JP2017167560A - Manufacturing method of anti-glare film, anti-glare film, polarizing plate, and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of an anti-glare film by which a surface shape of an anti-glare film can be freely controlled in a wide range.SOLUTION: A manufacturing method of an anti-glare film includes the steps of: applying coating liquid on at least one surface of translucent base material 20, and hardening the coating liquid to form an anti-glare layer. As coating liquid, the coating liquid including resin, particles 12, and a solvent is used. The manufacturing method further includes a shearing step of causing shear on the coating liquid applied on the translucent base material 20. In the shearing step, shear distance of coating defined by the following formula (I) is adjusted so as to adjust a surface shape of the anti-glare film. S=∫Vdt (I) (where V represents shear rate (m/s), and t represents shear holding time (s)).SELECTED DRAWING: Figure 2

Description

The present invention relates to a method for producing an antiglare film, an antiglare film, a polarizing plate, and an image display device.

Anti-glare films are used in various image display devices such as cathode ray tube display (CRT), liquid crystal display (LCD), plasma display panel (PDP), and electroluminescence display (ELD) to reflect external light. In order to prevent a decrease in contrast due to the reflection of the image, it is arranged on the display surface. In the antiglare film, various production methods have been proposed in order to realize appropriate antiglare properties and other physical properties.

For example, immediately after the particle-containing coating solution for forming the antiglare layer is applied onto the light-transmitting substrate in order to reduce point defects, the light-transmitting substrate is −40 ° to + 40 ° with respect to the horizontal direction. A method for producing an antiglare film that is conveyed at an angle of less than or equal to 0 ° has been proposed (Patent Document 1).

Further, in order to increase the aggregation rate of the particles, the particle-containing coating liquid for forming the antiglare layer is applied on the light-transmitting substrate, and then dried, when the light-transmitting substrate is 30 to 90. There has been proposed a method for producing an antiglare film that is held or transported in an inclined state (Patent Document 2).

JP 2010-102291 A JP 2010-54737 A

However, as in Patent Documents 1 and 2, it is possible to control the uneven shape of the antiglare film surface by particles only by adjusting the angle of the translucent substrate immediately after coating of the coating liquid or at the time of drying. It was difficult.

Then, an object of this invention is to provide the manufacturing method of the anti-glare film which can control the surface shape of an anti-glare film in a wide range freely, and the anti-glare film manufactured by it. Furthermore, it aims at providing the polarizing plate and image display apparatus using this anti-glare film.

In order to achieve the above object, the method for producing an antiglare film of the present invention comprises applying an application liquid to at least one surface of a translucent substrate, and curing the application liquid to provide an antiglare layer. A method for producing an anti-glare film, wherein the coating liquid contains a resin, particles, and a solvent, and a shearing step for causing shear to the coating liquid coated on the translucent substrate The surface shape of the anti-glare film is adjusted by adjusting the shear distance of the coating film defined by the following formula (I) in the shearing step.

S = ∫Vdt (I)

In the formula (I),
S: Shear distance (m)
V: Shear rate (m / s)
t: Shear retention time (s)
And
The shear rate V is defined by the following formula (II):

V = kah ² / η (II)

In the formula (II),
k: Specific gravity of coating film (kg / m ³ )
a: Acceleration (m / s ² )
h: Coating thickness (m)
η: coating film viscosity (Pa · s)
It is. However, the acceleration a may change with time or may be constant.

The antiglare film of the present invention is an antiglare film produced by the production method of the present invention.

The polarizing plate of the present invention is characterized by having a polarizer and the antiglare film of the present invention.

  The image display device of the present invention includes the antiglare film of the present invention.

  Alternatively, the image display device of the present invention includes the polarizing plate of the present invention.

According to the method for producing an antiglare film of the present invention, the surface shape of the antiglare film can be freely controlled in a wide range. Specifically, for example, on the surface of the antiglare film, the arithmetic average surface roughness Ra, the average inter-concave distance Sm, the average inclination angle θa, etc. described later can be freely adjusted (controlled) in a wide range. It is.

