JP5397589B2 - Laminated body - Google Patents

Description

The present invention relates to a laminate, and more particularly to a laminate that can be used in a display device having a polarizing substrate such as a liquid crystal display device.

As a layer structure of the liquid crystal display device, for example, a backlight device / lower polarizing plate / liquid crystal / upper polarizing plate / surface member are sequentially laminated. As the surface member, an antiglare film or a hard coat film can be used. Between the said structures, a brightness improvement film, a diffusion film, an adhesion layer, etc. are provided as needed.

An absorption polarizing substrate, a reflective polarizing substrate, or the like can be used as a constituent member of a conventional polarizing plate. Among these polarizing substrates, polarizing plates using an absorbing polarizing substrate are widely used for liquid crystal display devices, sunglasses, and the like (see, for example, Patent Document 1). For example, a polyvinyl alcohol (hereinafter referred to as “PVA”) film can be used for the absorptive polarizing substrate. The absorbing polarizing substrate and a polymer film characterized by low birefringence are attached via an adhesive and used as a polarizing plate.

Moreover, as a conventional anti-glare film, a film obtained by laminating a resin layer in which translucent fine particles are dispersed in a translucent resin can be used on a resin film (see, for example, Patent Document 2). . Then, by using the antiglare film as a constituent member of the outermost surface (observation surface side) of the liquid crystal display device, it is possible to prevent a decrease in screen glare and improve display contrast while maintaining antiglare properties. it can.

Furthermore, as a conventional hard coat film, a film in which a cured coating layer composed of a composition containing an ultraviolet curable polyol acrylate resin is formed on at least one surface of a transparent plastic film substrate can be used (for example, patents). Reference 3).

JP 2004-20830 A JP 2007-334294 A Japanese Laid-Open Patent Publication No. 9-11728

Here, in the liquid crystal display device in which the above backlight device / lower polarizing plate / liquid crystal / upper polarizing plate / surface member are sequentially laminated, light emitted from the backlight device is transmitted from the lower polarizing plate and the upper polarizing plate. It is emitted as polarized light (mainly linearly polarized light). The polarized light emitted from the upper polarizing plate is transmitted through the surface member in the state of polarized light (mainly linearly polarized light).
If the polarized light emitted from this surface member is viewed with sunglasses on, the display screen of the liquid crystal display device becomes black, and the display screen of the liquid crystal display device cannot be viewed without removing the sunglasses. Was. One cause of the problem is the use of a polarizing substrate as one of the constituent members of sunglasses.

Here, as a method for solving the above problem, use of a retardation film can be mentioned. The arrangement | positioning location of retardation film becomes an observation surface side from the upper polarizing plate which comprises a liquid crystal display device. Since this retardation film has the property of changing incident polarized light (mainly linearly polarized light) into circularly polarized light, it is possible to put the retardation film at an appropriate position on the liquid crystal display device so that sunglasses can be worn. Also, the display screen of the liquid crystal display device can be visually recognized.

However, since the retardation film itself does not have adhesiveness / adhesiveness, it is necessary to provide an adhesive layer or the like on the front and back surfaces of the retardation film in order to use it as a constituent member of a liquid crystal display device. . Therefore, when the retardation film is used as a constituent member of a liquid crystal display device, there is a problem that these thicknesses increase. This problem was contrary to the demand from the market where thinning was desired. In addition, when the retardation film is used as a constituent member of a liquid crystal display device, the number of parts increases, which causes a problem of increasing costs.

The present invention has been made in view of the above problems. That is, the laminate of the present invention has a function as a surface member (for example, if the surface member is a hard coat film, it means that it has a pencil hardness of 3H or more and steel wool wear resistance, and the surface member is an antiglare film. (This means that anti-glare properties, glare prevention and high contrast are maintained if necessary) and also has a function of eliminating polarized light, so that the thickness of a display device having a polarizing substrate such as a liquid crystal display device is increased. It aims at providing the laminated body which can achieve low cost without making it.

The present invention solves the above problems by the following technical configuration.

