JP5172986B2 - Method for producing antiglare antireflection film - Google Patents

Description

  The present invention relates to a method for producing an antiglare antireflection film.

  Anti-glare anti-reflection films are generally used for image display devices such as cathode ray tube display devices (CRT), plasma display devices (PDP), and liquid crystal display devices (LCD). In order to prevent this, it has a function of reducing the reflectance by scattering of light by the surface protrusion and thin film interference, and is disposed on the outermost surface of the display.

  In general, the anti-reflection film produced by coating is the most important point for determining the quality of the product because it is placed on the outermost surface of the display. It is an important factor.

  Since the main raw material constituting the antireflection film is easily soluble and dispersible in an organic solvent, the coating solution is selected from an organic solvent rather than an aqueous solution.

  At this time, if the drying conditions are not appropriate, appearance / defect failures such as brushing, unevenness, streaks, repelling, etc. may occur, which may not only reduce the product yield but also cause the quality to deteriorate. In particular, since the required level of surface quality and performance quality for antireflection films is very high, the selection of drying conditions, which is one of the manufacturing conditions, was very important.

  In addition, when applying the optical functional layer as described above by solvent coating, aggregation of particles added to the coating liquid, change in surface shape, layer structure, etc. due to delay in drying or liquid composition fluctuation during drying, etc. Due to phase separation of components, performance such as reflectance, antiglare property, and glare deteriorates.

In order to deal with such a problem, as a conventional technique, there is exemplified a method in which a coating liquid composed of an ultraviolet curable resin, a reaction initiator, and a solution is diluted and forcedly dried before solvent drying (for example, Patent Document 1). reference).
However, in this exemplary method, hot air at 100 ° C. is blown from the back surface for forced drying in order to avoid the back to the back surface from the end of the coating liquid, and when applied to the antireflection film of the present invention, Unevenness in drying was not suitable.

Japanese Patent No. 2523574 (Example 6 on page 6)

An object of the present invention is to provide an excellent antireflection film having a high product yield and having a sufficient antireflection performance and no coating surface failure.
Another object of the present invention is to supply an antireflection film that does not deteriorate performance such as reflectance, antiglare property, and glare.

As a result of diligent investigation, it was found that it is extremely important to set each layer under the conditions when forming the antireflection film.
In the present invention, setting the coating film means that the flow of the coating solution is substantially eliminated by drying, and that the flow of the coating solution is substantially eliminated means that the coating solution is evaporated and the coating solution is evaporated. This means that the concentration of solids in the liquid increases and the liquid viscosity of the coating liquid increases accordingly, and the coating liquid does not move due to the surrounding wind, gravity, and vertical movement of the film transport. Can be forcibly stopped halfway and it can be visually confirmed from which point the flow is lost.
According to the present invention, by maintaining the temperature after coating the coating solution at 10 ° C. to 40 ° C., it is possible to gradually bring it into a set state while avoiding rapid drying due to forced drying of the solvent. The object of the invention can be achieved.
Specifically, the above object is achieved by a method for producing an antireflection film having the following constitution .
<1>
An antiglare antireflection film is produced by forming at least one antiglare hard coat layer having a film thickness of 1 to 10 μm containing antiglare imparting particles having an average particle diameter of 1 to 10 μm on a transparent support. A way to
A coating step for forming the antiglare hard coat layer, a drying step by the first drying unit, a drying step by the second drying unit and a curing step;
The drying process by the first drying unit for forming the antiglare hard coat layer has a drying time of 5 seconds to 120 seconds, a windbreak cover is provided, and the wind speed of the wind hitting the coating surface is 0.5 m / s or less, 10 ° C. or more lower than the boiling point of the main solvent in the coating solution, and temperature control to 10 ° C. or more and 40 ° C. or less to complete the setting of the coating film,
The drying step by the second drying unit for forming the antiglare hard coat layer is at a temperature higher than that of the first drying unit, and the boiling point of the solvent having the lowest boiling point contained in the coating solution. As mentioned above, the manufacturing method of the anti-glare antireflection film which is a step of drying at the boiling point temperature of the solvent having the highest boiling point contained in the coating liquid + 20 ° C. or lower.
<2>
An antiglare antireflection film is produced by forming at least one antiglare hard coat layer having a film thickness of 1 to 10 μm containing antiglare imparting particles having an average particle diameter of 1 to 10 μm on a transparent support. A way to
A coating step for forming the antiglare hard coat layer, a drying step by the first drying unit, a drying step by the second drying unit and a curing step;
The drying process by the first drying unit for forming the antiglare hard coat layer has a drying time of 5 seconds to 120 seconds, a windbreak cover is provided, and the wind speed of the wind hitting the coating surface is 0.5 m / s or less, 10 ° C. or more lower than the boiling point of the main solvent in the coating solution, and temperature control to 10 ° C. or more and 40 ° C. or less to complete the setting of the coating film,
Anti-glare property, wherein the drying step by the second drying unit for forming the anti-glare hard coat layer is a step of drying at a temperature higher than the first drying unit by 50 ° C. or more and 140 ° C. or less. A method for producing an antireflection film.
<3>
The antiglare antireflection film according to <1> or <2>, wherein the drying step by the first drying unit for forming the antiglare hard coat layer is temperature-controlled at 15 ° C. or more and 35 ° C. or less. Production method.
<4>
The temperature control in the first drying section for forming the antiglare hard coat layer starts within 30 seconds after coating, and the antireflection according to any one of <1> to <3> Manufacturing method of dazzling antireflection film.
<5>
The antiglare antireflection film according to any one of <1> to <4>, wherein the temperature of the first drying part is 2 ° C. to 30 ° C. higher than the temperature of the coating part. Manufacturing method.
<6>
<1> to <5>, wherein the solvent composition in the coating solution of the antiglare hard coat layer includes a solvent having a boiling point of 100 ° C. or higher in an amount of 1% to 90% of the total solvent in the coating solution. The manufacturing method of the anti-glare antireflection film of any one of these.
<7>
A method for producing an antireflection film by forming at least one hard coat layer having a thickness of 1 to 10 μm on a transparent support,
Having a coating process for forming the hard coat layer, a drying process by a first drying section, a drying process by a second drying section and a curing process;
The drying process by the first drying section for forming the hard coat layer has a drying time of 5 seconds to 120 seconds, a windbreak cover is provided, and the wind speed of the wind hitting the coating surface is 0.5 m. Is a drying step that ends the set of the coating film by controlling the temperature to be 10 ° C. or more and 40 ° C. or less lower than the boiling point of the main solvent in the coating solution,
The drying step by the second drying section for forming the hard coat layer is higher than the first drying section and is applied at a temperature equal to or higher than the boiling temperature of the lowest boiling point solvent contained in the coating solution. It is a step of drying at the boiling point temperature of the solvent having the highest boiling point contained in the liquid + 20 ° C. or lower.
A method for producing an antireflection film.
<8>
A method for producing an antireflection film by forming at least one hard coat layer having a thickness of 1 to 10 μm on a transparent support,
Having a coating process for forming the hard coat layer, a drying process by a first drying section, a drying process by a second drying section and a curing process;
The drying process by the first drying section for forming the hard coat layer has a drying time of 5 seconds to 120 seconds, a windbreak cover is provided, and the wind speed of the wind hitting the coating surface is 0.5 m. Is a drying step that ends the set of the coating film by controlling the temperature to be 10 ° C. or more and 40 ° C. or less lower than the boiling point of the main solvent in the coating solution,
The method for producing an antireflection film, wherein the drying step by the second drying unit for forming the hard coat layer is a step of drying at a temperature higher than the first drying unit by 50 ° C. or more and 140 ° C. or less. .
<9>
A method for producing an antireflection film by forming at least one hard coat layer on a transparent support and further forming an outermost low refractive index layer,
A coating step for forming the hard coat layer, a drying step and a curing step, and
Having a coating step for forming the low refractive index layer, a drying step by a first drying unit and a drying step by a second drying unit;
The drying step by the first drying section for forming the low refractive index layer is provided with a cover for windbreak, and the wind speed of the wind hitting the coating film surface is 0.5 m / s or less, in the coating solution It is a drying step of controlling the temperature to be 10 ° C. or more and 40 ° C. or less lower than the boiling point of the main solvent and finishing the setting of the coating film,
The drying step by the second drying unit for forming the low refractive index layer is at a temperature higher than that of the first drying unit, and is equal to or higher than the boiling point of the lowest boiling point solvent contained in the coating liquid. A method for producing an antireflection film, which is a step of drying at the boiling point temperature of the solvent having the highest boiling point contained in the coating liquid + 20 ° C. or lower.
<10>
A method for producing an antireflection film by forming at least one hard coat layer on a transparent support and further forming an outermost low refractive index layer,
A coating step for forming the hard coat layer, a drying step and a curing step, and
Having a coating step for forming the low refractive index layer, a drying step by a first drying unit and a drying step by a second drying unit;
The drying step by the first drying section for forming the low refractive index layer is provided with a cover for windbreak, and the wind speed of the wind hitting the coating film surface is 0.5 m / s or less, in the coating solution It is a drying step of controlling the temperature to be 10 ° C. or more and 40 ° C. or less lower than the boiling point of the main solvent and finishing the setting of the coating film,
Production of an antireflection film, wherein the drying step by the second drying unit for forming the low refractive index layer is a step of drying at a temperature higher than the first drying unit at 50 ° C. or more and 140 ° C. or less. Method.
<11>
The antireflection film as described in <9> or <10>, wherein a solvent having a boiling point of 100 ° C. or lower is 50% to 100% as a solvent of the coating solution used for forming the low refractive index layer Manufacturing method.
The present invention is an invention according to the above <1> to <11>, but hereinafter, other matters are also described.

(1) In the method for producing an antireflection film formed by applying a coating liquid for each of at least one hard coat layer and an outermost low refractive index layer on a transparent support and drying it, The hard coat layer and the low-refractive index layer of the antireflection film are characterized in that after the coating solution is applied, the coating film is set at the first drying section maintained at 10 ° C. or higher and 40 ° C. or lower. A method for producing a film.
(2) In the above production method, the temperature of the first drying part is 10 ° C. or more lower than the boiling point of the main solvent of the coating liquid for the hard coat layer and the low refractive index layer, and the antireflection according to (1) A method for producing a film.
(3) In the said manufacturing method, 1st drying of any layer is started within 30 second after application | coating, The manufacturing method of the antireflection film as described in (1) or (2) characterized by the above-mentioned.
(4) In the manufacturing method described above, the temperature of the first drying part of any layer is 2 ° C. or more and 30 ° C. or less higher than the coating part temperature. Manufacturing method of antireflection film.
(5) The method for producing an antiglare antireflection film as described in any one of (1) to (4), wherein at least one of the hard coat layers is an antiglare hard coat layer.
(6) The inorganic fine particle filler contained in the antiglare hard coat layer is at least one selected from zirconium, titanium, aluminum, indium, zinc, tin, antimony, and silicon having a particle diameter in the range of 1 nm to 100 nm. The anti-glare imparting particles made of a metal oxide and contained in the anti-glare hard coat layer are organic polymer particles and / or inorganic particles having a particle size in the range of 2 μm to 7 μm. The particles contained in the hard hard coat layer that do not contribute to imparting anti-glare properties and are contained in the layer are organic polymer particles and / or further inorganic particles having a particle size in the range of 1 μm to 5 μm. The manufacturing method of the anti-glare antireflection film as described in (5).
(7) In the antiglare hard coat layer, the refractive index of the antiglare-imparting particles or / and the particles contained in the layer is 0 with respect to the refractive index of the composite of the organic resin and the inorganic filler. The method for producing an antiglare and antireflection film according to (5) or (6), wherein the difference is in the range of 0.05 to 0.15.
(8) The antireflective film according to any one of (1) to (4), which has a middle refractive index layer and a high refractive index layer between the hard coat layer and the low refractive index layer. Production method.
(9) The method for producing an antireflection film or an antiglare antireflection film according to any one of (1) to (8), wherein the transparent support is triacetylcellulose.
(10) The production of the antireflection film or antiglare antireflection film according to any one of (1) to (9), wherein the low refractive index layer has a refractive index of 1.38 to 1.49. Method.
(11) The antireflection film or the antiglare antireflection film produced by the production method according to any one of (1) to (10) is applied to one of the two protective films of the polarizer in the polarizing plate. A polarizing plate characterized by being used.
(12) Optical having an optical compensation layer in which the antireflection film or the antiglare antireflection film out of the two protective films of the polarizer in the polarizing plate includes an optically anisotropic layer. A compensation film, wherein the optically anisotropic layer is a layer having negative birefringence composed of a compound having a discotic structural unit, and the disc surface of the discotic structural unit is inclined with respect to the surface protective film surface And the angle formed by the disc surface of the discotic structural unit and the surface protective film surface varies in the depth direction of the optically anisotropic layer.
(13) A λ / 4 plate is disposed on the anti-reflection film or the protective film opposite to the anti-glare anti-reflection film of the polarizing plate according to (11) or (12). A circularly polarizing plate having an antireflection function.
(14) In the method in which the polarizer of the polarizing plate is stretched by applying tension while holding both ends of the continuously supplied polymer film by a holding means, 1.1 to 20.0 at least in the film width direction. The longitudinal travel speed difference of the holding devices at both ends of the film is within 3%, and the angle formed by the film traveling direction at the exit of the step of retaining both ends of the film and the substantial stretching direction of the film is 20 to 20 times. The polarizer according to any one of (11) to (13), wherein the polarizer is manufactured by a stretching method in which the film traveling direction is bent so that both ends of the film are held so as to be inclined by 70 °. Polarizer.
(15) An antireflection film or an antiglare antireflection film produced by the production method according to any one of (1) to (10), or a polarizing plate with an antireflection film according to (11) to (14) Or the display apparatus characterized by using the polarizing plate with an anti-glare antireflection film for the outermost surface of a display.
(16) A TN, STN, VA, IPS, OCB mode transmissive, reflective, or transflective display device having at least one polarizing plate according to any one of (11) to (14).
(17) A transmissive or transflective display device having at least one polarizing plate according to any one of (11) to (14), between the polarizing plate on the side opposite to the viewing side and the backlight. A display device comprising: a polarizing separation film having a polarization selective layer.