FIG. 1 is a schematic diagram illustrating a method for calculating the shear rate V of the coating film. 2A is a schematic diagram showing an example of a method for adjusting the shear rate V of the coating film in the production method of the present invention, and FIG. 2B is a shear rate V of the coating film in the production method of the present invention. It is a schematic diagram which shows the other example of this adjustment method. FIG. 3 is a schematic diagram for explaining the definition of the height of the convex portion. FIG. 4 is a schematic diagram showing an example in which the shear rate V changes depending on the shear holding time t. FIG. 5 is a schematic view showing the structure of an example of the antiglare film of the present invention. FIG. 6 is a schematic explanatory view schematically illustrating a mechanism inferred with respect to particle aggregation in the antiglare film of the present invention. FIG. 7 is a schematic diagram illustrating an example of definitions of the thickness direction and the surface direction of the antiglare layer in the antiglare film of the present invention. FIG. 8 is a schematic explanatory view schematically illustrating a mechanism inferred with respect to particle aggregation in the case where an osmotic layer is formed in the antiglare film of the present invention. FIG. 9 is a schematic diagram showing the relationship between the Ti value of the coating liquid and the assumed distribution state of the thixotropy imparting agent. FIG. 10 is a graph schematically showing an example of the antiglare film surface shape control according to the shear distance and the number of parts by weight of particles in the production method of the present invention. FIG. 11 is a graph showing the surface shape (average inter-concave distance Sm and average inclination angle θa) of the antiglare film of the example.

In the method for manufacturing the antiglare film of the present invention, the shear distance S of the coating film in the shear step, is preferably set to 0.005 × ¹⁰ -9 m~120 × range of ^{10 -9} m.

In the method for producing an antiglare film of the present invention, the shear rate V is set to 0.05 × 10 ^−.
Preferably in the range of ^{9 m / s~2.0 × 10 -9 m} / s, more preferably 0.
The range is from 05 × 10 ⁻⁹ m / s to 1.0 × 10 ⁻⁹ m / s.

In the method for producing an antiglare film of the present invention, the predetermined time is preferably set within a range of 0.1 to 60 s (seconds).

In the method for producing an antiglare film of the present invention, as the coating liquid, a thixotropic agent (
It is preferable to use a coating solution containing a thixotropic agent (thixotropic agent).

In the method for producing an antiglare film of the present invention, the thixotropy imparting agent is preferably at least one selected from the group consisting of organic clay, oxidized polyolefin and modified urea.

In the method for producing an antiglare film of the present invention, the thickness (d) of the antiglare layer is 3 to 12 μm.
It is preferable that the particle diameter (D) of the particles is in the range of 2.5 to 10 μm. In this case, the relationship between the thickness (d) and the particle diameter (D) is 0.3.
≦ D / d ≦ 0.9 is preferable.

In the method for producing an antiglare film of the present invention, the surface shape of the antiglare film can be further adjusted by adjusting the number of parts by weight of the particles with respect to 100 parts by weight of the resin in the coating liquid. preferable.

In the manufacturing method of the anti-glare film of this invention, it is preferable that the said particle | grain is contained in the range of 0.2-12 weight part with respect to 100 weight part of said resin in the said coating liquid.

In the antiglare film of the present invention, the antiglare layer is agglomerated of the particles,
It has an agglomerated part that forms a convex part on the surface of the antiglare layer, and in the agglomerated part that forms the convex part, a plurality of particles are gathered in the surface direction of the antiglare layer. Preferably it is present.

In the antiglare film of the present invention, the height of the convex portion from the roughness average line of the antiglare layer is preferably less than 0.4 times the thickness of the antiglare layer.

In the antiglare film of the present invention, in the antiglare layer, the appearance defect having a maximum diameter of 200 μm or more is preferably 1 or less per 1 m ^{2 of the} antiglare layer.

The anti-glare film of the present invention has a permeation layer formed by the resin penetrating into the translucent substrate between the translucent substrate and the anti-glare layer. preferable.

The image display device of the present invention has the antiglare film on the viewing side surface, further has a black matrix pattern, and the antiglare layer of the antiglare film is agglomerated of the particles, It has an agglomerated part that forms a convex part on the surface of the antiglare layer, and in the agglomerated part that forms the convex part, a plurality of particles are gathered in the surface direction of the antiglare layer. It is preferable that the anti-glare film is arranged so that one direction in which a plurality of the particles are collected and the long side direction of the black matrix pattern coincide with each other.

Below, an example is given and the manufacturing method of the anti-glare film of this invention is demonstrated below.
As described above, the method for producing an antiglare film of the present invention is to prevent the formation of an antiglare layer by coating a coating liquid on at least one surface of a translucent substrate and curing the coating liquid. It is a manufacturing method of a dazzling film. Moreover, according to the manufacturing method of the anti-glare film of this invention, as above-mentioned, the surface shape of the said anti-glare film can be adjusted by adjusting the shear distance of the coating film in the said shearing process. In addition, as described above, it is preferable to adjust the surface shape of the antiglare film by adjusting the number of parts by weight of the particles with respect to 100 parts by weight of the resin in the coating liquid as necessary. Accordingly, for example, even if the resin and the particle type are the same, the surface shape of the antiglare film can be freely changed (controlled) over a wide range. Specifically, for example, on the surface of the antiglare film, arithmetic average surface roughness Ra, average unevenness distance Sm, and average inclination angle θa described later
Etc. can be adjusted (controlled) freely within a wide range.