(1) A resin layer in which translucent fine particles are dispersed in a translucent resin is laminated on a translucent substrate, and the BET specific surface area of the translucent fine particles is 1.5 to 80 m ² / g. A laminate characterized by the above.
(2) The laminate according to (1), wherein the translucent fine particles have pores having a diameter of 0.01 to 0.2 μm.
(3) The laminate according to (1) or (2), wherein the translucent fine particles have a porosity index (RI) of 5 to 100.
(4) The laminate according to any one of (1) to (3), wherein the translucent fine particles are radial translucent fine particles.
(5) The laminate according to any one of (1) to (4), wherein the translucent fine particles are polyamide fine particles.

According to the laminate of the present invention, since the function as a surface member is maintained and the function of eliminating polarization is also provided, the thickness of a display device having a polarizing substrate such as a liquid crystal display device is not increased. An object of the present invention is to provide a laminate that can achieve low cost.

Hereinafter, the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view showing a laminate of the present invention. FIG. 1A shows a laminate of a resin layer 40 in which translucent fine particles 30 are dispersed in a translucent resin 20 on a translucent substrate 10. The laminated body 1 is formed, and (b) is the laminated body 2 in which the unevenness 41 is formed on one surface of the resin layer 40. The laminate 1 can be used as a hard coat film, and the laminate 2 can be used as an antiglare film. In the laminate 2, the unevenness may be formed on both surfaces of the resin layer 40, or may be formed on both surfaces of the translucent substrate 10.
When the laminates 1 and 2 are used as constituent members of a display device having a polarizing substrate such as a liquid crystal display device, the translucent substrate 10 side may be bonded to the polarizing substrate directly or via another layer.

The shape of the unevenness 41 is preferably such that the unevenness average interval (Sm) is in the range of 50 to 250 μm, more preferably 55 to 220 μm, and still more preferably 60 to 180 μm.
When the average interval of the unevenness is larger than 250 μm, the glare becomes worse. When it is smaller than 50 μm, the antiglare property is deteriorated.
In addition, the uneven | corrugated average space | interval (Sm) in this invention says the value measured using the surface roughness measuring device according to JISB0601-1994.

The laminate 1 in the present invention preferably has a transmitted image definition in a range of 5.0 to 70.0 (value measured using a 0.5 mm optical comb in accordance with JIS K7105), and more preferably 20.0 to 65.0. preferable. If the transmitted image definition is less than 5.0, the contrast deteriorates, and if it exceeds 70.0, the antiglare property deteriorates, so that it is not suitable for the laminate 1 used for the display surface.

ここで、Ｘ＋３５＜Ｙであるか、５０＜Ｙのいずれかであると、表面での光拡散効果が大きくなることにより表面が白っぽくなり、コントラストが低下する。特に明室でのコントラストが悪くなる。Ｘ＜ＹまたはＸ＜４０のいずれかであると、積層体１（特に樹脂層４０）内部の光拡散効果が大きくなることで、コントラストが低下する。特に暗室でのコントラストが低下する。Ｘ＜Ｙ、Ｙ≦Ｘ＋３５またはＸ＜５のいずれかであると、樹脂層４０内部の光拡散効果が小さくなるため、ギラツキが発現する。 When using the laminated body 1 in the present invention for a 10-30 type liquid crystal display device for medium and small size, the internal haze value (X) and the total haze value (Y) satisfying the following formulas (1) to (4) are satisfied. It is preferable to have. Here, the “total haze value” in the present invention refers to the haze value of the laminate 1, and the “internal haze value” in the present invention is the transparency with pressure-sensitive adhesive on the surface of the unevenness 41 of the resin layer 40 constituting the laminate 1. It refers to a value obtained by subtracting the haze value of the adhesive-attached transparent sheet from the haze value of the sheet with the sheets bonded together. It is preferable that the haze value of the adhesive-attached transparent sheet is measured in advance before being bonded to the surface of the laminate 1.
In addition, all the haze values of this invention point out the value measured according to JISK7015.

Here, if X + 35 <Y or 50 <Y, the light diffusion effect on the surface increases, and the surface becomes whitish and the contrast decreases. In particular, the contrast in the bright room is poor. If either X <Y or X <40, the light diffusion effect inside the laminate 1 (particularly the resin layer 40) is increased, thereby reducing the contrast. In particular, the contrast in the dark room decreases. If X <Y, Y ≦ X + 35, or X <5, the light diffusion effect inside the resin layer 40 becomes small, so that glare appears.

