflects other light. As the light absorbing polarizing gas, a film obtained by stretching polyvinyl alcohol, polyvinylene, or the like can be used. For example, a biaxially stretched polyvinyl alcohol obtained by adsorbing oxo or dye as a dichroic element can be obtained. Polyvinyl alcohol (PVA) film which can be mentioned. As a light reflection type polarizing substrate, for example, two types of polyester resins (PEN and PEN copolymer) having different refractive indices in the stretching direction when stretched are laminated by stretching several hundred layers alternately by extrusion molding technology. "DBEF" made by 3M Corporation of Japan, the cholesteric liquid crystal polymer layer and a 1/4 wave plate are laminated, and the light incident from the cholesteric liquid crystal polymer layer side is separated into two circularly polarized light opposite to each other and transmitted through one side. Nitto Electric Co., Ltd. "Nipox" of the structure which reflects the other, and converts circularly polarized light which permeate | transmitted the cholesteric liquid crystal polymer layer into linearly polarized light by a 1/4 wave plate, "Transmax" by Merck company, etc. are mentioned. have.

It can be used as a polarizing plate by laminating | stacking a polarizing base and an optical laminated body directly or via an adhesive layer.

<Display device>

The optical laminate of the present invention can be applied to a display device such as a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescent display (ELD), a cathode ray tube display (CRT), or a surface electric field display (SED). . Especially preferably, it is used for a liquid crystal display (LCD). Since the optical laminated body of this invention has a translucent base, it is used by adhering the translucent base side to the image display surface of an image display apparatus.

When the optical laminate of the present invention is used on one side of the surface protection film of the polarizing plate, twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), inplane switching (IPS), and optical compass It can use suitably for the mode transmissive, reflective, or semi-transmissive liquid crystal display devices, such as a shaped bend cell (OCB).

<Method for Manufacturing Optical Laminate>

As a method of apply | coating the coating material for optical function layer formation on a translucent base, the normal coating method and the printing method are applied. Specifically, Air Doctor Coating, Bar Coating, Blade Coating, Knife Coating, Reverse Coating, Transparol Coating, Gravure Roll Coating, Kiss Coating, Cast Coating, Spray Coating, Slot Orifice Coating, Calender Coating, Dam Coating, Dip Coating, Die Coating such as a coating, intaglio printing such as gravure printing, printing such as stencil printing such as screen printing, and the like can be used.

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to these.

[Example]

Production Example 1 Preparation of Synthetic Smectite

4 L of water is placed in a 10 L beaker, and 860 g of Lake No. 3 (28% of SiO ₂ , 9% of Na ₂ O, molar ratio 3.22) are dissolved, and 162 g of 95% sulfuric acid is added at once with stirring to obtain a silicate solution. Next, with MgCl _2? 6H ₂ O in water 1ℓ first class reagent (purity 98%) dissolved in 560 g, adding it to the silicate solution to prepare a homogeneous mixed solution. This was dripped for 5 minutes, stirring in 3.6 L of 2N-NaOH solutions. Filtration system (cross flow filter (ceramic membrane filter: pore diameter: 2 micrometers, tubular type, filtration area 400cm ² ), pressurization: 2 kg / cm by the cross-flow method of the Japan Kaishi Co., Ltd. immediately. ² , filter cloth: Tetron 1310], and after sufficiently washing, a solution consisting of 200 ml of water and 14.5 g of Li (OH) -H ₂ O was added to form a slurry. This was transferred to an autoclave and subjected to hydrothermal reaction at 41 kg / cm ² and 250 ° C for 3 hours. After cooling, the reaction product was taken out, dried at 80 ° C, and ground to obtain a synthetic smectite having the following formula. This synthetic smectite was analyzed and the following composition was obtained. Na _0.4 Mg _2.6 Li _0.4 Si ₄ O ₁₀ (OH) _2. The cation exchange capacity measured by the methylene blue adsorption method was 110 milliequivalents / 100 g.