(1) Translucent substrate The translucent substrate is not particularly limited, and for example, a transparent plastic film substrate can be used. Although it does not restrict | limit especially as said transparent plastic film base material, It is excellent in the light transmittance of visible light (preferably light transmittance 90% or more), and is excellent in transparency (preferably a haze value of 1% or less). Preferably, for example, a transparent plastic film substrate described in JP-A-2008-90263 can be used. As the transparent plastic film substrate, those having a small optical birefringence are preferably used. The antiglare film produced by the production method of the present invention can also be used for a polarizing plate as a protective film, for example. In this case, as the transparent plastic film substrate, triacetyl cellulose (TAC), Films formed from polycarbonate, acrylic polymers, polyolefins having a cyclic or norbornene structure are preferred. In the present invention, as described later, the transparent plastic film substrate may be a polarizer itself. With such a configuration, a protective layer made of TAC or the like is not required, and the structure of the polarizing plate can be simplified. Therefore, the number of manufacturing steps of the polarizing plate or the image display device can be reduced, and the production efficiency can be improved. Moreover, if it is such a structure, a polarizing plate can be made thinner. In addition, when the said transparent plastic film base material is a polarizer, an anti-glare layer will play the role as the conventional protective layer. Moreover, if it is such a structure, an anti-glare film will serve as a cover plate, for example, when it is mounted on the surface of a liquid crystal cell.

In the present invention, the thickness of the transparent plastic film substrate is not particularly limited,
For example, considering points such as strength, workability such as handleability and thin layer properties, 10 to 50
The range of 0 μm is preferable, more preferably in the range of 20 to 300 μm, optimally 3
It is in the range of 0 to 200 μm. The refractive index of the transparent plastic film substrate is not particularly limited. The refractive index is, for example, in the range of 1.30 to 1.80, preferably 1.
It is in the range of 40 to 1.70.

(2) Coating liquid The coating liquid contains a resin, particles, and a solvent. Examples of the resin include a thermosetting resin and an ionizing radiation curable resin that is cured by ultraviolet rays or light. As the resin, it is also possible to use a commercially available thermosetting resin or ultraviolet curable resin.

Examples of the thermosetting resin and the ultraviolet curable resin include heat, light (ultraviolet light, etc.).
Alternatively, a curable compound having at least one of an acrylate group and a methacrylate group that can be cured by an electron beam or the like can be used. For example, silicone resin, polyester resin, polyether resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin , Oligomers or prepolymers of polyfunctional compounds such as polybutadiene resins, polythiol polyene resins, polyhydric alcohols and the like, such as acrylates and methacrylates. These may be used alone or in combination of two or more.

For the resin, for example, a reactive diluent having at least one of an acrylate group and a methacrylate group can be used. The reactive diluent is, for example, JP-A-200.
The reactive diluent described in 8-88309 can be used, and includes, for example, monofunctional acrylates, monofunctional methacrylates, polyfunctional acrylates, polyfunctional methacrylates, and the like.
The reactive diluent is preferably a trifunctional or higher acrylate or a trifunctional or higher methacrylate. This is because the hardness of the antiglare layer can be made excellent. Examples of the reactive diluent include butanediol glycerin ether diacrylate, isocyanuric acid acrylate, isocyanuric acid methacrylate, and the like. These may be used alone or in combination of two or more.

The particles have a main function of imparting antiglare properties by making the surface of the antiglare layer formed uneven, and controlling the haze value of the antiglare layer. The haze value of the antiglare layer can be designed by controlling the refractive index difference between the particles and the resin. Examples of the particles include inorganic particles and organic particles. The inorganic particles are not particularly limited. For example, silicon oxide particles, titanium oxide particles, aluminum oxide particles, zinc oxide particles, tin oxide particles, calcium carbonate particles, barium sulfate particles, talc particles, kaolin particles, calcium sulfate particles, and the like. Can be given. The organic particles are not particularly limited. For example, polymethyl methacrylate resin powder (PMMA fine particles), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin Examples thereof include resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, and polyfluorinated ethylene resin powder. One kind of these inorganic particles and organic particles may be used alone, or two or more kinds thereof may be used in combination.