また、Ｘ＋１＜Ｙ＜Ｘ＋８、且つ、１８＜Ｘ＜４０の範囲にあることがさらに好ましく、Ｘ＋２≦Ｙ≦Ｘ＋６、且つ、２５≦Ｘ≦３５の範囲にあることが特に好ましい。 A preferable range of the 1 to 20 type liquid crystal display device for medium and small size has an internal haze value (X) and a total haze value (Y) satisfying the following formulas (1) and (5) to (7). preferable.

Further, X + 1 <Y <X + 8 and 18 <X <40 are more preferable, and X + 2 ≦ Y ≦ X + 6 and 25 ≦ X ≦ 35 are particularly preferable.

In addition, a preferable range in a liquid crystal display device (TV) larger than 30 type, which requires high definition and high contrast, is an internal haze value (X) satisfying the following expressions (8) and (9) and a total haze value ( Y) is preferred.

The laminate 1 in the present invention may have other layers in addition to the translucent substrate 10 and the resin layer 40 which are constituent members. Here, examples of the other layers include a polarizing substrate, a low reflection layer, and other function-imparting layers (for example, an antistatic layer and an antifouling layer). As the position of the other layer, for example, it may be provided on one side or both sides of the translucent substrate 10, may be provided between the translucent substrate 10 and the resin layer 40, or the translucent substrate. It may be laminated on the resin layer 40 laminated on the conductive substrate 10.
Hereinafter, the material constituting the present invention will be mainly described.

<Translucent fine particles>
BET specific surface area of the translucent fine particles constituting the present invention is required to be 1.5~80m ² / g, is preferably 2~60m ² / g, in 3~40m ² / g More preferably it is. By making the BET specific surface area of the translucent fine particles within the above range, light (for example, linearly polarized light) incident on the translucent fine particles is randomly emitted. Thus, for example, even when the laminate of the present invention is arranged on the outermost surface (observation surface side) of the liquid crystal display device and the display screen of the liquid crystal display device is visually confirmed through sunglasses, the display screen is confirmed well. can do.
When the BET specific surface area of the light-transmitting fine particles is less than 1.5 m ² / g, there is a problem that the action of depolarizing is reduced.
If the BET specific surface area of the translucent fine particles is more than 80 m ² / g, there is a problem that the action of depolarizing is reduced.

The shape of the translucent fine particles can take various shapes such as a spherical shape, an elliptical shape, and an indefinite shape.
As the translucent fine particles, it is preferable to use radial translucent fine particles 50 having a radial shape as shown in FIG. Here, the radial shape only needs to have a shape in which a plurality of radial protrusions extend from the vicinity of the center C of the translucent fine particle toward the outside. It does not have to be symmetric). Further, although not shown, the radial protrusion may be branched from the vicinity of the center to the tip, or may be branched at the tip of the radial protrusion. The number of radial projection branches is not limited. In addition, adjacent radial projections can also be present intertwined. By using the radial translucent fine particles having radial protrusions, the surface area of the translucent fine particles is increased, so that the depolarization effect can be improved.

It is preferable to have pores (fine irregularities) on the surface of the light-transmitting fine particles because the polarized light irradiated to the light-transmitting fine particles is eliminated. Specifically, the translucent fine particles preferably have pores having a diameter of 0.01 to 0.2 μm, and more preferably 0.02 to 0.1 μm.
When the light-transmitting fine particles are radial light-transmitting fine particles having radial protrusions, the pores may be measured near the surface. Specifically, the interval P between the tips of the radial projections 51 and the tips of the radial projections 52 shown in FIG.
If the diameter of the pores of the light-transmitting fine particles is less than 0.01 μm, there is a problem that the action of depolarizing light is reduced.
When the diameter of the pores of the light-transmitting fine particles is more than 0.2 μm, there is a problem that the action of depolarizing is reduced.

When the pores are present in the light-transmitting fine particles, the porosity index (RI) is preferably 5 to 100, more preferably 5 to 70.
The porosity index in the present invention is expressed by the ratio of the specific surface area of the porous spherical particles to the specific surface area of the smooth spherical particles having the same diameter, and can be represented by the formula (10).
When the porosity index is less than 5, there is a problem in that the action of depolarizing polarized light decreases.
If the porosity index is more than 100, there is a problem in that the action of depolarizing polarized light decreases.