It is a cross-sectional schematic diagram which shows the layer structure of an anti-glare antireflection film. It is the schematic of the tenter drawing machine used in the Example. It is a schematic diagram which shows the cutting of the polarizing film performed in the Example. It is a schematic diagram of the coating machine in the manufacturing method of this invention.

  A basic configuration of an antiglare antireflection film suitable as an embodiment of the present invention will be described with reference to the drawings.

  The embodiment schematically shown in FIG. 1 is an example of the antireflection film of the present invention. In this case, the antireflection film 1 includes a transparent support 2, an antiglare hard coat layer 3, and a low refractive index layer 4. Has an ordered layer structure. In the antiglare hard coat layer 3, antiglare imparting particles 5 that are translucent particles, or further, internal scattering imparting particles 6 that are translucent particles are dispersed.

  The antireflection film of the present invention has at least one hard coat layer on a transparent support, and further has an outermost low refractive index layer thereon. The coat layer may be an antiglare hard coat layer, or an antiglare layer may be provided on the hard coat layer. Further, an antiglare hard coat layer may be provided on a smooth hard coat layer. Thereby, film strength can be raised. For an antireflection film that does not require antiglare properties, the antiglare hard coat layer 3 is not provided, and a smooth hard coat layer may be used.

  In addition, as an antireflection film used in the present invention, an intermediate refractive index layer, a high refractive index layer, etc. are provided between a hard coat layer and a low refractive index layer, and an antireflection film having a three-layer structure due to thin film interference can also be used. good. At this time, the optical film thickness of each of the medium refractive index layer, the high refractive index layer, and the low refractive index layer, that is, the product of the refractive index and the film thickness is about nλ / 4 with respect to the design wavelength λ or a multiple thereof. It is described in Japanese Patent Application Laid-Open No. 59-50401 that it is preferable.

  In particular, in order to realize a reflectance characteristic with a low reflectance and a reduced color of reflected light, the middle refractive index layer has the following formula (I) for the design wavelength λ (= 500 nm), and the high refractive index. It is preferable that the layer satisfies the following formula (II) and the low refractive index layer satisfies the following formula (III).

  lλ / 4 × 0.80 <n1d1 <lλ / 4 × 1.00 (I)

  mλ / 4 × 0.75 <n2d2 <mλ / 4 × 0.95 (II)

  nλ / 4 × 0.95 <n3d3 <nλ / 4 × 1.05 (III)

In the formula, l is 1, n1 is the refractive index of the medium refractive index layer, d1 is the layer thickness (nm) of the medium refractive index layer, m is 2, and n2 is the high refractive index layer. And d2 is the thickness (nm) of the high refractive index layer, n is 1, n3 is the refractive index of the low refractive index layer, and d3 is the low refractive index layer. Layer thickness (nm). Furthermore, for example, n1 is 1.60 to 1.65 and n2 is 1 for a transparent support having a refractive index of 1.45 to 1.55 made of triacetylcellulose (refractive index: 1.49). .85 to 1.95, n3 is preferably a refractive index of 1.35 to 1.45, for example, a refractive index of 1.55 to 1.65 made of polyethylene terephthalate (refractive index: 1.66). N1 is preferably 1.65 to 1.75, n2 is 1.85 to 2.05, and n3 is preferably 1.35 to 1.45.

The production method of the present invention will be described below. An example of the process for manufacturing the antireflection film of the present invention is shown in FIG. In the process of FIG. 4, 1a for feeding a roll-shaped support film, a coating part 2a for applying a coating liquid, a first drying part 3a for volatilizing the solvent so as not to cause unevenness, and removal of the solvent by heating and heat curing The second drying unit 4a for performing the above, the step 5a for curing the coating film with heat, ionizing radiation, etc., the step 6a for winding the coated film, and the like are performed. However, the present invention is not limited to this.
In the present invention, on the transparent support, a hard coat layer and a low refractive index layer, which are constituent layers of the antireflection film, are applied with each coating solution and dried, and after the coating, kept at 10 ° C. or more and 40 ° C. or less. It is necessary to finish the setting of the coating film in the first drying unit 3a. When the temperature of the first drying section exceeds 40 ° C., the drying property is rapidly increased and the appearance surface shape and the defect are affected. If the temperature of the drying section is too low (less than 10 ° C), there are disadvantages that the drying time is delayed and a long drying zone is required, the reversing roll of the process due to undried, and the transfer to the back of the film after winding Is a problem. About the temperature of a 1st drying part, Preferably it is 15 to 40 degreeC, More preferably, it is 18 to 35 degreeC. It is also preferable to provide a drying temperature pattern in which the temperature is gradually increased in the late stage of drying.
In addition, the drying temperature of the first drying section should be 10 ° C. or less lower than the boiling point of the main solvent of the coating solution of each of the hard coat layer and the low refractive index layer, which are the constituent layers of the antireflection film. It is preferable in order to avoid drying unevenness due to drying. A more preferable temperature is 15 ° C. or lower, particularly preferably 20 ° C. or lower. The contents of the main solvent in these constituent layers will be described later.
It is desirable to start the temperature control in the first drying section within ˜30 seconds immediately after coating. More preferably, it is within 0.5 second to 20 seconds, and particularly preferably within 1 second to 15 seconds. The time for controlling the temperature depends on the concentration of the coating solution and the coating solution solvent used, but is within 5 seconds to 120 seconds, more preferably 10 seconds to 100 seconds, and particularly preferably 20 seconds to 90 seconds. It is.
It is effective to start the temperature control in the first drying section when the amount of residual solvent in the coating film is large. When the residual solvent in the coating film is 10% by mass or less at the time of coating, the fluidity of the liquid is almost lost. Therefore, it is necessary to carry out before the amount of the solvent at the time of coating reaches 10% by mass. More preferably, the residual solvent amount is 30% by mass or less, particularly preferably 50% by mass or less.
The temperature of the first drying part of the present invention is preferably 2 ° C. or more and 30 ° C. or less higher than the temperature of the coating part. This is considered to be because the volatilization of the solvent is promoted and the viscosity of the coating film tends to increase because the temperature of the first drying section is higher than the temperature of the coating film. When the temperature difference is 2 ° C. or less, the drying accelerating effect is small. When the temperature difference is 30 ° C. or more, drying unevenness is likely to occur due to the drying temperature difference being too large. More preferably, it is 3 to 25 ° C, particularly preferably 5 to 20 ° C.
As a temperature of a coating part, the range of 8 to 35 degreeC is preferable. More preferably, it is 15 to 30 degreeC, Most preferably, it is 18 to 25 degreeC.
The temperature control in the first drying unit is preferably performed while suppressing unevenness due to wind. As a method for this, there are a method of suppressing the wind speed on the coating surface, heating by blowing air from the back surface, heating by an infrared heater or the like, and a method of heating the entire first drying chamber by heat conduction or the like. In addition, it is also preferable to attach a windshield cover or the like to the initial drying section. It is preferable that the wind speed of the wind which hits the coating-film surface in an initial drying zone is 0.5 m / s or less. More preferably, it is 0.3 m / s or less, Most preferably, it is 0.2 m / s or less.
For coating films in which the coating film has been set and the flow of the coating liquid has been completed, the temperature is further increased after winding, or until the first drying section that has been kept at 10 ° C. or higher and 40 ° C. or lower until winding. In order to reduce the amount of residual solvent in the film by carrying out drying (second drying section 4a), it is possible to transfer the film to the reverse roll in the conveying line or to the back of the film after winding, or to form a film on the formed film. It is desirable in terms of strength and prevention of solvent crying. The temperature of the second drying section is preferably set with respect to the boiling point of the selected coating solution solvent, and the boiling point of the solvent having the lowest boiling point contained in the coating solution to the highest boiling point contained in the coating solution. The boiling point temperature of the solvent is preferably + 20 ° C., more preferably the boiling point temperature of the solvent having the lowest boiling point contained in the coating liquid + 20 ° C. to the boiling point temperature of the solvent having the highest boiling point contained in the coating liquid + 20 ° C. The temperature of the second drying section is 50 ° C. or higher and 140 ° C. or lower, particularly preferably 60 ° C. or higher and 120 ° C. or lower. The heating time is preferably 15 seconds or more and 30 minutes or less. More preferably, it is 20 seconds or more and 15 minutes or less, and particularly preferably 30 seconds or more and 10 minutes or less.
It is also preferable to provide a step 5a for curing the coating film between the first drying unit and the second drying unit or after the second drying unit, in some cases, in the middle of the second drying unit. As a method for curing the coating film, thermal curing by heating or irradiation with ionizing radiation such as UV or electron beam is conceivable. Thermosetting can be achieved by installing a reversing roll or the like at the time of heating in the second drying section and extending the heating time. In the ionizing radiation irradiation, it is preferable to provide equipment capable of continuously performing irradiation at a necessary place in the process.
The drying conditions of the present invention must be applied to at least one hard coat layer and a low refractive index layer, but are applied to drying conditions of other constituent layers such as a medium refractive index layer and a high refractive index layer. It is also preferable to do.

The antiglare hard coat layer of the present invention will be described below.
Anti-glare hard coat layer is a binder for imparting hard coat properties, translucent particles for imparting anti-glare and internal scattering properties, and for increasing the refractive index, preventing crosslinking shrinkage, or increasing the strength. Inorganic fine particle filler.
The refractive index of the part other than the light-transmitting particles in the antiglare hard coat layer is preferably in the range of 1.48 to 1.70.

The binder is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a polymer having a saturated hydrocarbon chain as a main chain.
The binder polymer preferably has a crosslinked structure.
As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.
In order to obtain a high refractive index, the monomer structure preferably contains an aromatic ring or at least one atom selected from halogen atoms other than fluorine, sulfur atoms, phosphorus atoms, and nitrogen atoms.

Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol tetra). (Meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives ( 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. It is done. Two or more of these monomers may be used in combination.

  Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4'-methoxyphenyl thioether, and the like. Two or more of these monomers may be used in combination.

Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, mat particles, and an inorganic filler is prepared, and the coating liquid is applied on a transparent support and then ionizing radiation or heat is applied. The antiglare antireflection film can be formed by curing by the polymerization reaction.
Examples of the photoradical polymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, -amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.
In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in the latest UV curing technology (P.159, issuer; Kazuhiro Takashiro, publisher; Technical Information Association, published in 1991).
Examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 907) manufactured by Ciba Geigy Japan.
It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.
Accordingly, a coating liquid containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, matte particles and an inorganic filler is prepared, and the coating liquid is applied onto a transparent support and then subjected to a polymerization reaction by ionizing radiation or heat. It can be cured to form an antiglare antireflection film.

Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

The antiglare hard coat layer has an average particle size of 1 to 10 μm, preferably 1.5 to 7.0 μm, more preferably 2.0 to 6.0 μm for the purpose of imparting antiglare properties and internal scattering properties. Translucent particles, for example, inorganic compound particles or organic polymer (resin) particles are contained. The refractive index of the light-transmitting fine particles should be selected in relation to the refractive index of the antiglare hard coat layer other than the light-transmitting particles, but is in the range of 1.40 to 1.80. It is preferable.
Specific examples of the translucent particles include silica particles (for example, Nippon Shokubai Co., Ltd. Seahosta series refractive index = 1.43), alumina particles (for example, Sumitomo Chemical Co., Ltd. Sumiko Random Series refractive index = 1.64), particles of inorganic compounds such as TiO ₂ particles, or crosslinked acrylic particles (for example, MX series manufactured by Soken Chemical Co., Ltd., refractive index = 1.49), cross-linked styrene particles (for example, SX series manufactured by Soken Chemical Co., Ltd.) Preferred examples include resin particles such as refractive index = 1.61), crosslinked melamine particles, and crosslinked benzoguanamine particles (for example, Nippon Shokubai Co., Ltd. Eposter series refractive index = 1.68). Of these, crosslinked styrene particles are preferred. As the shape of the translucent particle, either a true sphere or an indefinite shape can be used, but a true spherical particle having a uniform surface protrusion shape is preferable.
Further, two or more different kinds of translucent particles may be used in combination. Even if there are two or more kinds of material and two or more kinds of particle sizes, there is no limitation. The light-transmitting particles, the content of the formed antiglare hard coat layer is preferably 100-1000 mg / ^{m 2,} antiglare hard coat layer as more preferably a 300 to 800 / ^{m 2} Contained in
Of the light-transmitting particles, the particle imparting antiglare property is preferably a particle having a particle size larger than the thickness of the antiglare layer. On the other hand, the particles that contribute to internal scattering, which are different from the refractive index of the antiglare layer, may be particles that impart this antiglare property, and / or do not further contribute to imparting the antiglare property and are contained in the layer. It may be an embedded particle. In this case, in order not to increase the antiglare property too much, it is preferable that the particles have a particle size smaller than the thickness of the antiglare layer. In order to exhibit the light scattering property described in the present claims, the particle size of the particle imparting antiglare property is preferably 3 μm to 7 μm, more preferably 4 to 6 μm, and the particle imparting internal scattering property The particle size of is preferably 2 to 5 μm, more preferably 3 to 4 μm. In order to adjust the scattering property, a plurality of particles having the same particle diameter or different refractive indexes may be used. Although there is a preferable range as described above, the content and the particle diameter are not particularly limited as long as the requirements described in the present invention are satisfied.

In order to adjust the refractive index of the antiglare layer, the antiglare hard coat layer is selected from silicon, titanium, zirconium, aluminum, indium, zinc, tin, and antimony separately from the above light-transmitting particles. It is preferable that an inorganic filler having an average particle size of 0.2 μm or less, preferably 0.1 μm or less, and more preferably 0.06 μm or less is contained. The shape of the inorganic filler is not particularly limited, and for example, any of a spherical shape, a plate shape, a fiber shape, a rod shape, an indefinite shape, a hollow shape, and the like are preferably used. This inorganic filler can contribute to curling prevention and surface hardness improvement by the filling amount. When the antiglare layer contains an inorganic filler, the refractive index of the antiglare layer is determined by the refractive index of each of the transparent resin and the inorganic filler constituting the antiglare layer and the mixing ratio thereof. The refractive index difference between the refractive index of the antiglare layer and the internal scattering particles among the translucent particles is preferably 0.05 to 0.15. If it is less than 0.05, the internal scattering property is low, it must contain a large volume of internal scattering particles, and there is a concern that the film strength of the antiglare antireflection film may be lowered.
On the other hand, if it exceeds 0.15, the scattering angle of the scattered light becomes large, resulting in a direction in which the character blur becomes intense, which is not preferable as an antireflection film. Most preferably, the refractive index difference is 0.07 to 0.13.
The magnitude of the refractive index of the antiglare layer hard coat layer and the translucent particles is not particularly limited, but in order to reduce the character blur, within the range of the refractive index difference described above, the string protective layer hard coat It is preferable to lower the refractive index of the layer, and in order to further reduce the reflectance as an antiglare antireflection film, it is preferable to increase the refractive index of the antiglare layer hard coat layer, depending on the design concept. Selected.

Specific examples of the inorganic filler used in the antiglare hard coat layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO, and SiO _2. It is done. Among the inorganic fillers, SiO ₂ , TiO ₂ , and ZrO ₂ are particularly preferable from the viewpoint of handleability. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
The amount of these inorganic fillers added is preferably 10 to 90% of the total mass of the antiglare hard coat layer, more preferably 20 to 70%, and particularly preferably 30 to 50%.
In addition, since such an inorganic filler has a particle size sufficiently smaller than the wavelength of light, scattering does not occur, and a composite in which the filler is dispersed in a resin binder behaves as an optically uniform substance as described above. .

  The refractive index of the antiglare hard coat layer made of a resin binder or the antiglare hard coat layer containing an inorganic filler in the present invention is preferably 1.48 to 1.70, more preferably. Is 1.50 to 1.65. In order to set the refractive index within the above range, as described above, the types and amount ratios of the resin binder and the inorganic filler may be appropriately selected. How to select can be easily known experimentally in advance.

The antiglare hard coat layer of the present invention prevents fluorine or silicone surfactants or both, particularly in order to ensure surface uniformity such as coating unevenness, drying unevenness, and point defects. It can contain in the coating composition for glare layer formation. In particular, a fluorine-based surfactant is preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects of the antiglare antireflection film of the present invention appears in a smaller addition amount.
Preferable examples of the fluorosurfactant include perfluoroalkylsulfonic acid amide group-containing nonions such as 3M's Fluorard FC-431, Daifuku Ink's MegaFuck F-171, F-172, F- Perfluoroalkyl group-containing oligomers such as 173 and F-176PF. Examples of the silicone-based surfactant include polydimethylsiloxane in which a side chain or a main chain terminal is modified with various substituents such as oligomers such as ethylene glycol and propylene glycol.

However, the surface energy of the antiglare layer is increased by using the surfactant as described above, because the functional groups containing F atoms and / or the functional groups having Si atoms are segregated on the surface of the antiglare layer. When the low refractive index layer is overcoated on the antiglare layer, there may be a problem that the antireflection performance deteriorates. This is presumably because minute unevenness that cannot be detected by visual observation of the film thickness of the low refractive index layer deteriorates because the wettability of the coating composition used for forming the low refractive index layer deteriorates. In order to solve such a problem, the surface energy of the antiglare layer is preferably 25 mN · m ^{−1 to} 70 mN · by adjusting the structure and addition amount of the fluorine-based and / or silicone-based surfactant. to m ^-1, more preferably it is effective to control the ^{35mN · m -1 ~70mN · m -1} , further 50 to 100 weight percent of the coating solvent of the low refractive index layer as described later 100 ° C. It was found in the examination that it is effective to have the following boiling point. In order to realize the surface energy as described above, F / C, which is the ratio of the peak derived from the F atom and the peak derived from the C atom measured by X-ray photoelectron spectroscopy, is 0.40 or less, and / or It has also been found that Si / C, which is the ratio of the Si atom-derived peak to the C atom-derived peak, needs to be 0.30 or less.

  The film thickness of the antiglare hard coat layer of the present invention is preferably 1 to 10 μm, more preferably 2 to 7 μm, still more preferably 3 to 5 μm. If the film thickness is too thin, the surface hardness as an antiglare and antireflection film is lowered, and it becomes impossible to contain translucent particles in a preferable range. On the other hand, if the film thickness is too thick, This is because the ratio of the binder component becomes high, resulting in problems such as poor applicability due to an increase in liquid viscosity.

The surface protrusion shape of the string-proof antireflection film of the present invention includes (1) material type, particle size, addition amount of light-transmitting fine particles imparting antiglare property and internal scattering property, and (2) resin or The thickness of the antiglare layer composed of a composite of resin and inorganic filler, (3) solvent composition of coating solution, (4) wet coating amount, (5) drying conditions, (6) curing conditions for ionizing radiation curable resin, etc. It can be mentioned as a control factor, and the influence of (1) and (2) is great among them. As a result of our investigation, even if it is an anti-glare antireflection film that gives the same anti-glare property, the display power is turned off if each surface protrusion shape is different to express this total anti-glare property. At the time of black display of liquid crystal, it was found that the appearance of black tightening (in other words, whiteness) differs due to the difference in surface scattering. When the protrusion inclination angle of the surface protrusion is large, the surface scattering property to a wide angle region becomes strong, so that black tightening is lost, whitish, and high-class feeling is lost. The black tightening clearly shows that there is a good correlation with the angle of 95% frequency from the small angle side of the protrusion inclination angle distribution, preferably 20 ° or less, more preferably 15 ° or less, and further preferably 13 ° or less. is there.
The average surface protrusion inclination angle that correlates well with the antiglare property is more preferably 1 to 5 °, more preferably 1.5 to 4.5 °, and further preferably 2 to 4 °.
When manufacturing by the manufacturing method of the present invention, the above (3), (4), (5), etc. are important influencing factors, and therefore it is easy to achieve both surface shape control and surface / defect control. Selection is desirable.

The solvent of the coating solution used for forming the low refractive index layer, hard coat layer, and other constituent layers according to the present invention includes solubility of constituent components of each layer, stability of added particles, coating, etc. It can be appropriately selected from the viewpoints of solubility / diffusibility in the underlying layer, drying property in the drying process, viscosity adjustment, and the like. The composition of the solvent may be either single or mixed, but it is more preferable to mix appropriately in order to adjust the drying property, viscosity and the like. In particular, mixing a high boiling point solvent and a low boiling point solvent is a preferred method.
Moreover, the main solvent in the coating liquid of this invention shows the solvent with the largest mass ratio among the solvents contained in a coating liquid.

  As the low boiling point solvent (the solvent having a boiling point of 100 ° C. or lower), for example, hexane (boiling point 68.7 ° C., hereinafter “° C.” is omitted), heptane (98.4), cyclohexane (80.7), Hydrocarbons such as benzene (80.1), dichloromethane (39.8), chloroform (61.2), carbon tetrachloride (76.8), 1,2-dichloroethane (83.5), trichloroethylene (87. 2) and other halogenated hydrocarbons, diethyl ether (34.6), diisopropyl ether (68.5), dipropyl ether (90.5), ethers such as tetrahydrofuran (66), ethyl formate (54.2) ), Methyl acetate (57.8), ethyl acetate (77.1), esters such as isopropyl acetate (89), acetone (56.1), 2-butanone (= Ketones such as tilethylketone, 79.6), methanol (64.5), ethanol (78.3), 2-propanol (82.4), 1-propanol (97.2), 2-butanol (99) .5), alcohols such as t-butanol (82.5), cyano compounds such as acetonitrile (81.6) and propionitrile (97.4), and carbon disulfide (46.2). . Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

Examples of the high boiling point solvent (the solvent having a boiling point of 100 ° C. or higher) include octane (125.7), toluene (110.6), xylene (138), tetrachloroethylene (121.2), and chlorobenzene (131.7). ), Dioxane (101.3), dibutyl ether (142.4), butyl acetate (126), isobutyl acetate (118), cyclohexanone (155.7), 2-methyl-4-pentanone (= MIBK, 115.9). ), 2-octanone (173), 1-butanol (117.7), iso-butanol (107.9), propylene glycol monomethyl ether (120), diacetone alcohol (168), N, N-dimethylformamide (153) ), N, N-dimethylacetamide (166), dimethyl sulfoxide (18) ), And the like. Preferred are cyclohexanone, 2-methyl-4-pentanone, and the like.
As the solvent composition of the antiglare hard coat layer of the present invention, a solvent having a boiling point of 100 ° C. or higher is 1% to 90% of the total solvent in the coating liquid, more preferably 3% to the total solvent in the coating liquid. It is preferable that 80% is contained. If there is no solvent having a boiling point of 100 ° C. or higher, a brushed surface is likely to occur during drying.
Further, from the viewpoint of obtaining the solubility and dispersibility of the raw materials constituting the antireflection film, a ketone solvent is preferable, methyl ethyl ketone (boiling point 80 ° C.), cyclohexanone (boiling point 156 ° C.), diacetone alcohol (boiling point 168 ° C.), Examples include methyl isobutyl ketone (boiling point 113 ° C.) and acetone (boiling point 56 ° C.). Further, Wet coating amount is also subject restrictions from coating ^{system, 3cc / m 2 ~20cc / m} 2, more preferably from ^{3cc / m 2 ~10cc / m 2} . If the amount of wet coating is too small, the viscosity of the coating solution for obtaining the necessary solid content coating amount is increased, and the coating properties (such as streaks) are likely to be affected, and the amount of wet coating increases. If too much, it becomes difficult to dry, which is disadvantageous.
The solid content concentration of the coating solution is preferably 3% to 60%, more preferably 5% to 50%. The drying condition factor is appropriately selected, and the temperature of the drying air, the supply / exhaust balance, the base temperature, the temperature of the coating solution, and the like are controlled.