The particle diameter (D) (weight average particle diameter) of the particles is preferably in the range of 2.5 to 10 μm. By setting the weight average particle diameter of the particles in the above range, for example, it is possible to obtain an antiglare film that is more excellent in antiglare property and prevents white blurring. The weight average particle diameter of the particles is more preferably 3 μm or more and less than 10 μm, for example, in the range of 3 to 7 μm. In the antiglare film described in JP 2010-54737 A, the film thickness of the antiglare layer is 1.
It is appropriate to make it 0 μm or more, and it is not appropriate to make it less than 10 μm. The weight average particle diameter of the particles can be measured by, for example, a Coulter count method. For example, by using a particle size distribution measuring apparatus (trade name: Coulter Multisizer, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method, an electrolyte solution corresponding to the volume of the particles when the particles pass through the pores. By measuring the electrical resistance, the number and volume of the particles are measured, and the weight average particle diameter is calculated. Further, in the antiglare film, for example, even if there is white blur, it is only necessary to prevent white blur to the extent that there is no practical problem. Rather, by generating some white blur,
A matte feeling (matte, calm appearance) is obtained and may be preferable. According to the method for producing an antiglare film of the present invention, as described above, the surface shape of the antiglare film can be freely controlled in a wide range. For this reason, for example, the surface shape for reducing white blurring or the surface shape for obtaining a matte feeling can be arbitrarily controlled.

The shape of the particles is not particularly limited, and may be, for example, a bead-like substantially spherical shape or an indefinite shape such as a powder, but is preferably substantially spherical, more preferably an aspect. Spherical particles having a ratio of 1.5 or less, and most preferably spherical particles.

In the present invention, as described above, in addition to the shear distance of the coating film in the shearing process, further, by adjusting the number of parts by weight of the particles with respect to 100 parts by weight of the resin in the coating liquid, It is preferable to freely control the surface shape. The ratio of the particles in the coating liquid is more preferably in the range of 0.2 to 12 parts by weight, still more preferably in the range of 0.5 to 12 parts by weight, particularly preferably 100 parts by weight of the resin. Is in the range of 1 to 7 parts by weight. By setting it as the said range, the anti-glare film which was more excellent in anti-glare property and was prevented from white blurring can be obtained, for example.

The coating liquid preferably further contains a thixotropic agent. For example, when the coating liquid contains the thixotropy-imparting agent, an effect of preventing sedimentation of the particles (thixotropic effect) can be obtained, and the surface shape of the antiglare film can be obtained by shear aggregation of the thixotropy-imparting agent itself. Can be freely controlled in a wider range. Moreover, when the said coating liquid contains the said thixotropy imparting agent, the anti-glare film in which white blurring was prevented more can be obtained, for example. Examples of the thixotropic agent include organic clay,
Examples thereof include oxidized polyolefin and modified urea. Further, in the case where the coating liquid contains a thixotropy imparting agent, the difference between the particles where the particles are not aggregated (dense) and the regions where the particles are not aggregated (rough) Since it is easy to obtain a large state (dense / dense state), it is easy to further improve the white blur prevention effect. More specifically, when the coating solution contains a thixotropy imparting agent, in order to further improve the white blurring preventing effect, the ratio of the particles in the coating solution is based on 100 parts by weight of the resin. More preferably, it is 12 parts by weight or less, more preferably 10 parts by weight or less, further preferably 6 parts by weight or less, further preferably 5 parts by weight or less, further preferably 4 parts by weight or less, and particularly preferably 3 parts by weight or less. Moreover, when the said coating liquid contains a thixotropy imparting agent, the lower limit of the said particle | grain with respect to 100 weight part of said resin becomes like this. More preferably, it is 0.2 weight part or more.

In order to improve the affinity with the resin, the organic clay is preferably a layered clay subjected to an organic treatment. The organoclay may be prepared in-house or a commercially available product may be used. Examples of the commercially available products include Lucentite SAN, Lucentite STN, Lucentite SEN, Lucentite SPN, Somasif ME-100, Somasif ME, Somasif MTE, Somasif MEE, Somasif MPE (trade names, all of which are Co-op Chemical Co., Ltd. ) Made)
; Esben, Esven C, Esben E, Esben W, Esben P, Esben WX, Esben N-400, Esben NX, Esben NX80, Esben NO12S, Esben NEZ
, Esven NO12, Esben NE, Esben NZ, Esben NZ70, Organite,
Organite D, Organite T (trade names, both manufactured by Hojun Co., Ltd.); Kunipia F
, Kunipia G, Kunipia G4 (trade names, both manufactured by Kunimine Industries, Ltd.); Thixogel V
Z, Clayton HT, Clayton 40 (trade names, all manufactured by Rockwood Additives) and the like.

The oxidized polyolefin may be prepared in-house or a commercially available product may be used. Examples of the commercially available products include Disparon 4200-20 (trade name, manufactured by Enomoto Kasei Co., Ltd.), Flownon SA300 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

The modified urea is a reaction product of an isocyanate monomer or an adduct thereof and an organic amine. The modified urea may be prepared in-house or a commercially available product may be used. Examples of the commercially available product include BYK410 (manufactured by Big Chemie).