Preparation Example 2 Preparation of Synthetic Smectite Layered Organic Clay A

20 g of the synthetic smectite synthesized in Preparation Example 1 was dispersed in 1000 ml of tap water to prepare a suspension. 500 ml of an aqueous solution in which the quaternary ammonium salt (98% -containing product) of the following formula (II) was dissolved in an amount equivalent to 1.00 times the cation exchange capacity of the synthetic smectite was added to the synthetic smectite suspension and allowed to react for 2 hours at room temperature while stirring. The product was solid-liquid separated, washed to remove by-product salts, and dried to obtain synthetic smectite-based layered organic clay A.

[Formula 7]

Example 1

TAC (Fujifilm) of transparent gas which consists of 60 micrometers of film thickness, and 92% of total light transmittance of the coating material for optical function layer formation obtained by stirring the predetermined | prescribed mixture of Table 1 containing the said layered organic clay A in a disper for 30 minutes. Co., Ltd .; TD60UL) was applied on one surface by a roll coating method (line speed; 20 m / min), preliminarily dried at 30 to 50 ° C. for 20 seconds, and then dried at 100 ° C. for 1 minute to replace nitrogen atmosphere (nitrogen gas substitution). ), The coating film was cured by performing ultraviolet irradiation (lamp; condensing-type high-pressure mercury lamp, lamp output; 120 W / cm, lamp number: 4 lamps, irradiation distance; 20 cm). Thus, the optical laminated body of Example 1 which has an optical function layer of 5.9 micrometers in thickness was obtained. The SEM results from the optical functional layer surface of the optical laminate obtained here are shown in Fig. 2, the SEM results of the cross-sectional view of the optical laminate in Fig. 3, and the EDS results from the optical functional layer surface of the optical laminate in Fig. 4 Shown in From these results, it was confirmed that the optical functional layer which comprises the obtained optical laminated body has at least a 1st phase and a 2nd phase, and forms the random aggregation structure.

Example 2

Except having changed the coating material for optical function layer formation into the predetermined liquid mixture of Table 1, it carried out similarly to Example 1, and obtained the optical laminated body of Example 2 which has an optical function layer of 4.1 micrometers in thickness. It was confirmed that the optical functional layer which comprises the laminated body obtained by SEM and the EDS result has at least a 1st phase and a 2nd phase, and forms the random aggregation structure.

Example 3

Except having changed the coating material for optical function layer formation into the predetermined liquid mixture of Table 1, it carried out similarly to Example 1, and obtained the optical laminated body of Example 3 which has an optical function layer of 5.5 micrometers in thickness. It was confirmed that the optical functional layer which comprises the laminated body obtained by SEM and the EDS result has at least a 1st phase and a 2nd phase, and forms the random aggregation structure.

Example 4

Except having changed the coating material for optical function layer formation into the predetermined liquid mixture of Table 1, it carried out similarly to Example 1, and obtained the optical laminated body of Example 4 which has an optical function layer of 5.5 micrometers in thickness. It was confirmed that the optical functional layer which comprises the laminated body obtained by SEM and the EDS result has at least a 1st phase and a 2nd phase, and forms the random aggregation structure.

EXAMPLE 5

Except having changed the coating material for optical function layer forming into the predetermined liquid mixture of Table 1, it carried out similarly to Example 1, and obtained the optical laminated body of Example 5 which has an optical function layer of 5.0 micrometers in thickness. It was confirmed that the optical functional layer which comprises the laminated body obtained by SEM and the EDS result has at least a 1st phase and a 2nd phase, and forms the random aggregation structure.

[Example 6]

Except having changed the coating material for optical function layer forming into the predetermined liquid mixture of Table 1, it carried out similarly to Example 1, and obtained the optical laminated body of Example 5 which has an optical function layer of 5.4 micrometers in thickness. The SEM and EDS results confirmed that the optical functional layer constituting the obtained laminate had at least a first phase and a second phase to form a random aggregation structure.