  In the antiglare antireflection film of the present invention, a so-called smooth hard coat layer having no antiglare property for the purpose of improving the film strength is also preferably used, and a transparent support and an antiglare hard coat layer or a transparent support are used. It is coated between the low, medium and high refractive index layers.

A smooth hard coat layer will be described.
The material used for the smooth hard coat layer is the same as that described in the anti-glare hard coat layer except that the light-transmitting particles for imparting anti-glare properties are not used, and the resin binder or resin It is formed from a mixture of a binder and an inorganic filler.

  In the smooth hard coat layer of the present invention, silica and alumina are preferable as the inorganic filler in terms of strength and versatility, and silica is particularly preferable. Further, the surface of the inorganic filler is preferably subjected to silane coupling treatment, and a surface treatment agent having a functional group capable of reacting with the binder species on the filler surface is preferably used.

  The amount of these inorganic fillers added is preferably 10 to 90% of the total mass of the hard coat layer, more preferably 20 to 70%, and particularly preferably 30 to 50%. The film thickness of the smooth hard coat layer is preferably 1 to 10 μm, more preferably 2 to 7 μm, and still more preferably 3 to 5 μm.

The low refractive index layer of the present invention will be described below.
The refractive index of the low refractive index layer of the antiglare antireflection film of the present invention is preferably from 1.38 to 1.49, more preferably from 1.38 to 1.44.
Further, the low refractive index layer preferably satisfies the following formula (I) from the viewpoint of reducing the reflectance.

  mλ / 4 × 0.7 <n1d1 <mλ / 4 × 1.3 Formula (I)

In the formula, m is a positive odd number, n ₁ is the refractive index of the low refractive index layer, and d ₁ is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is a value in the range of 500 to 550 nm.
In addition, satisfy | filling said numerical formula (I) means that m (positive odd number, usually 1) which satisfy | fills numerical formula (I) exists in the said wavelength range.

The material for forming the low refractive index layer of the present invention will be described below.
For the low refractive index layer, as a low refractive index binder, a fluorinated polymer that crosslinks by heat or ionizing radiation having a dynamic friction coefficient of 0.03 to 0.15, a contact angle with water of 90 to 120 °, and a film strength improvement An inorganic filler is preferably used.

Examples of the crosslinkable fluorine-containing polymer used in the low refractive index layer include a perfluoroalkyl group-containing silane compound (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane), and other fluorine-containing monomers. And a fluorine-containing polymer having a monomer for providing a crosslinkable group as a structural unit.
Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc. ), A part of (meth) acrylic acid or a fully fluorinated alkyl ester derivative (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) or M-2020 (manufactured by Daikin)), a complete or partially fluorinated vinyl ether, and the like. Perfluoroolefins are preferred, and hexafluoropropylene is particularly preferred from the viewpoints of refractive index, solubility, transparency, availability, and the like.

  As structural units for imparting crosslinking reactivity, structural units obtained by polymerization of monomers having a self-crosslinkable functional group in advance in the molecule such as glycidyl (meth) acrylate and glycidyl vinyl ether, carboxyl groups, hydroxy groups, amino groups Obtained by polymerization of a monomer having a sulfo group or the like (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc.) And a structural unit obtained by introducing a crosslinking reactive group such as a (meth) acryloyl group into these structural units by a polymer reaction (for example, it can be introduced by a technique such as allowing acrylic acid chloride to act on a hydroxy group) And the like.

  In addition to the above-mentioned fluorine-containing monomer units and structural units for imparting crosslinking reactivity, monomers not containing fluorine atoms can be copolymerized as appropriate from the viewpoints of solubility in solvents and film transparency. There are no particular limitations on the monomer units that can be used in combination. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2) -Ethylhexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl) Vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate etc.), acrylamides (N-tertbutylacrylamide, N-silane) B hexyl acrylamide), methacrylamides, and acrylonitrile derivatives.

  As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the above polymer.

  The fluorine-containing polymer particularly useful in the present invention is a random copolymer of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing a crosslinking reaction alone (a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group). These crosslinkable group-containing polymerized units preferably occupy 5 to 70 mol% of the total polymerized units of the polymer, particularly preferably 30 to 60 mol%.

  Moreover, it is preferable that the polysiloxane structure is introduce | transduced in the fluorine-containing polymer of this invention in order to provide antifouling property. There is no limitation on the method of introducing the polysiloxane structure, but the polysiloxane block copolymer component is prepared using a silicone macroazo initiator as described in, for example, JP-A Nos. 11-189621, 11-2288631, and 2000-313709. A method of introducing a polysiloxane graft copolymer component using a silicone macromer as described in JP-A-2-251555 and JP-A-2-308806 is preferred. These polysiloxane components are preferably 0.5 to 10% by mass in the polymer, and particularly preferably 1 to 5% by mass.

  For imparting antifouling properties, reactive group-containing polysiloxanes other than the above (for example, KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22- 5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS (above trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), AK-5, AK-30, AK-32 (above A trade name, manufactured by Toa Gosei Co., Ltd.), Silaplane FM0275, Silaplane FM0721 (manufactured by Chisso Corporation), etc.) is also preferred. In this case, these polysiloxanes are preferably added in the range of 0.5 to 10% by mass of the total solid content of the low refractive index layer, and particularly preferably 1 to 5% by mass.

  Further, not only a polymer having the above-mentioned fluorine-containing monomer as a structural unit but also a copolymer with a monomer not containing a fluorine atom may be used. There are no particular limitations on the monomer units that can be used in combination. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2) -Ethylhexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl) Vinyl ether), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, Krilo nitrile derivatives and the like can be mentioned.

As the inorganic filler used in the low refractive index layer, those having a low refractive index are preferably used. Preferred inorganic fillers are silica and magnesium fluoride, and silica is particularly preferable.
The average particle size of the inorganic filler is preferably 0.001 to 0.2 μm, and more preferably 0.001 to 0.05 μm. The particle diameter of the filler is preferably as uniform (monodispersed) as possible.
As the inorganic filler, two kinds of fillers having different particle diameters may be used in combination. In particular, when an inorganic filler having a particle size of 0.02 to 0.05 μm and an inorganic filler having a particle size of 0.01 μm or less are used in combination, both reflectance and scratch resistance can be achieved. The ratio of the added amount of each of the two types of inorganic fillers having different particle diameters can be freely changed between 0 and 1 depending on the desired balance between reflectivity and scratch resistance. When it is desired to reduce the reflectance, it is preferable that the inorganic filler having a small particle diameter occupies the majority, and when it is desired to enhance the scratch resistance, it is preferable to increase the proportion of the inorganic filler having a large particle diameter.
The amount of the inorganic filler added is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and particularly preferably 15 to 30% by mass with respect to the total mass of the low refractive index layer.

The inorganic filler is preferably used after being subjected to a surface treatment. The surface treatment method includes physical surface treatment such as plasma discharge treatment and corona discharge treatment and chemical surface treatment using a coupling agent, but the use of a coupling agent is preferred. As the coupling agent, an organoalkoxymetal compound (eg, titanium coupling agent, silane coupling agent) including the compound of the general formula (1) described later is preferably used. When the inorganic filler is silica, silane coupling treatment is particularly effective.
The compound of the general formula (1) may be used as a surface treatment agent for the inorganic filler of the low refractive index layer in order to perform surface treatment in advance before the preparation of the layer coating solution, and further added during the preparation of the layer coating solution. And may be added to the layer.

The compound of the following general formula (1) may be contained in at least one of the hard coat layer (including those having antiglare properties) and the low refractive index layer of the antireflection film of the present invention. , Preferred for scratch resistance.
This compound is contained in a state in which the alkoxysilyl group is not hydrolyzed, or in the state of a hydrolyzate of an organosilane compound / or a partial condensate thereof, so-called sol component (hereinafter referred to as such). These organosilane compounds are particularly preferably contained as a sol component.
General formula (1)
(R ¹ ) m-Si (OR ² ) n
In the general formula (1), R ¹ represents a substituted or unsubstituted alkyl group or an aryl group. R ² represents a substituted or unsubstituted alkyl group or acyl group. m represents an integer of 0 to 3. n represents an integer of 1 to 4. The sum of m and n is 4.
The compound represented by the general formula (1) will be described.
In the general formula (1), R ¹ represents a substituted or unsubstituted alkyl group or aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, t-butyl, sec-butyl, hexyl, decyl, hexadecyl and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
Although there is no restriction | limiting in particular as a substituent, Halogen (fluorine, chlorine, bromine, etc.), a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), Aryl groups (phenyl, naphthyl, etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl, etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy, etc.), aryloxy (phenoxy, etc.), alkylthio groups (methylthio) , Ethylthio etc.), arylthio group (phenylthio etc.), alkenyl group (vinyl, 1-propenyl etc.), alkoxysilyl group (trimethoxysilyl, triethoxysilyl etc.), acyloxy group (acetoxy, acryloyloxy, methacryloyloxy etc.), Alkoxycarbonyl group Bonyl, ethoxycarbonyl, etc.), aryloxycarbonyl groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (acetylamino) Benzoylamino, acrylamino, methacrylamino and the like.
Of these, more preferred are a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group, and an acylamino group, and particularly preferred are an epoxy group and a polymerizable acyloxy group (acryloyloxy, methacryloyloxy). ) And a polymerizable acylamino group (acrylamino, methacrylamino). These substituents may be further substituted.
R ² represents a substituted or unsubstituted alkyl group or acyl group. The description of the alkyl group, acyl group and substituent is the same as R ¹ . R ² is preferably an unsubstituted alkyl group or an unsubstituted acyl group, and particularly preferably an unsubstituted alkyl group.
m represents an integer of 0 to 3. n represents an integer of 1 to 4. The sum of m and n is 4. When R ¹ or R ² there are a plurality, it may be different even multiple of R ¹ or R ² respectively the same. m is preferably 0, 1, 2 and particularly preferably 1.
Although the specific example of a compound represented by General formula (1) below is shown, it is not limited to these.

  Among these specific examples, (1), (12), (18), (19) and the like are particularly preferable.

The organosilane compound of the present invention is also preferably used in a state of being solated by hydrolysis / condensation reaction. Sollation can be performed in the absence of a solvent or in a solvent, but an organic solvent is preferably used in order to mix the components uniformly. For example, alcohols, aromatic hydrocarbons, ethers, ketones, esters, etc. Is preferred.
The solvent for solification is preferably one that dissolves the organosilane and the catalyst. In addition, it is preferable in the process that an organic solvent is used as a coating solution or a part of the coating solution, and those that do not impair the solubility or dispersibility when mixed with other materials such as a fluorine-containing resin are preferable.

  Among these, examples of the alcohols include monohydric alcohols and dihydric alcohols. Among these, monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether and ethylene glycol monoethyl ether acetate.

Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like. Specific examples of ethers include tetrahydrofuran and dioxane. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, Specific examples of esters such as diisobutyl ketone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.
These organic solvents can be used alone or in combination of two or more. The concentration of the solid content in the reaction is not particularly limited, but is usually in the range of 1% to 90%, preferably in the range of 20% to 70%.
The hydrolysis / condensation reaction of organosilane is preferably performed in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Examples include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium. From the viewpoint of production stability of the sol solution and storage stability of the sol solution, acid catalysts (inorganic acids, organic Acids) are preferred. Among inorganic acids, hydrochloric acid, sulfuric acid, and organic acids preferably have an acid dissociation constant in water (pKa value (25 ° C.)) of 4.5 or less, and an acid dissociation constant in hydrochloric acid, sulfuric acid, or water of 3.0 or less. More preferred is an organic acid, hydrochloric acid, sulfuric acid, an organic acid having an acid dissociation constant of 2.5 or less in water is more preferred, an organic acid having an acid dissociation constant in water of 2.5 or less is more preferred, and methanesulfonic acid Further, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.
The hydrolysis / condensation reaction is usually performed by adding 0.3 to 2 mol, preferably 0.5 to 1 mol of water to 1 mol of the hydrolyzable group of organosilane, and in the presence or absence of the solvent. Under stirring and preferably in the presence of a catalyst at 25-100 ° C.
When the hydrolyzable group is an alkoxide and the catalyst is an organic acid, the carboxyl group or sulfo group of the organic acid supplies protons, so that the amount of water added can be reduced, so The amount of water added is 0 to 2 mol, preferably 0 to 1.5 mol, more preferably 0 to 1 mol, and particularly preferably 0 to 0.5 mol. When alcohol is used as the solvent, it is also preferred that substantially no water is added.
The catalyst is used in an amount of 0.01 to 10 mol%, preferably 0.1 to 5 mol%, based on the hydrolyzable group when the catalyst is an inorganic acid, and when the catalyst is an organic acid, The optimum amount used varies depending on the amount of water added, but in the case of adding water, it is 0.01 to 10 mol%, preferably 0.1 to 5 mol% with respect to the hydrolyzable group. When water is not added, it is 1 to 500 mol%, preferably 10 to 200 mol%, more preferably 20 to 200 mol%, still more preferably 50 to 150 mol%, based on the hydrolyzable group. And particularly preferably 50 to 120 mol%.
The reaction is carried out by stirring at 25 to 100 ° C., but it is preferably adjusted as appropriate depending on the reactivity of the organosilane.

When the compound of the general formula 1 is not hydrolyzed, 1 to 300% by mass of the total solid content of the layer containing the compound is preferable, and 3 to 200% by mass is more preferable. 5-100 mass% is the most preferable.
The appropriate content in the case of the organosilane sol varies depending on the layer to be added, but the added amount of the low refractive index layer is preferably 0.1 to 50% by mass of the total solid content of the containing layer (added layer), 0.5-20 mass% is more preferable, and 1-10 mass% is especially preferable. The amount added to the optical thin film layer other than the low refractive index layer is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass, based on the total solid content of the containing layer (added layer). 10 mass% is more preferable, and 1-5 mass% is especially preferable.
In the low refractive index layer, the use amount of the organosilane sol with respect to the fluorine-containing resin is preferably 5 to 100% by mass, more preferably 5 to 40% by mass, still more preferably 8 to 35% by mass, 30% by mass is particularly preferred. If the amount used is small, it is difficult to obtain the effect of the present invention, and if the amount used is too large, the refractive index increases or the shape / surface shape of the film deteriorates.
As described above, it is preferable that the compound represented by the general formula (1) is coated by being included in at least one coating liquid of these hard coat layer to low refractive index layer.

  As the solvent of the coating solution used for forming the low refractive index layer according to the present invention, the solvents described above can be used. The solvent may be either alone or mixed, but when mixed, the solvent having a boiling point of 100 ° C. or lower is preferably 50 to 100%, more preferably 80 to 100%, more preferably 90 to 100%. More preferably, it is 100%. When the solvent having a boiling point of 100 ° C. or less is 50% or less, the drying speed is very slow, the coating surface condition is deteriorated, and the coating film thickness is also uneven, and the optical characteristics such as reflectance are also deteriorated. This problem is solved by using a coating solution containing a large amount of a solvent having a boiling point of 100 ° C. or lower.

Next, the high refractive index layer in the present invention will be described below.
The medium refractive index layer and the high refractive index layer of the present invention are coatings containing inorganic fine particles having a high refractive index, thermal or ionizing radiation curable monomers, initiators, or the aforementioned organosilane compounds and / or sols, and solvents. Formed by applying the composition, drying the solvent, curing by heat and / or ionizing radiation. As the inorganic fine particles, those composed of at least one metal oxide selected from Ti, Zr, In, Zn, Sn, and Sb oxides are preferable. The medium refractive index layer and the high refractive index layer thus formed are excellent in scratch resistance and adhesion as compared with those obtained by applying and drying a polymer solution having a high refractive index. In order to ensure dispersion stability, film strength after curing, etc., it contains a polyfunctional (meth) acrylate monomer and an anionic group as described in JP-A-11-153703, US Pat. No. 6,610,858B1, etc. It is preferable that a (meth) acrylate dispersant is contained in the coating composition.

  The average particle diameter of the inorganic fine particles is preferably 1 to 100 nm as an average particle diameter measured by a Coulter counter method. If it is 1 nm or less, the specific surface area is too large, so that the stability in the dispersion is poor, which is not preferable. When the thickness is 100 nm or more, scattering of visible light due to a difference in refractive index from the binder occurs, which is not preferable. The haze of the high refractive index layer and the medium refractive index layer is preferably 3% or less, more preferably 1% or less, and still more preferably 0.5% or less.

As the transparent support of the antiglare antireflection film of the present invention, it is preferable to use a plastic film. Examples of the polymer forming the plastic film include cellulose esters (eg, triacetylcellulose, diacetylcellulose, typically TAC-TD80UL, TD80UF, 60 μmTAC, T40UZ, FTUV50F, etc., manufactured by Fuji Photo Film Co., Ltd.), polyamide, polycarbonate, polyester ( Examples include polyethylene terephthalate, polyethylene naphthalate), polystyrene, polyolefin, norbornene resin (Arton: trade name, manufactured by JSR Corporation), amorphous polyolefin (ZEONEX: trade name, manufactured by Nippon Zeon Corporation), and the like. Of these, triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable.
Triacetyl cellulose consists of a single layer or a plurality of layers. A single-layer triacetyl cellulose is prepared by drum casting or band casting disclosed in Japanese Patent Laid-Open No. 7-11055, etc. of the published patent publication. It is prepared by the so-called co-casting method disclosed in JP-A-61-94725 and JP-B-62-43846. That is, the raw material flakes are solvents such as halogenated hydrocarbons (dichloromethane, alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate, etc.), ethers (dioxane, dioxolane, diethyl ether, etc.), etc. A solution (called a dope) with various additives such as a plasticizer, an ultraviolet absorber, an anti-degradation agent, a slipping agent, and a peeling accelerator is added to the horizontal endless as necessary. When casting by a dope supply means (called a die) on a support composed of a metal belt or a rotating drum, a single dope is cast in a single layer if it is a single layer, and a high concentration in the case of multiple layers. A low-concentration dope is co-cast on both sides of the cellulose ester dope, and the film is dried to some extent on the support to release the rigid film, and then peeled off from the support. A process comprising passed through a drying section by species of the conveying means to remove the solvent.

  A typical solvent for dissolving triacetylcellulose as described above is dichloromethane. However, from the viewpoint of the global environment and working environment, the solvent preferably does not substantially contain a halogenated hydrocarbon such as dichloromethane. “Substantially free” means that the proportion of halogenated hydrocarbon in the organic solvent is less than 5% by mass (preferably less than 2% by mass). When adjusting the dope of triacetyl cellulose using a solvent substantially free of dichloromethane or the like, a special dissolution method as described later is essential.

  The first dissolution method is called a cooling dissolution method and will be described below. First, triacetyl cellulose is gradually added to a solvent at a temperature around room temperature (-10 to 40 ° C.) while stirring. The mixture is then cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, most preferably -50 to -30 ° C). The cooling can be performed, for example, in a dry ice / methanol bath (−75 ° C.) or a cooled diethylene glycol solution (−30 to −20 ° C.). When cooled in this manner, the mixture of triacetyl cellulose and solvent solidifies. Furthermore, when this is heated to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C., most preferably 0 to 50 ° C.), a solution in which triacetyl cellulose flows in the solvent is obtained. The temperature can be raised by simply leaving it at room temperature or in a warm bath.

  The second method is called a high temperature melting method and will be described below. First, triacetyl cellulose is gradually added to a solvent at a temperature around room temperature (-10 to 40 ° C.) while stirring. The triacetyl cellulose solution of the present invention is preferably swollen beforehand by adding triacetyl cellulose to a mixed solvent containing various solvents. In this method, the dissolution concentration of triacetyl cellulose is preferably 30% by mass or less, but is preferably as high as possible from the viewpoint of drying efficiency during film formation. Next, the organic solvent mixed solution is heated to 70 to 240 ° C. under a pressure of 0.2 MPa to 30 MPa (preferably 80 to 220 ° C., more preferably 100 to 200 ° C., most preferably 100 to 190 ° C.). Next, since these heated solutions cannot be applied as they are, it is necessary to cool them below the lowest boiling point of the solvent used. In that case, it is common to cool to -10-50 degreeC and to return to a normal pressure. For cooling, the high-pressure and high-temperature vessel or line containing the triacetylcellulose solution may be left at room temperature, and more preferably, the apparatus may be cooled using a coolant such as cooling water. A cellulose acetate film substantially free of halogenated hydrocarbons such as dichloromethane and a process for producing the same are disclosed in JIII Journal of Technical Disclosure (Publication No. 2001-1745, published on March 15, 2001, hereinafter Published Technical Report 2001-1745). (Abbreviated as No.).

  When the antireflection film of the present invention is used in a liquid crystal display device, it is disposed on the outermost surface of the display by providing an adhesive layer on one side. When the transparent support is triacetylcellulose, triacetylcellulose is used as a protective film for protecting the polarizing layer of the polarizing plate. Therefore, it is preferable in terms of cost to use the antireflection film of the present invention as it is for the protective film.

The polarizing plate with an antireflection film of the present invention can be obtained by forming an outermost layer mainly composed of a fluorine-containing polymer on a transparent support and then performing a saponification treatment. The saponification treatment is performed by a known method, for example, by immersing the film in an alkali solution for an appropriate time. After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by dipping in a dilute acid so that the alkaline component does not remain in the film.
By saponification treatment, the surface of the transparent support opposite to the side having the outermost layer is hydrophilized.
The hydrophilized surface is particularly effective for improving the adhesion with a deflection film containing polyvinyl alcohol as a main component. In addition, the hydrophilic surface makes it difficult for dust in the air to adhere to it, so that it is difficult for dust to enter between the deflection film and the antireflection film when bonded to the deflection film, thus preventing point defects due to dust. It is valid.
The saponification treatment is preferably carried out so that the contact angle of water on the surface of the transparent support opposite to the side having the outermost layer is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 20 ° or less.

  The polarizing plate with an antireflection film of the present invention is formed by using the antireflection film as at least one of the two protective films of the polarizing layer. By using the antireflection film of the present invention on the outermost surface, reflection of external light and the like can be prevented, and a polarizing plate having excellent antifouling property, scratch resistance and the like having high definition can be obtained. Moreover, in the polarizing plate of this invention, when an antireflection film serves as a protective film, manufacturing cost can be reduced.

  When the antireflection film of the present invention is used as one side of the surface protective film of the polarizer, it is necessary to saponify the surface of the transparent support opposite to the surface on which the antireflection layer is formed with an alkali. This is as described above. Specific means for the alkali saponification treatment can be selected from the following two. (1) is excellent in that it can be processed in the same process as a general-purpose triacetyl cellulose film, but since the surface is saponified to the antiglare antireflection film surface, the surface is hydrolyzed with alkali and the film deteriorates. There may be a problem in that there is a concern, and when the dried product of the saponification liquid component remains, it becomes dirty. In that case, although it becomes a special process, (2) is excellent. (1) After the antireflection layer is formed on the transparent support, the back surface of the film is saponified by immersing it in an alkaline solution at least once. (2) Before or after forming the antireflection layer on the transparent support, the alkaline solution is applied to the surface of the antiglare antireflection film opposite to the surface on which the antiglare antireflection film is formed, and heated. Only the back surface of the film is saponified by washing with water and / or neutralizing.

The antireflection film of the present invention can be formed by the following method, but is not limited to this method.
First, a coating solution containing components for forming each layer is prepared. Next, the coating liquid for forming the hard coat layer is reverse gravure method (classified as gravure coating method, micro gravure coating method, etc.), dip coating method, air knife coating method, curtain coating method, roller coating method The coating is applied on the transparent support by the wire bar coating method and the extrusion coating method (see US Pat. No. 2,681,294), followed by heating and drying. The microgravure coating method is particularly preferred. Thereafter, the monomer for forming the hard coat layer is polymerized and cured by light irradiation or heating. Thereby, a hard coat layer is formed.
Here, if necessary, the hard coat layer may be an antiglare hard coat layer, and a smooth hard coat layer may be applied and cured by the same method before application. Next, a coating solution for forming a low refractive index layer is applied onto the hard coat layer in the same manner, and light irradiation or heating is performed to form the low refractive index layer. In this way, the antireflection film of the present invention is obtained.