ここで、ＲＩは多孔度指数、Ｓは多孔粒子の比表面積［ｍ^２／ｋｇ］、Ｓ_０は同一粒子径の円滑な球状粒子の比表面積［ｍ^２／ｋｇ］である。
円滑な球の比表面積Ｓ_０は、観測された数平均球状粒子径ｄ_ｏｂｓ［ｍ］、透光性樹脂の密度ρ［ｋｇ／ｍ^３］とすると、式（１１）で表すことができる。

Here, RI is a porosity index, S is a specific surface area [m ² / kg] of porous particles, and S ₀ is a specific surface area [m ² / kg] of smooth spherical particles having the same particle diameter.
The specific surface area S ₀ of the smooth sphere can be expressed by the following equation (11), where the observed number average spherical particle diameter d _obs [m] and the density of the translucent resin ρ [kg / m ³ ].

By making the resin layer contain translucent fine particles, fine irregularities can be formed on the surface of the resin layer. When translucent fine particles are contained in the resin layer, it is preferable to use a radiation curable resin composition as the resin layer. By using the radiation curable resin composition, the refractive index difference from the light-transmitting fine particles can be easily reduced to 0.2 or less, and the total light transmittance can be suitably maintained. Further, the difference in refractive index between the translucent fine particles constituting the resin layer and the translucent resin is preferably 0.01 or more and 0.1 or less, and more preferably 0.02 or more and 0.05 or less. . Since the light scattering effect is improved by setting the difference in refractive index between 0.01 and 0.1, it is economical because a depolarization function can be imparted with a smaller addition amount.

As the translucent fine particles, for example, an organic translucent material made of acrylic resin, polystyrene resin, polyamide resin, styrene-acrylic copolymer, polyethylene resin, epoxy resin, silicone resin, polyvinylidene fluoride, polyvinyl fluoride resin, and the like. Fine particles can be used. Among these translucent fine particles, it is preferable to use a polyamide resin. The refractive index of the translucent fine particles is preferably 1.40 to 1.75. When the refractive index is less than 1.40 or greater than 1.75, the translucent substrate or the resin matrix (resin excluding the translucent fine particles) The difference in refractive index from the total solid content of the layer becomes too large, and the total light transmittance decreases.

The average particle size of the translucent fine particles is preferably in the range of 0.3 to 15 μm, more preferably 1 to 10 μm, and particularly preferably in the range of 2 to 7 μm. When the particle diameter is smaller than 0.3 μm, the action of depolarizing may be reduced. When the particle diameter is larger than 15 μm, the contrast is deteriorated, which is not preferable when the laminate is used as an optical laminate for optical applications. Further, the ratio of the light-transmitting fine particles contained in the resin is not particularly limited, but 1 to 20 parts by mass with respect to 100 parts by mass of the resin composition is sufficient for satisfying characteristics such as an antiglare function and glare. Preferably, it is easy to control the fine uneven shape and haze value on the surface of the resin layer.
Here, “refractive index” refers to a measured value according to JIS K-7142. Further, “average particle diameter” refers to an average value of the diameters of 100 particles actually measured with an electron microscope.

<Translucent substrate>
The translucent substrate constituting the present invention is not particularly limited as long as it is translucent, and glass such as quartz glass and soda glass can also be used. Polyethylene terephthalate (PET), triacetyl cellulose (TAC) , Polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cycloolefin Various resin films such as copolymer (COC), norbornene-containing resin, polyethersulfone, cellophane, and aromatic polyamide can be suitably used. In addition, when using the laminated body of this invention for the medium which has polarizing bases, such as a liquid crystal display device and sunglasses, it is preferable to use a material with little birefringence as the translucent base | substrate. Examples of the material having little birefringence include TAC, COC, norbornene-containing resin, and the like.
In addition, a polarizing substrate may be used as the translucent substrate in the present invention.

The higher the transparency of these translucent substrates, the better. However, the total light transmittance (JIS K7105) is 80% or more, more preferably 90% or more. Further, the thickness of the translucent substrate is preferably thinner from the viewpoint of weight reduction, but considering the productivity and handling properties, the one in the range of 1 to 700 μm is preferable, and the thickness of 25 to 250 μm is preferable. Further preferred.