The ratio of the thixotropy imparting agent in the coating liquid is preferably in the range of 0.2 to 5 parts by weight, more preferably in the range of 0.4 to 4 parts by weight with respect to 100 parts by weight of the resin.

The thixotropy-imparting agent may be used alone or in combination of two or more.

The solvent is not particularly limited, and various solvents can be used. One type may be used alone, or two or more types may be used in combination. Depending on the composition of the resin, the type of particles and the thixotropy imparting agent, the content, etc., there are optimum solvent types and solvent ratios. Examples of the solvent include, but are not limited to, alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and 2-methoxyethanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone; methyl acetate and acetic acid Esters such as ethyl and butyl acetate; ethers such as diisopropyl ether and propylene glycol monomethyl ether; glycols such as ethylene glycol and propylene glycol; cellosolves such as ethyl cellosolve and butyl cellosolve; aliphatic carbonization such as hexane, heptane and octane Hydrogen: aromatic hydrocarbons such as benzene, toluene, xylene and the like.

As a translucent substrate, for example, when triacetyl cellulose (TAC) is employed to form a permeation layer, a good solvent for TAC can be suitably used. As the solvent, for example,
Examples thereof include ethyl acetate, methyl ethyl ketone, and cyclopentanone.

Moreover, the thixotropy (thixotropic property) to the coating liquid by a thixotropy imparting agent can be made to express favorably by selecting a solvent suitably. For example, when using an organic clay, toluene and xylene can be preferably used alone or in combination. For example, when using an oxidized polyolefin, methyl ethyl ketone, ethyl acetate, propylene glycol monomethyl meter is preferably used alone. Can be used or used together, for example
When using a modified urea, butyl acetate and methyl isobutyl ketone can be preferably used alone or in combination.

Various leveling agents can be added to the coating liquid. As the leveling agent, for example, a fluorine-based or silicone-based leveling agent can be used for the purpose of preventing coating unevenness (coating surface uniformity). In the present invention, when antifouling properties are required on the surface of the antiglare layer, or when a layer containing an antireflection layer (low refractive index layer) or an interlayer filler is formed on the antiglare layer as described later. Depending on the leveling agent, a leveling agent can be appropriately selected. In the present invention, for example, by including the thixotropy imparting agent, thixotropy can be expressed in the coating liquid, so that coating unevenness hardly occurs. For this reason, this invention has the advantage that the choice of the said leveling agent can be expanded, for example.

The amount of the leveling agent is, for example, 5 parts by weight or less, preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin.

In the coating liquid, pigments, fillers, dispersants, plasticizers, ultraviolet absorbers, surfactants, antifouling agents, antioxidants, etc. are added as necessary, as long as the performance is not impaired. Also good. These additives may be used alone or in combination of two or more.

For the coating liquid, for example, a conventionally known photopolymerization initiator as described in JP-A-2008-88309 can be used.

The coating solution preferably exhibits thixotropy, and the Ti value defined by the following formula is:
It is preferable that it exists in the range of 1.3-3.5, More preferably, it is the range of 1.4-3.2, More preferably, it is the range of 1.5-3.

Ti value = β1 / β2

In the above formula, β1 is a shear rate of 20 (1 /
The viscosity measured under the condition of s), β2, is a viscosity measured under the condition of a shear rate of 200 (1 / s) using a rheo-stress RS6000 manufactured by HAAKE.

When the Ti value is less than 1.3, appearance defects are likely to occur, and the antiglare property and white blur characteristics may be deteriorated. On the other hand, when the Ti value exceeds 3.5, the particles are less likely to agglomerate and tend to be in a dispersed state, making it difficult to obtain the antiglare film of the present invention.

In the schematic diagram of FIG. 9, the relationship between Ti value of the coating liquid in the manufacturing method of an anti-glare film and the assumption distribution state of a thixotropy imparting agent is shown. As shown in FIG. 9, when the Ti value is less than 1.3, it is assumed that the distribution of the thixotropy imparting agent is depopulated, and as described above, appearance defects are likely to occur, antiglare properties, and white blurring. The characteristics may deteriorate. Ti value is 3
. If it exceeds 5, the anti-settling effect increases, but the thixotropy-imparting agent is assumed to be overcrowded, and as described above, the particles are less likely to agglomerate and tend to be in a dispersed state. On the other hand, by setting the Ti value in the range of 1.3 to 3.5, it is assumed that the state in which the thixotropy imparting agent is appropriately distributed can be secured, and the particles can be appropriately aggregated. In addition, the distribution state of the thixotropy imparting agent shown in FIG. 9 is an assumption, and the present invention is based on this assumption.
There are no restrictions or limitations.