  The micro gravure coating method used for coating each layer of the antireflection film of the present invention is a support having a gravure roll having a diameter of about 10 to 100 mm, preferably about 20 to 50 mm and having a gravure pattern engraved on the entire circumference. The gravure roll is rotated in the reverse direction with respect to the conveying direction of the support, and the surplus coating liquid is scraped off from the surface of the gravure roll by a doctor blade. The coating method is characterized in that the coating solution is transferred to the lower surface of the support at a position in a free state. A roll-shaped transparent support is continuously unwound, and at least one layer of at least one of a hard coat layer or a low refractive index layer containing a fluorine-containing polymer is provided on one side of the unwound support. Can be applied by.

  As coating conditions by the micro gravure coating method, the number of gravure patterns imprinted on the gravure roll is preferably 50 to 800 lines / inch, more preferably 100 to 300 lines / inch, and the depth of the gravure pattern is 1 to 600 μm. Is preferable, 5 to 200 μm is more preferable, the rotation speed of the gravure roll is preferably 3 to 800 rpm, more preferably 5 to 200 rpm, and the conveyance speed of the support is 0.5 to 100 m / min. It is preferably 1 to 50 m / min.

  The antireflection film of the present invention thus formed has a haze value in the range of 10 to 70%, preferably 30 to 50%, and an average reflectance of 450 nm to 650 nm is preferably 2.2% or less, preferably Is 1.9% or less.

  When the antireflection film of the present invention has a haze value and an average reflectance in the above range, good antireflection properties can be obtained without causing deterioration of the transmitted image.

The antireflection film of the present invention can be applied to display devices such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display device (CRT). Since the antireflection film of the present invention has a transparent support, the transparent support side is adhered to the image display surface of the display device.

  The antireflection film of the present invention is used in combination with a polarizer, a transparent support, an optical compensation film composed of an optical anisotropic layer in which the orientation of the discotic liquid crystal is fixed, and a polarizing plate composed of a light scattering layer. It is preferable. Furthermore, the film other than the antireflection film among the two protective films of the polarizer in the polarizing plate is an optical compensation film having an optical compensation layer comprising an optical anisotropic layer, and the optical anisotropic layer is A layer having a negative birefringence composed of a compound having a discotic structural unit, the disc surface of the discotic structural unit is inclined with respect to the surface protective film surface, and the disc surface of the discotic structural unit; A polarizing plate in which the angle formed with the surface protective film surface changes in the depth direction of the optically anisotropic layer is more preferable. A polarizing plate comprising a light scattering layer is described in, for example, JP-A No. 11-305010. More specifically, when the antireflection film of the present invention is used as one side of a surface protective film of a polarizer, twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching. (IPS), optically compensatory bend cell (OCB), etc., can be preferably used for transmissive, reflective, or transflective liquid crystal display devices. In particular, for a TN mode or IPS mode liquid crystal display device, as described in JP-A-2001-100043, an optical compensation film having an effect of widening the viewing angle is used for the protective film on the back and front of the polarizer. By using it on the surface opposite to the antireflection film of the present invention, a polarizing plate having an antireflection effect and a viewing angle widening effect can be obtained with the thickness of one polarizing plate, which is particularly preferable.

Any polarizing film can be applied as the polarizing film. For example, when a polyvinyl alcohol film is continuously supplied and stretched while holding both ends by holding means and stretched, the locus of the holding means from the substantial holding start point to the substantial holding release point at one end of the film L1 and the locus L2 of the holding means from the substantial holding start point at the other end to the substantial holding release point are in the relationship of the following expression (2) with respect to the distance W between the left and right substantial holding release points, The straight line connecting the holding start points is approximately perpendicular to the center line of the film introduced into the holding process, and the straight line connecting the left and right substantial holding release points is approximately orthogonal to the center line of the film sent to the next process. (See FIG. 2; see US Patent Publication 2002-8840A1.)
Formula (2) | L2-L1 |> 0.4W

  When used in a transmissive or transflective liquid crystal display device, it is used in combination with a commercially available brightness enhancement film (a polarized light separation film having a polarization selective layer, such as D-BEF manufactured by Sumitomo 3M Co., Ltd.). Thus, a display device with higher visibility can be obtained. Further, by combining with a λ / 4 plate, it can be used to reduce reflected light from the surface and the inside as a polarizing plate for reflective liquid crystal or a surface protective plate for organic EL display. Furthermore, the antireflection layer of the present invention can be formed on a transparent support such as PET or PEN, and can be applied to an image display device such as a plasma display panel (PDP) or a cathode ray tube display (CRT).

  In order to describe the present invention in detail, examples will be described below, but the present invention is not limited thereto.

[Example 1]
(Preparation of coating solution (1) for antiglare hard coat layer)
Commercially available silica-containing UV curable hard coat solution (Desolite KZ7317, manufactured by JSR Corporation, solid content concentration of about 72%, SiO ₂ content of solid content of about 38%, polymerizable monomer DPHA, containing polymerization initiator) 61.3 Part by weight was diluted with 8.4 parts by weight of methyl isobutyl ketone. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.51.
Furthermore, a 25% methyl isobutyl ketone dispersion of crosslinked polystyrene particles having an average particle size of 3.5 μm (trade name: SX-350H, manufactured by Soken Chemical Co., Ltd.) was dispersed in this solution at 10,000 rpm for 30 minutes using a Polytron disperser. Next, 11.0 parts by mass of the dispersion was added, and then a 25% methyl isobutyl ketone dispersion of crosslinked polystyrene particles having an average particle diameter of 5 μm (trade name: SX-500H, manufactured by Soken Chemical Co., Ltd., refractive index 1.61) was added. 14.4 parts by mass of the dispersion liquid dispersed at 10,000 rpm for 30 minutes with a Polytron disperser was added. Further, 4.9 parts by mass of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was added. The solvent composition of this coating solution was MEK (boiling point 79.6 ° C.) / MIBK (boiling point 115.9 ° C.) = 3/7.
The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution (1) for an antiglare hard coat layer.

(Preparation of coating solution A for low refractive index layer)
Thermally crosslinkable fluorine-containing polymer having a refractive index of 1.42 (JN-7228, solid content concentration 6%, manufactured by JSR Corporation) was added to 55.2 parts by mass of colloidal silica dispersion (MEK-ST, average particle size of 10 to 10%). 20 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.) 4.8 parts by mass, methyl ethyl ketone 28.0 parts by mass, cyclohexanone 2.8 parts by mass, 3-acryloxypropyltrimethoxysilane (KBM-5103 Shin-Etsu Chemical Co., Ltd.) ) Was added, and after stirring, the mixture was filtered with a polypropylene filter having a pore size of 1 μm to prepare a coating solution A for a low refractive index layer. The solvent composition of this coating solution was MEK / cyclohexanone (boiling point 155.7 ° C.) = 97/3.

The antiglare hard coating layer coating solution (1) and the low refractive index layer coating solution A were applied as follows using a coating machine as shown in FIG. The stacking combination was performed as described in Table 1.
(1) Coating of antiglare hard coat layer Triacetyl cellulose film (TAC-TD80UL, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm is unwound in a roll form, and the above antiglare hard coat layer is applied. The coating liquid (1) was applied under the conditions of a gravure roll rotation speed of 40 rpm and a conveyance speed of 10 m / min using a micro gravure roll with a diameter of 110 mm / inch and a gravure pattern with a depth of 35 μm and a doctor blade. . The temperature of the coating part at this time was 18 degreeC. After drying at 30 ° C. for 2 minutes in the first (first) drying zone, further drying at 100 ° C. for 2 minutes in the subsequent drying zone, and 240 W / min under a nitrogen purge with an oxygen concentration of 0.1% or less. Using an air-cooled metal halide lamp (produced by Eye Graphics Co., Ltd.), the coating layer is cured by irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² , and a dry film thickness of 4.0 μm is prevented. A dazzling hard coat layer was formed and wound up. The maximum wind speed in the first drying zone was 0.2 m / s, and it was confirmed that the coating film was set in the drying zone.
The refractive index of the antiglare layer hard coat layer was 1.51.
(2) Coating of low refractive index layer The film coated with the antiglare hard coat layer is unwound again, and the coating liquid A for the low refractive index layer is a gravure pattern having a line number of 200 lines / inch and a depth of 35 μm. Using a microgravure roll having a diameter of 50 mm and a doctor blade, the coating was performed under the conditions of a gravure roll rotation speed of 40 rpm and a conveyance speed of 10 m / min. The temperature of the coating part at this time was 18 degreeC. After drying at 30 ° C. for 2 minutes in the first drying zone, drying at 100 ° C. for 2 minutes in the subsequent drying zone, followed by post-heating at 140 ° C. for 8 minutes, and further with an oxygen concentration of 0.1% or less Using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge, irradiation was performed with ultraviolet light having an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² , and subsequently at 140 ° C. for 8 minutes. Heating was performed to form a low refractive index layer having a thickness of 0.096 μm and wound. The maximum wind speed in the first drying zone was 0.3 m / s, and it was confirmed that the coating film was set in the drying zone. The refractive index of the low refractive index layer was 1.43. (Completion of the antiglare antireflection film of Example Sample 1)

(Saponification treatment of antiglare antireflection film)
Example Sample 1 was subjected to the following treatment.
A 1.5N aqueous sodium hydroxide solution was prepared and kept at 50 ° C. Furthermore, a 0.01N dilute sulfuric acid aqueous solution was prepared. The produced anti-glare antireflection film was immersed in the aqueous sodium hydroxide solution for 2 minutes and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the above-mentioned dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Furthermore, this antiglare antireflection film was sufficiently dried at a temperature of 100 ° C.
In this manner, a saponified antiglare antireflection film was produced. Thereby, the TAC on the back surface of the antiglare antireflection film of Example Sample 1 was hydrophilized by being saponified.

(Preparation and mounting of anti-glare anti-reflection film polarizing plate)
Next, an antiglare antireflection polarizing plate was prepared using the saponified Example Sample 1.
Furthermore, the anti-glare antireflection film on the outer surface of a commercially available high-definition type notebook PC (manufactured by DELL Co., Ltd., 15-inch UXGA notebook PC) was peeled off together with the adhesive layer, and the back surface was saponified again. It was applied to TAC and pasted and mounted so that the antiglare antireflection layer faced the outer surface.

(Evaluation of antiglare antireflection film)
About the obtained film, the following items were evaluated.

(1) Appearance surface shape The produced anti-glare antireflection film was mounted on a 15-inch UXGA notebook PC manufactured by DELL Co., Ltd., and a detailed appearance inspection was performed with tungsten light.
No problem with the appearance of the surface: ○
No problem in practical use, but detects weak unevenness: △
Detects slightly strong unevenness: ×
Detects very strong unevenness: XX
Also, the amount of residual solvent in the coating layer was large, the coating film component was transferred to the reverse roll in the process, and the appearance of adhesion marks was also determined as (NG) ×.
(2) Evaluation of antiglare property An exposed fluorescent lamp (8000 cd / m ² ) without a louver was projected on the prepared antiglare film, and the degree of blur of the reflected image was evaluated according to the following criteria.
I do not know the outline of the fluorescent lamp at all: ◎
Slightly understand the outline of the fluorescent lamp: ○
The fluorescent lamp is blurred, but the outline can be identified: △
Fluorescent lamp is hardly blurred: ×
(3) Glitter evaluation Fluorescent lamp diffused light with a louver was projected on the created antiglare film, and surface glare was evaluated according to the following criteria.
Almost no glare seen: ○
There is slight glare: △
There is glare of a size that can be discerned by the eyes: ×
(4) Average reflectance Using a spectrophotometer (manufactured by JASCO Corporation), spectral reflectance by integrating sphere measurement was measured in a wavelength region of 380 to 780 nm. For the results, an integrating sphere average reflectance of 450 to 650 nm was used.

[Example Sample, Comparative Sample]
By adjusting the additive solvent and the solvent component of the raw material according to Example Sample 1, the coating solution of MEK / ethyl acetate (boiling point 57.8 ° C.) = 2/8, low refractive index layer for the antiglare hard coat layer Application of acetone (boiling point 56.1 ° C.) / MEK = 6/4, dichloromethane (boiling point 39.8 ° C.) / MEK = 6/4, and MEK / diacetone alcohol (boiling point 168 ° C.) = 95/5 Create a solution and change it to the coating solution solvent as described in Table 1 above, and change the temperature of the first drying section after the coating section when coating the antiglare hard coat layer and the low refractive index layer Samples prepared in exactly the same manner as Example Sample 1 except for the above are referred to as Example Samples 2-22 and Comparative Samples 1-10.