  In addition, surface treatment such as alkali treatment, corona treatment, plasma treatment, sputtering treatment, saponification treatment, application of surfactant, silane coupling agent, etc., or surface modification treatment such as Si deposition on the translucent substrate. By performing the above, it is possible to improve the adhesion between the translucent substrate and the resin layer and between the translucent substrate and another layer.

<Translucent resin>
Next, the translucent resin in the present invention will be described in detail. Although the material which comprises the resin layer which concerns on this invention is not specifically limited, It is preferable to use a radiation curable resin composition. The radiation curable resin composition means a resin composition that is cured by radiation such as heat or ultraviolet rays, and can reduce equipment costs and improve productivity. As the radiation curable resin composition, a monomer having a radical polymerizable functional group such as acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, and a cationic polymerizable functional group such as epoxy group, vinyl ether group, oxetane group, A composition in which an oligomer and a prepolymer are used alone or appropriately mixed is used. Examples of monomers include methyl acrylate, methyl methacrylate, methoxy polyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, ethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and the like. it can. As oligomers and prepolymers, polyester acrylate, polyurethane acrylate, polyfunctional urethane acrylate, epoxy acrylate, polyether acrylate, acrylate compounds such as alkit acrylate, melamine acrylate, silicone acrylate, unsaturated polyester, tetramethylene glycol diglycidyl ether, Epoxy compounds such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether and various alicyclic epoxies, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[((3- Oxeta such as ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether Mention may be made of the compound. These can be used alone or in combination.

The radiation curable resin composition can be cured by electron beam irradiation as it is. However, when curing by ultraviolet irradiation, it is necessary to add a photopolymerization initiator. In addition, as a radiation used, any of an ultraviolet-ray, visible light, infrared rays, and an electron beam may be sufficient. Further, these radiations may be polarized or non-polarized.
Photopolymerization initiators include radical polymerization initiators such as acetophenone, benzophenone, thioxanthone, benzoin, and benzoin methyl ether, and cationic polymerization starts such as aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, and metallocene compounds. The agents can be used alone or in appropriate combination.

To the radiation curable resin composition, a polymer resin can be added and used as long as the polymerization and curing is not hindered. This polymer resin is a thermoplastic resin that is soluble in an organic solvent used in the resin layer coating described later, and specifically includes acrylic resins, alkyd resins, polyester resins, and the like. It preferably has an acidic functional group such as a carboxyl group, a phosphoric acid group, or a sulfonic acid group.

Moreover, additives, such as a leveling agent, a thickener, and an antistatic agent, can be contained in a radiation curable resin composition. The leveling agent has a function of uniforming the tension on the surface of the coating film and correcting defects before forming the coating film, and a substance having lower interfacial tension and surface tension than the radiation curable resin composition is used. The thickener has a function of imparting thixotropy to the radiation curable resin composition, and is effective in forming fine uneven shapes on the surface of the resin layer by preventing sedimentation of translucent fine particles and pigments.

The resin layer in the present invention is preferably composed of a cured product in which a radiation curable resin composition contains a polymer resin and an additive as necessary. As a method for forming the radiation curable resin layer, for example, a coating made of a radiation curable resin composition and an organic solvent is applied on a translucent substrate, and the organic solvent is volatilized, and then radiation (for example, electron beam or ultraviolet light) is used. It can be cured by irradiation. As the organic solvent used here, it is necessary to select a solvent suitable for dissolving the radiation curable resin composition. Specifically, in consideration of coating suitability such as wettability to a light-transmitting substrate, viscosity, and drying speed, an alcohol type, an ester type, a ketone type, an ether type, or an aromatic hydrocarbon is used alone or in combination. Solvents can be used.

The thickness of the resin layer is preferably in the range of 1.0 to 12.0 μm, more preferably in the range of 2.0 to 11.0 μm, and still more preferably in the range of 3.0 to 10.0 μm. . When the resin layer is thinner than 1.0 μm, curing failure due to oxygen inhibition occurs at the time of ultraviolet curing, and the wear resistance of the resin layer tends to deteriorate. When the resin layer is thicker than 12.0 μm, curling due to curing shrinkage of the resin layer, generation of microcracks, lowering of adhesion with the light-transmitting substrate, and lowering of light transmittance may occur. And it becomes a cause of the cost increase by the increase in the amount of required coating materials accompanying the increase in film thickness.