[Comparative Example 1]

Except having changed the coating material for optical function layer formation into the predetermined liquid mixture of Table 1, it carried out similarly to Example 1, and obtained the optical laminated body of the comparative example 1 which has an optical function layer of 4.3 micrometers in thickness. Here, it was confirmed by SEM and EDS results of the obtained laminate that the optical functional layer constituting the obtained optical laminate did not form a random aggregation structure, but formed an island-in-the-sea structure that was completed from aggregation of light-transmitting organic fine particles.

[Comparative example 2]

Except having changed the coating material for optical function layer formation into the predetermined liquid mixture of Table 1, it carried out similarly to Example 1, and obtained the optical laminated body of the comparative example 2 which has an optical function layer of 5.8 micrometers in thickness. Here, the SEM and EDS results of the obtained laminate result in that the optical functional layer constituting the obtained optical laminate does not form a random aggregation structure, and the first and second phases form an island-in-water structure dispersed throughout the membrane surface. It was confirmed.

[Comparative Example 3]

Except having changed the coating material for optical function layer forming into the predetermined liquid mixture of Table 1, it carried out similarly to Example 1, and obtained the optical laminated body of the comparative example 3 which has an optical function layer of 6.6 micrometers in thickness. Here, the SEM result seen from the optical functional layer surface of the obtained optical laminated body is shown in FIG. 5, and the EDS result seen from the optical functional layer surface of the optical laminated body is shown in FIG. Although the optical functional layer which comprises the obtained optical laminated body phase-separates into a 1st phase and a 2nd phase, since it did not contain microparticles | fine-particles in an optical functional layer, it was confirmed that it does not form the random aggregation structure.

[Comparative Example 4]

Except having changed the coating material for optical function layer formation into the predetermined liquid mixture of Table 1, it carried out similarly to Example 1, and obtained the optical laminated body of the comparative example 4 which has an optical function layer of 5.5 micrometers in thickness. Here, SEM and EDS results of the obtained optical laminated body confirmed that the optical functional layer which comprises the obtained optical laminated body does not form a random aggregation structure, but forms the island-in-water structure completed from aggregation of translucent organic microparticles | fine-particles. .

[Comparative Example 5]

Except having changed the coating material for optical function layer formation into the predetermined liquid mixture of Table 1, it carried out similarly to Example 1, and obtained the optical laminated body of the comparative example 4 which has an optical function layer of 4.8 micrometers in thickness. Here, the SEM result was shown in FIG. 7 from the optical functional layer surface of the obtained optical laminated body. It was confirmed that the optical function layer which comprises the obtained optical laminated body does not form a random aggregation structure, but forms the island-in-water structure completed from aggregation of translucent organic microparticles | fine-particles.

[Comparative Example 6]

Except having changed the coating material for optical function layer forming into the predetermined liquid mixture of Table 1, it carried out similarly to Example 1, and obtained the optical laminated body of the comparative example 4 which has an optical function layer of 4.0 micrometers in thickness. Here, the SEM and EDS results of the obtained optical laminated body confirmed that the optical functional layer which comprises the obtained optical laminated body does not form a random aggregation structure, but forms the island-in-water structure completed from aggregation of amorphous silica.

The material used about the said Example was put in Table 1, and the material used about the comparative example is put in Table 2.

SEM and EDS were image | photographed on condition of the following.

SEM

SEM information was observed for the coating layer surface state and the containing element of the laminate obtained in the examples and the comparative examples. Observation was performed after depositing gold or carbon on the surface of the coating layer. Below, the conditions of SEM observation are shown.

Analysis device ?????? JSM-6460 LV (product made in Japan Electronics Corporation)

Preprocessing unit? ? ? ? ? C (carbon) coating: 45nm SC-701C (product made by Sanyu Electronics Co., Ltd.)

? ? ? ? ? ? ? ?? Au (gold) coating: 10nm SC-701 AT pieces (product made by Sanyu Electronics Co., Ltd.)