Next, the saponified films of Example Samples 1 to 22 and Comparative Samples 1 to 10 were bonded to a polarizing plate to prepare a polarizing plate with antiglare and antireflection, and the polarizing plate was used for antiglare property. When a liquid crystal display device having an antireflection layer disposed on the outermost layer was produced, Example Samples 1 to 22 had excellent contrast because there was no reflection of external light, and the surface appearance was very good. The liquid crystal display device has excellent visibility and appearance. On the other hand, in Comparative Samples 1 to 10, when the temperature of the first drying part from the application part exceeds 40 ° C., the appearance surface shape deteriorates, and when it is less than 10 ° C., the setting is completed. All of them were unsuitable as a display device because the adhesion marks on the reversing roll because they were not dried became visible.
Further, in Comparative Examples 7 and 8 in which the temperature of the first drying part was set to 80 ° C. and 100 ° C., which is equal to or higher than the boiling point of the main solvent of the antiglare hard coat coating solution, the unevenness in appearance was particularly severe, and this antireflection film It was not suitable as a forming method. Further, in the low refractive index layer, when dichloromethane having a low boiling point is used as a main solvent, the unevenness is strong when the first drying part is set to 35 ° C., which is 5 ° C. lower than the boiling point, and the appearance is reduced to 15 ° C. and 25 ° C. Improved.

[Examples 31 to 44]
(Preparation of organosilane sol composition a)
A reactor equipped with a stirrer and a reflux condenser, 161 parts of acryloyloxypropyltrimethoxysilane, 123 parts of oxalic acid, and 415 parts of ethanol were added and mixed, reacted at 70 ° C. for 5 hours, cooled to room temperature, and organosilane. A sol composition a was obtained.

(Preparation of coating solution for antiglare hard coat layer (2))
272 g of commercially available silica-containing UV curable hard coat liquid (solvent composition modified from Desolite Z7526, manufactured by JSR, solid content concentration of about 72%, SiO ₂ content of solid content of about 38%, polymerizable monomer, polymerization initiator contained) , 91 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.), 19.6 g of organosilane sol composition a, and 26.2 g of methyl isobutyl ketone Diluted with The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.52.
Further, a 30% methyl isobutyl ketone dispersion of classified reinforcing cross-linked polystyrene particles having an average particle size of 3.5 μm (trade name: SXS-350H, manufactured by Soken Chemical Co., Ltd.) was dispersed in this solution at 10,000 rpm for 20 minutes using a Polytron disperser. 44 g of the obtained dispersion was added, and then a 30% methyl isobutyl ketone dispersion of classified reinforcing cross-linked polystyrene particles having an average particle diameter of 5 μm (trade name: SXS-500H, manufactured by Soken Chemical Co., Ltd.) at 10,000 rpm with a Polytron disperser. 57.8 g of the dispersion dispersed for 30 minutes was added. The solvent composition of this coating solution was MEK / MIBK = 3/7.
The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution (2) for an antiglare hard coat layer.

(Preparation of coating solution for antiglare hard coat layer (3))
Commercially available zirconia-containing UV curable hard coat solution (Desolite Z7404, manufactured by JSR Corporation, solid content concentration of about 61.2%, ZrO ₂ content of solid content of about 69.6%, containing polymerizable monomer and polymerization initiator) 2 g, 28.8 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), acryloyloxypropyltrimethoxysilane (KBM5103 (trade name); manufactured by Shin-Etsu Chemical Co., Ltd.) 9.6 g was added, and further diluted with 20.1 g of methyl isobutyl ketone and 5.4 g of methyl ethyl ketone. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.62. The solvent composition of this coating solution was MEK / MIBK = 1/9.
Further, a 30% methyl isobutyl ketone dispersion of silica particles having an average particle size of 1.5 μm (trade name: Seahoster KE-P150, manufactured by Nippon Shokubai Co., Ltd.) was dispersed in this solution at 10,000 rpm for 20 minutes using a Polytron disperser. 29.5 g of the solution was added, and then a 30% methyl isobutyl ketone dispersion of classified reinforcing cross-linked methyl polymethacrylate particles having a mean particle size of 3 μm (trade name: MXS-300, manufactured by Soken Chemical Co., Ltd.) Was added for 30 minutes at 10,000 rpm, and 11.3 g of the dispersion which was aged for one week was added.
The mixture solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution (3) for an antiglare hard coat layer.

(Preparation of coating solution B for low refractive index layer)
Thermally crosslinkable fluorinated polymer having a refractive index of 1.42 (JN-7228, solid content concentration 6%, manufactured by JSR Corporation) 177 g and silica sol (MEK-ST, average particle size 10-20 nm, solid content concentration 30%, 7.0 g, manufactured by Nissan Chemical Co., Ltd., silica sol (MEK-ST particle size different product, average particle size 50 nm, solid content concentration 25%, manufactured by Nissan Chemical Co., Ltd.) 8.2 g, organosilane sol composition a 4.0 g Then, 90 g of methyl ethyl ketone and 9.0 g of cyclohexanone were added, and after stirring, the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution B for a low refractive index layer. The solvent composition of this coating solution was MEK / cyclohexanone = 97/3.

About said anti-glare hard-coat layer (2), (3) and the low-refractive-index layer B, it apply | coated like Example 31 to 44 according to the method as described in Example 1, respectively. At this time, the drying conditions were changed by appropriately changing the coating part temperature, the temperature of the drying zone, the arrangement of the zone, the coating speed, and the like. The combinations of lamination and drying conditions at this time are as shown in Table 2. In addition, the sample samples 41 to 44 using the antiglare hard coat liquid (3) were applied by adjusting the coating thickness so that the antiglare property was low (Δ level).
The antiglare antireflection film prepared as described above was subjected to saponification treatment, polarizing plate preparation and mounting in the same manner as in Example 1 and evaluated.

  As a result, Example Samples 31 to 44 did not reflect external light, provided excellent contrast, and had a good appearance. In particular, the time from the coating part to the first drying part may be shorter than 30 seconds, and the temperature of the first drying part may be 2 ° C. or more higher than the coating part in terms of surface, reflectance, and glare. The liquid crystal display device has good visibility and appearance.

[Example 51]
(Preparation of coating solution for hard coat layer)
306 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was dissolved in a mixed solvent of 16 parts by mass of methyl ethyl ketone and 220 parts by mass of cyclohexanone. After adding 7.5 parts by mass of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) to the obtained solution and stirring until dissolved, 450 parts by mass of MEK-ST (average particle size of 10 to 20 nm, solid content) 30 wt% SiO ₂ sol methyl ethyl ketone dispersion (manufactured by Nissan Chemical Co., Ltd.) was added and stirred to obtain a mixture, which was filtered through a polypropylene filter (PPE-03) with a pore size of 3 μm for the hard coat layer. A coating solution was prepared.
(Preparation of titanium dioxide dispersion)
Titanium dioxide ultrafine particles (TTO-55B, manufactured by Ishihara Techno Co., Ltd.) 30 parts by mass, dimethylaminoethyl acrylate (DMAEA, manufactured by Kojin Co., Ltd.) 1 part by mass, phosphate group-containing anionic dispersant (KAYARAD PM- 21, Nippon Kayaku Co., Ltd.) 6 parts by mass and cyclohexanone 63 parts by mass were dispersed with a sand grinder until the average particle size measured by the Coulter method was 42 nm to prepare a titanium dioxide dispersion.

(Preparation of coating solution for medium refractive index layer)
To 75 parts by mass of cyclohexanone and 19 parts by mass of methyl ethyl ketone, 0.11 part by mass of photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 0.04 parts by mass of photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) Was dissolved. Further, 3.1 parts by mass of titanium dioxide dispersion and 2.1 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) were added and stirred at room temperature for 30 minutes. Then, it filtered with 0.4 micrometer profile star (Nippon Pole Co., Ltd. product) with the hole diameter of 0.4 micrometer, and prepared the coating liquid for medium refractive index layers.

(Preparation of coating solution for high refractive index layer)
54 parts by mass of cyclohexanone and 18 parts by mass of methyl ethyl ketone, 0.13 parts by mass of photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 0.04 parts by mass of photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) Was dissolved. Furthermore, 26.4 parts by mass of titanium dioxide dispersion and 1.6 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) were added and stirred at room temperature for 30 minutes. Thereafter, the mixture was filtered through a profile star 0.4 μm (manufactured by Nippon Pole Co., Ltd.) having a pore diameter of 0.4 μm to prepare a coating solution A for a high refractive index layer.

(Preparation of coating solution C for low refractive index layer)
Refractive index is 1.42, and 6 mass percent of methyl ethyl ketone solution (JN-7228, manufactured by JSR Corporation) of thermally crosslinkable fluorine-containing resin is solvent-substituted to obtain 85 mass% of methyl isobutyl ketone and 15 mass of 2-butanol. A polymer solution containing 10% by mass of solid content in a mixed solvent consisting of% was obtained. In 70 parts by mass of this polymer solution, 10 parts by mass of MEK-ST (Methyl ethyl ketone dispersion of SiO ₂ sol having an average particle size of 10 to 20 nm and a solid content concentration of 30% by mass, manufactured by Nissan Chemical Co., Ltd.), organosilane sol composition A2 .17 parts by mass, and 42 parts by mass of methyl isobutyl ketone and 28 parts by mass of cyclohexanone were added. A coating liquid C for the rate layer was prepared.
(Creation of antireflection film)
About said hard-coat layer, medium refractive index layer, high refractive index layer, and low refractive index layer, it apply | coated according to the application | coating and drying method as described in Example 1, respectively. A hard coat layer coating solution was applied to a triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd., refractive index: 1.47) with a thickness of 80 μm using a gravure coater. After drying for 2 minutes at 30 ° C. in the first) drying zone, after further drying at 100 ° C. for 2 minutes in the subsequent drying zone, air cooling at 240 W / cm under a nitrogen purge with an oxygen concentration of 0.1% or less Using a metal halide lamp (manufactured by Eye Graphics Co., Ltd.), the coating layer was cured by being irradiated with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² , and wound up. The maximum wind speed in the first drying zone was 0.2 m / s, and it was confirmed that the coating film was set in the drying zone. This hard coat layer had a refractive index of 1.51 and a film thickness of 6 μm.
Subsequently, the medium refractive index layer coating solution was applied using a gravure coater, dried and cured under the same conditions as the hard coat, and the medium refractive index layer (refractive index: 1.63, film thickness: 67 nm) was formed. Provided.
On the medium refractive index layer, the above high refractive index layer coating solution is similarly applied, dried and cured using a gravure coater to form a high refractive index layer (refractive index: 1.90, film thickness: 107 nm). Provided.
Further, the coating liquid C for the low refractive index layer is applied on the high refractive index layer using a gravure coater, dried at 30 ° C. for 2 minutes in the first (first) drying zone, and then at 120 ° C. After drying for 1 minute, an irradiance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² using an air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) of 240 W / cm under a nitrogen purge with an oxygen concentration of 0.1% or less. Then, the coating layer was thermally cured at 120 ° C. for 8 minutes to provide a low refractive index layer (refractive index: 1.43, film thickness: 86 nm). In this way, an antireflection film 51 was prepared.
The antireflection film produced as described above was subjected to saponification treatment, polarizing plate production and mounting in the same manner as in Example 1 and evaluated.
As a result, the example sample 51 had no reflection of external light, an excellent contrast was obtained, and the surface appearance was good.

[Example Sample 1A]
A polarizing film was produced by the following method. The PVA film was immersed in an aqueous solution of 2.0 g / l iodine and 4.0 g / l potassium iodide at 25 ° C. for 240 seconds, and further immersed in an aqueous solution of boric acid 10 g / l for 60 seconds at 25 ° C. The film was introduced into a tenter stretching machine having a shape of 5 and stretched 5.3 times. The tenter was bent as shown in FIG. 2 with respect to the stretching direction, and thereafter the width was kept constant. After drying in an atmosphere of 80 ° C., it was detached from the tenter. The difference in transport speed between the left and right tenter clips was less than 0.05%, and the angle between the center line of the introduced film and the center line of the film sent to the next process was 46 °. Here, | L1-L2 | is 0.7 m, W is 0.7 m, and | L1-L2 | = W. The substantial stretching direction Ax-Cx at the tenter outlet was inclined by 45 ° with respect to the center line 22 of the film sent to the next process. Wrinkles and film deformation at the tenter exit were not observed.
Furthermore, it was bonded to Fuji Photo Film Co., Ltd. Fujitac (cellulose triacetate, retardation value 3.0 nm), which was saponified using an aqueous solution of PVA (Pura-117H, Kuraray Co., Ltd.) 3%, and further bonded at 80 ° C. It dried and the polarizing plate of effective width 650mm was obtained. The absorption axis direction of the obtained polarizing plate was inclined 45 ° with respect to the longitudinal direction. The polarizing plate had a transmittance at 550 nm of 43.7% and a polarization degree of 99.97%. Further, when cut into a size of 310 × 233 mm as shown in FIG. 3, a polarizing plate having an absorption efficiency of 91.5% and an inclination angle of 45 ° with respect to the side was obtained.
Next, the saponified film of Example Sample 1 was bonded to the above polarizing plate to produce a polarizing plate with antiglare and antireflection. Using this polarizing plate, a liquid crystal display device having an antiglare antireflection layer disposed on the outermost layer was produced. As a result, there was no reflection of external light, so that excellent contrast was obtained, and excellent visibility and appearance were obtained. It became a display device.