<Other layers>
In the present invention, a polarizing substrate may be laminated on a translucent substrate. Further, a polarizing substrate may be laminated on the opposite surface of the translucent substrate on which the resin layer is laminated. Here, the polarizing substrate uses a light-absorbing polarizing film that transmits only specific polarized light and absorbs other light, or a light reflective polarizing film that transmits only specific polarized light and reflects other light. I can do it. As the light-absorbing polarizing film, a film obtained by stretching polyvinyl alcohol, polyvinylene or the like can be used. For example, it can be obtained by uniaxially stretching polyvinyl alcohol adsorbed with iodine or a dye as a dichroic element. Polyvinyl alcohol (PVA) film. As the light reflection type polarizing film, for example, two kinds of polyester resins (PEN and PEN copolymer) having different refractive indexes in the stretching direction when stretched are alternately laminated and stretched by several hundreds of extrusion techniques. "DBEF" manufactured by 3M, or a cholesteric liquid crystal polymer layer and a quarter-wave plate are laminated, and light incident from the cholesteric liquid crystal polymer layer side is separated into two circularly polarized light beams that are opposite to each other. Nitto Denko's “Nipox” and Merck's “Transmax”, which are configured to convert circularly polarized light that is transmitted through the cholesteric liquid crystal polymer layer and converted into linearly polarized light by a quarter-wave plate, and the like. .

Furthermore, it is preferable to provide a low reflection layer on the resin layer because the contrast is improved. The low reflection layer may be provided on the resin layer, and examples thereof include a layer configuration composed of a resin layer / low reflection layer and a layer configuration composed of a translucent substrate / resin layer / low reflection layer. . In this case, the refractive index of the low reflective layer needs to be lower than the refractive index of the resin layer. Specifically, the refractive index of the low reflection layer is preferably 1.45 or less. Examples of the material having these characteristics include LiF (refractive index n = 1.4), MgF ₂ (n = 1.4), 3NaF · AlF ₃ (n = 1.4), AlF ₃ (n = 1. 4), inorganic low reflection material in which inorganic material such as Na ₃ AlF ₆ (n = 1.33) is finely divided and contained in acrylic resin or epoxy resin, fluorine-based, silicone-based organic compound, Examples thereof include organic low reflection materials such as thermoplastic resins, thermosetting resins, and radiation curable resins. Among them, a fluorine-based fluorine-containing material is particularly preferable in terms of preventing contamination. The low reflective layer preferably has a critical surface tension of 18 dyne / cm or less. When the critical surface tension is larger than 18 dyne / cm, it becomes difficult to remove the dirt attached to the low reflection layer.

  Examples of the fluorine-containing material include vinylidene fluoride copolymers, fluoroolefin / hydrocarbon copolymers, fluorine-containing epoxy resins, fluorine-containing epoxy acrylates, fluorine-containing silicones, which are easily dissolved in organic solvents. , Fluorine-containing alkoxysilanes, and the like. These can be used alone or in combination.

  Further, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate, 2- (perfluoro- 9-methyldecyl) ethyl methacrylate, fluorine-containing methacrylate such as 3- (perfluoro-8-methyldecyl) -2-hydroxypropyl methacrylate, 3-perfluorooctyl-2-hydroxylpropyl acrylate, 2- (perfluorodecyl) ethyl acrylate , Fluorine-containing acrylates such as 2- (perfluoro-9-methyldecyl) ethyl acrylate, 3-perfluorodecyl-1,2-epoxypropane, 3- (perfluoro-9-methyldecyl) -1,2-epoxypropane It epoxide, radiation-curable fluorine-containing monomers such as epoxy acrylate, oligomers, and the like prepolymer. These can be used alone or in combination.

Furthermore, a low-reflective material in which a sol obtained by dispersing ultrafine silica particles of 5 to 30 nm in water or an organic solvent and a fluorine-based film forming agent can be used. A sol in which 5 to 30 nm ultrafine silica particles are dispersed in water or an organic solvent is a method in which alkali metal ions in an alkali silicate salt are dealkalized by ion exchange or the like, or a method in which an alkali silicate salt is neutralized with a mineral acid A known silica sol obtained by condensing active silicic acid known in the art, a known silica sol obtained by condensing alkoxysilane with hydrolysis in an organic solvent in the presence of a basic catalyst, and the above-mentioned aqueous sol An organic solvent-based silica sol (organosilica sol) obtained by substituting water in the silica sol with an organic solvent by a distillation method or the like is used. These silica sols can be used in both aqueous and organic solvent systems. In producing the organic solvent-based silica sol, it is not necessary to completely replace water with the organic solvent. The silica sol, a solid content of 0.5 to 50% strength by weight as SiO _2. Various structures such as a spherical shape, a needle shape, and a plate shape can be used as the structure of the silica ultrafine particles in the silica sol.