SEM condition? ? ? ? Acceleration voltage: 20 KV or 15 KV

                    Irradiation current: 0.15nA

                    Vacuum degree ： High vacuum

                    Image detector: Reflective electron detector

                    Sample slope: 0 degrees

EDS

The containing element information of the laminated body obtained by the Example and the comparative example was observed by EDS. Observation was performed after carbon vapor deposition on the application layer surface. Below, the conditions of EDS observation are shown.

Analysis device ?????? JSM-6460 LV (made in Japan Electronics Corporation)

Preprocessing unit ?????? C (carbon) coating: 45nm SC-701C (product made by Sanyu Electronics Co., Ltd.)

EDS condition ?????? Acceleration voltage ： 20KV

                    Irradiation current: 0.15nA

                    Vacuum degree ： High vacuum

                    Image detector: Reflective electron detector

                    MAP resolution: 128 X 96 pixels

                    Image resolution: 1024 X 768 pixels

(Assessment Methods)

Next, the following items were evaluated about the optical laminated body of an Example and a comparative example.

(Haze value)

Haze value (before Hz) was measured using the haze meter (brand name: NH2000, the Nippon Denshoku make) according to JISK7105.

(Surface roughness)

Surface roughness Ra, Rz, and Sm were measured using the said surface roughness measuring instrument in accordance with JIS B0601-1994.

(Average tilt angle)

The average inclination angle was calculated | required the average inclination using the surface roughness measuring instrument (brand name: Surfcoder SE1700α Kosaka Research Institute company) according to ASME95, and the average inclination angle was computed according to the following formula.

Mean slope angle = tan ^-1 (mean slope)

(Image sharpness)

According to JIS K7105, the measuring instrument was set to the transmission mode using a filamentous measuring instrument (brand name: ICM-1DP, manufactured by Suga Test Corp.) and measured at an optical comb width of 0.5 mm.

(Repellency)

Anti-glare was numerically determined by two methods, quantitative evaluation and qualitative evaluation. When the sum total of both evaluation judgment values was 5 or more points, it was set as X when (circle) and 4 or more points (circle) and 3 or less points.

(Quantitative evaluation of anti-glare)

When the value of image sharpness was 5 or more and less than 40, it was set as 3 points, 2 or more points when 40 or more and less than 80 was set as 1 point when it is 80 or more.

(Quality Evaluation of Anti-glare)

On the opposite side of the optical stack forming surface, it is attached to a black acrylic plate (Acrylate L502 made by Mitsubishi Rayon) through a colorless and transparent adhesive, and two fluorescent lamps of 400 lux environmental illumination are arranged in parallel in an exposed state. The light was projected at an angle of 45 to 60 degrees with the light source, and the reflected image was visually observed in the direction of specular reflection to determine the degree of inclusion of the image of the fluorescent lamp. Two points can be recognized when the image is blurred as one reflection image of two fluorescent lamps is seen, but two points when the outline of the fluorescent lamp is blurred, and one point when the outline of the two fluorescent lamps is clearly seen without being blurred. I did.

(Black degree)

The degree of blackness under clear light was numerically determined by two methods, quantitative evaluation and qualitative evaluation. When the sum of both evaluation judgment values was 6 points | pieces, (circle), 5 points | pieces, (circle) and 4 points or less were made into X.

(Quantitative evaluation of black degree)

It pastes on the screen surface of a liquid crystal display (brand name: LC-37GX1W, product of Sharp Corporation) through the colorless transparent adhesive layer on the opposite surface to the optical laminated body formation surface of an Example and a comparative example, and is 60 degrees of the front upper part of a liquid crystal display screen After making illuminance of liquid crystal display surface become 200 lux with fluorescent lamp (brand name: HH4125GL, product made in National) from direction, color luminance meter (brand name: BM-5A,) when we made liquid crystal display white indication and black indication luminance in the black display is obtained by measuring a tower konsa claim) (cd / m ²⁾ and the brightness at white display (calculated by the following equation to the cd / m ^2), and below with the contrast of a plane polarizer to 100% The reduction rate was calculated by the equation. When the reduction rate was less than 5%, three points were used, and when the reduction rate was 5% or more and less than 10%, two points were set and one point was 10% or more.