(3) Coating film forming step In the present invention, when the coating liquid is applied to at least one surface of the translucent substrate to form a coating film, it is defined by the following formula (I). By adjusting the shear distance S of the coating film, the surface shape of the antiglare film can be freely controlled. The shear distance S of the coating film is 0.005 ×
It is preferable that the 10 ^-9 m~120 × range of ^{10 -9} m. The shear distance S is
More preferably, in the range of ^{0.005 × 10 -9 m~60 × 10 -9} m, more preferably in the range of ^{0.01 × 10 -9 m~15 × 10 -9} m. In the case where the coating liquid contains a thixotropy imparting agent, the shear distance S is more preferably 0.5 × 10 ⁻⁹ m to 8.0 × in order to further improve the white blur prevention effect. 10 ^-9 m in the range of, more preferably, in the range of ^{0.5 × 10 -9 m~7.5 × 10 -9} m, more preferably, 0.5 × ¹⁰ -9 m to It is in the range of 7.0 × 10 ⁻⁹ m.

∫Vdt (I)

In the formula (I),
S: Shear distance (m)
V: Shear rate (m / s)
t: Shear retention time (s)
And
The shear rate V is defined by the following formula (II):

V = kah ² / η (II)

In the formula (II),
k: Specific gravity of coating film (kg / m ³ )
a: Acceleration (m / s ² )
h: Coating thickness (m)
η: coating film viscosity (Pa · s)
It is. However, the acceleration a may change with time or may be constant.

Examples of a method for forming the coating film by coating the coating liquid on the light-transmitting substrate include, for example, a fountain coating method, a die coating method, a spin coating method, a spray coating method, a gravure coating method, and a roll coating. A coating method such as a coating method or a bar coating method can be used.

A method for calculating the shear rate V will be described with reference to FIG. For convenience of explanation, it is assumed that the acceleration a and the shear rate V do not change with time and are constant in FIG. Assuming that the mass of the fluid shown in FIG. 1 is m (kg), the thickness of the fluid is h (m), and the contact area between the fixed flat plate and the fluid is A (m ² ), the upper velocity of the fluid (shear rate) ) V
(M / s) is obtained by the equation V = mah / Aη. Here, a is acceleration (m / s ² ),
η is the viscosity (Pa · s) of the fluid. Since the specific gravity k (kg / m ³ ) of the fluid is k = m / hA, V = mah / Aη = kah ² / η. Therefore, as described above, the shear rate V of the coating film applied on the translucent substrate is defined by the following formula (II).

V = kah ² / η (II)

k: Specific gravity of coating film (kg / m ³ )
a: Acceleration (m / s ² )
h: Coating thickness (m)
η: coating film viscosity (Pa · s)

As can be seen from the above formula (II), if (1) the acceleration a is increased, (2) the coating film thickness h is increased, or (3) the coating film viscosity η is decreased, the shear rate V of the coating film Can be increased. If the shear rate V of the coating film is increased, a difference occurs in the moving speed of the resin and the particles in the thickness direction of the coating film, and the opportunity for the particles to contact each other increases. As a result, aggregation of the particles (shear aggregation) occurs. In the present invention, the shear distance S is as described above,
It is represented by the following formula (I). In FIG. 1, as described above, the acceleration a and the shear rate V
However, since it does not change with time and is constant, the shear distance S is represented by the following formula (I ′). From the following formulas (I) and (I ′), in the production method of the present invention, the shear holding time t
Is constant, it can be seen that increasing the shear rate V increases the shear distance S.

S = ∫Vdt (I)

S = V × t (I ′)

The shear aggregation is more likely to occur by using a coating solution containing a thixotropic agent. Rate in the case of using a coating solution containing no thixotropy-imparting agent, to the shear velocity V (the shear distance S of the coating film, 0.005 × ¹⁰ -9 m~120 × range of ^{10 -9} m ) Within the range of 0.05 × 10 ⁻⁹ m / s to 2.0 × 10 ⁻⁹ m / s, more preferably 0.05 × 10 ⁻⁹ m / s to 1.0. It is in the range of × 10 ⁻⁹ m / s, more preferably in the range of 0.10 × 10 ⁻⁹ m / s to 0.25 × 10 ⁻⁹ m / s. The specific gravity, thickness, viscosity, etc. of the coating film are affected by the drying of the coating film. Therefore, the shear rate V is affected by the drying rate of the solvent. Drying rate (coating film reduction rate)
Is faster, the shear rate V becomes slower and shear aggregation is less likely to occur. That is, the degree of aggregation can be dealt with by adjusting the drying speed.