  As the film forming agent, alkoxysilane, metal alkoxide, hydrolyzate of metal salt, or fluorine-modified polysiloxane can be used. Among the film forming agents as described above, it is particularly preferable to use a fluorine compound because the critical surface tension of the low reflection layer is lowered and adhesion of oil can be suppressed. The low reflection layer of the present invention is prepared by diluting the above-mentioned materials with a solvent, for example, spin coater, roll coater, printing, etc. on the radiation curable resin layer, drying, heat, radiation (in the case of ultraviolet rays) Can be obtained by curing using the above-mentioned photopolymerization initiator. Radiation curable fluorine-containing monomers, oligomers, and prepolymers are excellent in stain resistance, but have poor wettability, so depending on the composition, when a radiation curable resin composition is used as the resin layer, a low reflective layer may be used. There is a possibility that a problem of repelling or a problem that the low reflection layer is peeled off from the resin layer may occur. In order to prevent this problem, the radiation curable resin composition used for the resin layer is appropriately mixed with a monomer having a polymerizable unsaturated bond such as acryloyl, methacryloyl, acryloyloxy, and methacryloyloxy groups, an oligomer, and a prepolymer. It is desirable to use it.

When a plastic film such as PET or TAC that is easily damaged by heat is used for the translucent substrate, it is preferable to select a radiation curable resin composition as the material of the low reflection layer.
The thickness of the low reflection layer is preferably around 0.1 μm, more preferably in the range of 0.1 ± 0.01 μm.

Next, the manufacturing method of the laminated body which concerns on this best form is explained in full detail.
As a method of coating or printing, for example, a coating material in which translucent fine particles are dispersed in a resin matrix on a translucent substrate is applied and printed by a conventional coating method or printing method, and then dried. There is a method of providing a resin layer having a fine concavo-convex shape on the surface by curing treatment, but there is no particular limitation. Specific examples of coating and printing methods include air doctor coating, bar coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, slot orifice coating, calendar Examples thereof include coating such as coating, dam coating, dip coating and die coating, intaglio printing such as gravure printing, and printing such as stencil printing such as screen printing.

EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to these Examples at all.

A resin film (translucent substrate) having a film thickness of 80 μm and a total light transmittance of 92% is obtained by stirring a mixture of paint components shown in Table 1 below for 1 hour with a disper as a resin layer paint. TAC (product name: TD80UL manufactured by FUJIFILM Corporation) was applied on one side by reverse coating, dried at 100 ° C for 1 minute, and then irradiated with ultraviolet rays using two 120W / cm concentrating high-pressure mercury lamps in a nitrogen atmosphere. (The irradiation distance was 10 cm, the irradiation time was 30 seconds), the coating film was cured, and the laminate of Example 1 was obtained.
The thickness of the cured resin layer was 10 μm.

A laminate of Example 2 was obtained in the same manner as Example 1 except that the mixture composed of the coating components shown in Table 2 below was used (the thickness of the cured resin layer was 10 μm).

A laminate of Example 3 was obtained in the same manner as in Example 1 except that the mixture of coating components shown in Table 3 below was used and the thickness of the cured resin layer was 15 μm.

[Comparative Example 1]
A laminate of Comparative Example 1 was obtained in the same manner as in Example 1 except that a mixture of coating components shown in Table 4 below was used and the thickness of the cured resin layer was 7 μm.

[Comparative Example 2]
A laminate of Comparative Example 2 was obtained in the same manner as in Example 1 except that a mixture of coating components shown in Table 5 below was used and the thickness of the cured resin layer was 3 μm.

<Evaluation>
The laminates of Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated as follows, and the results obtained are summarized in Table 6.

(Total light transmittance)
The total light transmittance of the laminate was measured according to JIS K7105.