Contrast = luminance of white display / luminance of black display

Reduction ratio = contrast (optical laminate) / contrast (plane polarizer)

In the present invention, the plane polarizing plate refers to a laminate in which a TAC film is attached to both surfaces of a polyvinyl alcohol (PVA) film obtained by uniaxial stretching of polyvinyl alcohol obtained by adsorbing iodine or dye as a dichroic element.

(Quality Evaluation of Black Degree)

Fluorescent lamps are placed in parallel with a colorless transparent adhesive on the opposite side of the optical laminate body, pasted together to a black acrylic plate (Acrylite L502, manufactured by Mitsubishi Rayon), and exposed in parallel with two fluorescent lamps exposed to 400 lux of ambient light. Is a light source, and the light is incident at an angle of 45 to 60 degrees, and blackness of portions other than the reflection image of the light source is visually observed in the direction of specular reflection, and blackness is superior to that of the film shown in Example 1 3 2 points were used when the point and blackness were the same, and 1 point was used when the blackness was inferior.

(Darkroom contrast)

The darkroom contrast is pasted to the screen surface of a liquid crystal display (brand name: LC-37 GX1W, manufactured by Sharp Co., Ltd.) via a colorless transparent adhesive layer on the opposite side to the optical laminate formation surface of the Examples and Comparative Examples, and the liquid crystal display is combined under dark conditions. The luminance (cd / m ² ) at the time of black display and the luminance (cd at the time of white display) obtained by measuring the brightness | luminance at the time of white display and black display by a color luminance meter (brand name: BM-5A, product made from Topcon) / M ² ) was calculated by the following formula, and the reduction ratio was calculated by the following formula with the contrast of the plane polarizing plate being 100%. ? When the reduction rate was less than 3%,? When 3% or more and 7% or less, and X when 7% or more.

Contrast = luminance of white display / luminance of black display

Reduction ratio = contrast (optical laminate) / contrast (plane polarizer)

The obtained results are shown in Table 3.

As described above, according to the present invention, it is possible to provide an optical laminate having excellent anti-glare property and blackness under bright room and at the same time high dark contrast, and excellent in manufacturing stability, and a method for producing the optical laminate. Moreover, the polarizing plate and display apparatus which comprise the said optical laminated body can also be provided.

1 first phase
2 second phase
3 fine particles
15, 16 optical functional layer
20 translucent gases
30, 31 particulates
40 resin

Claims (7)

In the optical laminated body in which an optical function layer is laminated | stacked on the translucent base,
The optically functional layer comprises a first phase containing more resin components than the second phase, a second phase containing more inorganic components than the first phase, and fine particles, wherein the second phase around the fine particles is different. The optical laminated body which is unevenly distributed. The method of claim 1,
The said inorganic component is an inorganic nanoparticle, The optical laminated body characterized by the above-mentioned. The method of claim 1,
The second phase is an optical laminate, characterized in that the aggregate of inorganic nanoparticles. The method of claim 1,
The said 2nd phase contains 0.2 weight% or more of inorganic components, The optical laminated body characterized by the above-mentioned. The polarizing plate is laminated | stacked on the translucent base which comprises the optical laminated body of any one of Claims 1-4. The polarizing plate characterized by the above-mentioned. A display device comprising the optical laminate according to any one of claims 1 to 4. A drying process for applying a solution comprising a resin component, an inorganic component, fine particles, a first solvent, and a second solvent onto a light-transmissive substrate, and generating convection with volatilization of the first solvent and the second solvent, and a dried coating film And a curing step of curing the resin to form an optical functional layer.

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