With reference to FIG. 2, the adjustment method of the shear rate V of the said coating film is demonstrated. In FIG. 2, 20 indicates a translucent substrate, 21 indicates a coating film, 12 indicates particles, and 13 indicates a thixotropic agent. FIG. 2A shows an example in which the translucent substrate 20 is inclined to increase the shear rate V of the coating film 21. As shown in FIG. 2A, for example, by tilting the translucent substrate 20, the component along the tilt direction of the gravitational acceleration becomes the acceleration a,
The shear rate V of the coating film 21 can be increased. FIG. 2B is an example in which the translucent substrate 20 kept horizontal is rotated on a rotating body to increase the shear rate V of the coating film 21. As shown in FIG. 2 (b), for example, by rotating the translucent substrate 20 kept horizontal on the rotating body, the acceleration a is increased by the centrifugal force, and the shear rate V of the coating film 21 is increased. Can be bigger. By adjusting the shear rate V in this way, for example, the shear rate V can be kept constant.

The shear holding time t (the shear distance S is set to 0.005 × 10 ⁻⁹ m to 120 × 10
^-9 m) is preferably adjusted within a range of 0.1 to 60 s (seconds), and when using a coating solution containing a thixotropy imparting agent, it should be 1 second or longer. Is preferred. When using the coating liquid which does not contain a thixotropy imparting agent, it is preferable to set it as 30 seconds or more. By setting the predetermined time to 30 seconds or more, the shear aggregation is more likely to occur. The predetermined time is more preferably 60 seconds or longer. Further, in the case of using a coating solution containing a thixotropy imparting agent, in order to further prevent white blurring, the shear holding time t can be dealt with in a short time (30 seconds or less) although it depends on the shear rate. is there. However, the present invention is not limited to this, and in the case of using a coating solution containing a thixotropy imparting agent, the shear holding time t may be 30 seconds or more or more than 30 seconds.

As described above, the shear distance S can be adjusted by adjusting at least one of the shear rate V and the shear holding time t. In the present invention, JP 2010-102911 A
As in the manufacturing methods described in Japanese Patent Laid-Open No. 2010-54737 and Japanese Patent Application Laid-Open No. 2010-54737, the translucent base material is not simply tilted at a predetermined angle, but the shear distance calculated from the shear rate V and the shear holding time t. By adjusting (controlling) S to cause shear aggregation of particles, the above-described effects of the present invention can be obtained. In addition, although the said description demonstrated the case where the said shear rate V was constant, this invention is not limited to this example. In the coating film forming step, the shear rate V may be appropriately changed over time as described above, for example. More specifically, for example, as shown in FIG. 4, in the coating film forming step, for example, the shear rate V is changed from the shear rate V ₁ (shear retention time t ₁ ) to the shear rate V ₂ (shear retention). It may be changed to time t ₂ ), and may be further changed to shear rate V ₃ (shear holding time t ₃ ). In this case, the shear distance S is, for example, a shear distance at each shear rate, that is, a shear distance S ₁ (V ₁ × t ₁ ), a shear distance S ₂ (V ₂ × t ₂ ), and a shear distance S ₃ ( V
₃ × t ₃ ) (S = S ₁ + S ₂ + S ₃ ). In the figure, translucent substrate 2
0 is conveyed from the left side to the right side of the figure by the coater line, and at the left end of the figure,
The coating liquid 22 is applied to the translucent substrate 20. And the inclination angle at the time of conveyance of the translucent base material 20 changes from the first inclination angle θ ₁ to the second inclination angle θ ₂ , and further changes to the third inclination angle θ ₃ , whereby the acceleration a changes. Therefore, the shear rate V is changed as described above.

(4) Anti-glare layer formation process Next, the said coating film is hardened and an anti-glare layer is formed. Prior to the curing, it is preferable to dry the coating film (remove the solvent). The drying may be, for example, natural drying,
Air drying by blowing air, heat drying, or a combination of these may be used.

The means for curing the coating film is not particularly limited, but ultraviolet curing is preferable. The irradiation amount of the energy ray source is preferably 50 to 500 mJ / cm ² as an integrated exposure amount at an ultraviolet wavelength of 365 nm. When the irradiation amount is 50 mJ / cm ² or more, the curing becomes more sufficient and the hardness of the formed antiglare layer becomes more sufficient. Moreover, if it is 500 mJ / cm < ² > or less, coloring of the anti-glare layer formed can be prevented.

The thickness (d) of the antiglare layer is not particularly limited, but is preferably in the range of 3 to 12 μm. By setting the thickness (d) of the antiglare layer in the above range, for example, the occurrence of curling in the antiglare film can be prevented, and the problem of lowering productivity such as poor transportability can be avoided. Further, when the thickness (d) is in the above range, the weight average particle diameter (D) of the particles is preferably in the range of 2.5 to 10 μm as described above. Thickness (d) of the antiglare layer
And the weight average particle diameter (D) of the said particle | grain can be set as the anti-glare film which is further excellent in anti-glare property because it is the above-mentioned combination. The thickness (d) of the antiglare layer is more preferably in the range of 3 to 8 μm.