(Porosity index (RI))
The porosity index (RI) was calculated according to the formula (10) described in the specification.

(Pencil hardness)
It measured based on JIS5400 using the pencil hardness meter (made by Yoshimitsu Seiki Co., Ltd.). The number of measurements was 5 and the number of scratches was counted. For example, if there are no 3 scratches with a 3H pencil, 3/5 (3H) is used. The pencil hardness was 4/5 (3H) or higher.

(Steel wool wear resistance)
Steel wool # 0000 manufactured by Nippon Steel Wool was attached to an abrasion resistance tester (Ablation Tester, Model: 339 manufactured by Fu Chicn), and the resin layer surface was reciprocated 10 times at a load of 250 g / cm ² . Thereafter, scratches on the worn part were confirmed under a fluorescent lamp. When the number of scratches was 0, ◎, when the number of scratches was less than 1-10, ◯, when the number of scratches was less than 10-30, Δ, and when the number of scratches was 30 or more, x.

(Contrast, depolarization)
The depolarization is pasted to the surface of the liquid crystal display (LC-37GX1W, manufactured by Sharp Corporation) via a colorless and transparent adhesive layer on the opposite side of the resin layer forming surface of the laminate of each Example and each Comparative Example, In addition, a polarizing plate is installed above the resin layer forming surface of the laminated body so that the upper polarizing plate of the liquid crystal display and crossed Nicols are arranged, and the brightness when the liquid crystal display is displayed in white and black the color luminance meter (BM-5A, manufactured by Topcon Corporation) was measured by at resulting black state luminance (cd / cm ²⁾ and the white display of the luminance (cd / cm ²⁾ the following equation When the calculated contrast value was 0-30, it was marked with x, when it was 31-500, it was marked with ◯, and when it was 501 or more.
Contrast = Brightness when displaying white / Brightness when displaying black

As mentioned above, since the specific surface area of the translucent fine particle mix | blended with the resin layer which comprises the said laminated body in the laminated body of this invention in Examples 1-3 is 1.5-80 m < ² > / g, While having the property of being used as a surface member, it had a depolarization function.
On the other hand, the laminates of Comparative Examples 1 and ² have a depolarization function because the specific surface area of the translucent fine particles blended in the resin layer constituting the laminate is out of the range of 1.5 to 80 m ² / g. Was not enough.

As described above, according to the present invention, the thickness of a display device having a polarizing substrate such as a liquid crystal display device can be increased because it has a function of eliminating polarization while maintaining the function as a surface member. There can be provided the laminated body which can achieve low cost.

It is sectional drawing of the laminated body of this invention, Comprising: It is sectional drawing of (a) hard coat film and (b) anti-glare film. It is sectional drawing of radial translucent fine particles.

Explanation of symbols

Laminated body 10 Translucent substrate 20 Translucent resin 30 Translucent fine particle 40 Resin layer 41 Concavity and convexity 50 Radial translucent fine particles 51 and 52 Radial protrusion C Center P Distance

Claims (4)

A resin layer in which translucent fine particles are dispersed in a translucent resin is laminated on the translucent substrate,
The BET specific surface area of the translucent fine particles is 1.5 to 80 m ² / g,
The translucent resin uses a radiation curable resin composition, includes a photopolymerization initiator,
A hard coat film, wherein the resin layer has a pencil strength of 3H or more, and the resin layer has steel wool wear resistance. The hard coat film according to claim 1, wherein the translucent fine particles are radial translucent fine particles and are polyamide fine particles. A resin layer in which translucent fine particles are dispersed in a translucent resin is laminated on the translucent substrate,
The BET specific surface area of the translucent fine particles is 1.5 to 80 m ² / g,
The translucent resin uses a radiation curable resin composition, includes a photopolymerization initiator,
Luminance at the time of black display (cd ) when a polarizing plate having an upper piece polarizing plate and a crossed Nicol arrangement of the liquid crystal display device is installed on the upper surface of the resin layer formed on the screen surface of the liquid crystal display device. / Cm ² ) and the brightness at the time of white display (cd / cm ² ), the contrast value calculated by the following formula is 31 or more.
Contrast = Brightness when displaying white / Brightness when displaying black 4. The antiglare film according to claim 3, wherein the translucent fine particles are radial translucent fine particles and are polyamide fine particles.

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