[Example Sample 1B]
Saponification of Example Sample 1 instead of “Fujitack (cellulose triacetate, retardation value: 3.0 nm) manufactured by Fuji Photo Film Co., Ltd.” in the production of polarizing plate having 45 ° absorption axis inclined of Example Sample 1A. The processed film was laminated to produce a polarizing plate with antiglare and antireflection. Using this polarizing plate, a liquid crystal display device having an antiglare antireflection layer disposed on the outermost layer was produced. As in Example Sample 1, there was no reflection of external light, and an excellent contrast was obtained. It became a display device having high visibility and appearance.

[Example Sample 1C]
The above Example Sample 1 was immersed in an aqueous 1.5 N NaOH solution at 55 ° C. for 2 minutes, neutralized, washed with water, and the triacetyl cellulose surface on the back surface of the film was saponified to give 80 μm thick triacetyl. A film obtained by saponifying cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) under the same conditions is adsorbed with iodine on polyvinyl alcohol, and stretched to adhere and protect both sides of the polarizer to protect the polarizing plate. Produced. A liquid crystal display device of a notebook personal computer equipped with a transmissive TN liquid crystal display device (Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer) so that the anti-reflection film side is the outermost surface. When the D-BEF made of D-BEF is attached to the polarizing plate on the viewing side of the backlight and the liquid crystal cell), excellent contrast is obtained because there is no reflection of external light, and excellent visibility. As a liquid crystal display device having an external appearance, there was very little reflection of the background, and a display device with very high display quality was obtained.

[Example Sample 1D]
The discotic structural unit circle is applied to the protective film on the liquid crystal cell side of the polarizing plate on the viewing side of the transmission type TN liquid crystal cell to which the sample sample 1 is attached, and the protective film on the liquid crystal cell side of the polarizing plate on the backlight side. A field of view having an optical compensation layer in which the disc surface is inclined with respect to the transparent support surface, and the angle formed by the disc surface of the discotic structural unit and the transparent support surface changes in the depth direction of the optical anisotropic layer. When using a wide angle film (wide view film SA-12B, manufactured by Fuji Photo Film Co., Ltd.), it has excellent contrast in bright rooms, excellent visibility and appearance, and has a vertical, horizontal, and horizontal viewing angle. A very wide and very good display device with high display quality was obtained.

[Example Sample 1E]
When Example Sample 1 was bonded to a glass plate on the surface of an organic EL display device via an adhesive, reflection on the glass surface was suppressed, and a display device with a very high visibility and good appearance was obtained. It was.

[Example 1F]
Using Example Sample 1, a polarizing plate with a single-sided antireflection film was prepared, and a λ / 4 plate was bonded to the opposite surface of the polarizing plate on the side having the antireflection film, and the glass on the surface of the organic EL display device When affixed to the plate, the surface reflection and the reflection from the inside of the surface glass were cut, and a display device with a good appearance and extremely high visibility was obtained.

[Example 1G]
A sample prepared in exactly the same manner except that the 80 μm TAC support of Example Sample 1D was changed to 40 μm TAC manufactured by Fuji Photo Film Co., Ltd. is referred to as Example Sample 1G. This Example Sample 1G was an excellent display device having a polarizing plate with an antireflection film that was very thin and effective for thinning portable terminals and notebook PCs.

DESCRIPTION OF SYMBOLS 1 Anti-glare antireflection film 2 Transparent support 3 Anti-glare hard coat layer 4 Low refractive index layer 5 Anti-glare imparting particle 6 Internal scattering imparting particle (A) Film introduction direction (B) Film transport to the next process Direction (a) Step of introducing a film (b) Step of stretching a film (c) Step of sending a stretched film to the next step A1 Position of biting into the film holding means and starting position of film stretching (substantially holding start point: right)
B1 Biting position of film holding means (left)
C1 Film stretch starting position (substantially holding start point: left)
Cx film release position and film stretching end point reference position (actual holding release point: left)
Ay Film drawing end point reference position (substantially holding release point: right)
| L1-L2 | Stroke difference W between left and right film holding means W Substantially width θ at the end of the film stretching process Angle 11 formed by stretching direction and film traveling direction Center line 12 of introduction side film Center line 13 of film sent to next process Trajectory of film holding means (left)
14 Trajectory of film holding means (right)
15 Introducing film 16 Film 17, 17 ′ sent to the next step Left and right film holding start (engagement) points 18, 18 ′ Disengagement point 21 from the left and right film holding means Center line 22 of the introducing side film Sent to the next step The center line 23 of the film to be filmed The trajectory of the film holding means (left)
24 Trajectory of film holding means (right)
25 Introduction-side film 26 Films 27, 27 'sent to the next step 28, 28' Left and right film holding start (biting) points 28, 28 'Left and right film holding points 81 Polarizing plate absorption shaft 82 Longitudinal direction 1a Delivery part 2a Application unit 3a First drying unit 4a Second drying unit 5a Curing unit, reversing roll 6a Winding unit

Claims (11)

On a transparent support, antiglare and antireflection by forming an average particle size antiglare hard coat layer of the antiglare property-imparting particles to contain RumakuAtsu small without even one layer of 1 to 10 [mu] m 1 to 10 [mu] m a way to manufacture the fill-time,
A coating step for forming the antiglare hard coat layer, a drying step by the first drying unit, a drying step by the second drying unit and a curing step;
The drying process by the first drying unit for forming the antiglare hard coat layer has a drying time of 5 seconds to 120 seconds, a windbreak cover is provided, and the wind speed of the wind hitting the coating surface is 0.5 m / s or less, wherein 10 ° C. or more lower than the boiling point of the main solvent in the coating solution, and 1 0 ° C. or higher 40 ° C. in a temperature controlled below, in Ru drying step to end the set of coating the fabric layer Yes,
The proof for forming the antiglare hard coat layer a second drying section by the drying step, a high temperature than the previous SL first drying section, the lowest boiling point solvent contained in the coating cloth liquid the boiling point temperature or higher, a step of drying at least a high boiling point boiling point + 20 ° C. or less of a solvent contained in the coating solution, the manufacturing method of the anti-glare and anti-reflection film. On a transparent support, antiglare and antireflection by forming an average particle size antiglare hard coat layer of the antiglare property-imparting particles to contain RumakuAtsu small without even one layer of 1 to 10 [mu] m 1 to 10 [mu] m a way to manufacture the fill-time,
A coating step for forming the antiglare hard coat layer, a drying step by the first drying unit, a drying step by the second drying unit and a curing step;
The drying process by the first drying unit for forming the antiglare hard coat layer has a drying time of 5 seconds to 120 seconds, a windbreak cover is provided, and the wind speed of the wind hitting the coating surface is 0.5 m / s or less, wherein 10 ° C. or more lower than the boiling point of the main solvent in the coating solution, and 1 0 ° C. or higher 40 ° C. in a temperature controlled below, in Ru drying step to end the set of coating the fabric layer Yes,
Drying process by the second drying section for forming the antiglare hard coat layer is the step of drying at 140 ° C. hereinafter 5 0 ° C. or higher at a higher temperature than the previous SL first drying section the method of anti-glare and anti-reflection film.   The manufacturing method of the anti-glare antireflection film according to claim 1 or 2, wherein the drying step by the first drying unit for forming the anti-glare hard coat layer is temperature-controlled at 15 ° C or more and 35 ° C or less. . Antiglare according to claim 1, wherein the temperature control in the first dry燥部for forming the antiglare hard coat layer, and wherein the start that within 30 seconds after coating For producing antireflective film. Temperature of the first dry燥部is, the anti-glare and anti-reflection film according to any one of the preceding claims, characterized in that a temperature higher 2 ℃ least 30 ° C. less than the temperature of the coated portion Production method.   6. The solvent composition in the coating solution of the antiglare hard coat layer includes 1% to 90% of a solvent having a boiling point of 100 [deg.] C. or more, based on the total solvent in the coating solution. The manufacturing method of the anti-glare antireflection film of Claim 1.   A method for producing an antireflection film by forming at least one hard coat layer having a thickness of 1 to 10 μm on a transparent support,
  Having a coating process for forming the hard coat layer, a drying process by a first drying section, a drying process by a second drying section and a curing process;
  The drying process by the first drying section for forming the hard coat layer has a drying time of 5 seconds to 120 seconds, a windbreak cover is provided, and the wind speed of the wind hitting the coating surface is 0.5 m. Is a drying step that ends the set of the coating film by controlling the temperature to be 10 ° C. or more and 40 ° C. or less lower than the boiling point of the main solvent in the coating solution,
  The drying step by the second drying section for forming the hard coat layer is higher than the first drying section and is applied at a temperature equal to or higher than the boiling temperature of the lowest boiling point solvent contained in the coating solution. It is a step of drying at the boiling point temperature of the solvent having the highest boiling point contained in the liquid + 20 ° C. or lower.
A method for producing an antireflection film.   A method for producing an antireflection film by forming at least one hard coat layer having a thickness of 1 to 10 μm on a transparent support,
  Having a coating process for forming the hard coat layer, a drying process by a first drying section, a drying process by a second drying section and a curing process;
  The drying process by the first drying section for forming the hard coat layer has a drying time of 5 seconds to 120 seconds, a windbreak cover is provided, and the wind speed of the wind hitting the coating surface is 0.5 m. Is a drying step that ends the set of the coating film by controlling the temperature to be 10 ° C. or more and 40 ° C. or less lower than the boiling point of the main solvent in the coating solution,
  The method for producing an antireflection film, wherein the drying step by the second drying unit for forming the hard coat layer is a step of drying at a temperature higher than the first drying unit by 50 ° C. or more and 140 ° C. or less. .   A method for producing an antireflection film by forming at least one hard coat layer on a transparent support and further forming an outermost low refractive index layer,
  A coating step for forming the hard coat layer, a drying step and a curing step, and
  Having a coating step for forming the low refractive index layer, a drying step by a first drying unit and a drying step by a second drying unit;
  The drying step by the first drying section for forming the low refractive index layer is provided with a cover for windbreak, and the wind speed of the wind hitting the coating film surface is 0.5 m / s or less, in the coating solution It is a drying step of controlling the temperature to be 10 ° C. or more and 40 ° C. or less lower than the boiling point of the main solvent and finishing the setting of the coating film,
  The drying step by the second drying unit for forming the low refractive index layer is at a temperature higher than that of the first drying unit, and is equal to or higher than the boiling point of the lowest boiling point solvent contained in the coating liquid. A method for producing an antireflection film, which is a step of drying at the boiling point temperature of the solvent having the highest boiling point contained in the coating liquid + 20 ° C. or lower.   A method for producing an antireflection film by forming at least one hard coat layer on a transparent support and further forming an outermost low refractive index layer,
  A coating step for forming the hard coat layer, a drying step and a curing step, and
  Having a coating step for forming the low refractive index layer, a drying step by a first drying unit and a drying step by a second drying unit;
  The drying step by the first drying section for forming the low refractive index layer is provided with a cover for windbreak, and the wind speed of the wind hitting the coating film surface is 0.5 m / s or less, in the coating solution It is a drying step of controlling the temperature to be 10 ° C. or more and 40 ° C. or less lower than the boiling point of the main solvent and finishing the setting of the coating film,
  Production of an antireflection film, wherein the drying step by the second drying unit for forming the low refractive index layer is a step of drying at a temperature higher than the first drying unit at 50 ° C. or more and 140 ° C. or less. Method.   11. The production of an antireflection film according to claim 9, wherein a solvent having a boiling point of 100 ° C. or lower is 50% to 100% as a solvent of the coating solution used for forming the low refractive index layer. Method.

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