The relationship between the thickness (d) of the antiglare layer and the weight average particle diameter (D) of the particles is 0.3 ≦ D / d
It is preferable to be within the range of ≦ 0.9. By having such a relationship, it is possible to obtain an antiglare film that is more excellent in antiglare property, can prevent white blurring, and further has no appearance defect.

As described above, an antiglare film can be produced by forming the antiglare layer on at least one surface of the translucent substrate.

(5) Anti-glare film As described above, in the anti-glare film of the present invention, the anti-glare layer has an agglomerated portion that forms a convex portion on the surface of the anti-glare layer when the particles aggregate. And in the agglomerated part forming the convex part, it is preferable that a plurality of the particles are present in a gathered state in the surface direction of the antiglare layer. Thereby, the said convex-shaped part can be made into a more gentle shape. While having such a convex portion, while maintaining the antiglare property of the antiglare film, and
White blur can be prevented, and appearance defects can be made difficult to occur.

In the antiglare film of the present invention, the height of the convex portion from the roughness average line of the antiglare layer is preferably less than 0.4 times the thickness of the antiglare layer. More preferably, the range is 0.01 times or more and less than 0.4 times, and still more preferably, the range is 0.01 times or more and less than 0.3 times. If it is this range, it can prevent suitably that the protrusion which becomes an external appearance defect is formed in the said convex-shaped part. The anti-glare film of the present invention has a convex portion having such a height,
Appearance defects can be made difficult to occur. Here, with respect to the height from the average line, FIG.
Will be described with reference to FIG. FIG. 3 is a schematic diagram of a two-dimensional profile of a cross section of the antiglare layer,
A straight line L is a roughness average line (center line) in the two-dimensional profile. The height H of the top (convex portion) from the roughness average line in the two-dimensional profile is defined as the convex portion height in the present invention. In FIG. 3, a portion of the convex portion that exceeds the average line is given a parallel oblique line. The thickness of the antiglare layer is the thickness of the antiglare layer calculated by measuring the total thickness of the antiglare film and subtracting the thickness of the translucent substrate from the total thickness. The total thickness and the thickness of the translucent substrate can be measured by, for example, a micro gauge thickness gauge.

In the antiglare film of the present invention, when the translucent base material is formed from a resin or the like, it is preferable to have a permeation layer at the interface between the translucent base material and the antiglare layer. The penetration layer is formed by the resin component contained in the material for forming the antiglare layer penetrating the translucent substrate. When the osmotic layer is formed, the adhesion between the translucent substrate and the antiglare layer can be improved, which is preferable. The penetration layer preferably has a thickness in the range of 0.2 to 3 μm, more preferably in the range of 0.5 to 2 μm. For example, when the translucent substrate is triacetyl cellulose and the resin contained in the antiglare layer is an acrylic resin, the permeation layer can be formed. For example, the permeation layer may be formed by using a transmission electron microscope (T
It can be confirmed by observing with EM), and the thickness can be measured.

In the production method of the present invention, even when applied to an antiglare film having such a permeation layer, the surface shape of the antiglare film can be freely controlled in a wide range. For example, according to the manufacturing method of the present invention, as described above, it is possible to easily form a desired smooth surface uneven shape that satisfies both the antiglare property and the prevention of white blur. It is preferable that the penetration layer is formed thicker so as to improve the adhesion as the light-transmitting substrate has less adhesion with the antiglare layer.

In FIG. 5, the structure of an example of the anti-glare film of this invention is shown typically. However, this figure is an example and does not limit the present invention. Moreover, the figure is an example in case the anti-glare film of this invention contains a thixotropy imparting agent. As shown in the figure, the antiglare film has a convex portion 1 on the surface of the antiglare layer 11 in which the particles 12 and the thixotropic agent 13 are aggregated in the antiglare layer 11.
4 is formed. The aggregation state of the particles 12 and the thixotropic agent 13 is not particularly limited, but the thixotropic agent 13 tends to be present at least around the particles 12. In the agglomerated part forming the convex part 14, a plurality of particles 12 are present in a state of being collected in the surface direction of the antiglare layer 11. As a result, the convex portion 14 has a gentle shape.

It is inferred that the gentle convex portion as described above is formed by the following mechanism. However, the present invention is not limited or limited by this inference.

FIG. 6 schematically shows a state in which the cross section in the thickness direction of the antiglare film of the present invention is viewed from the side in order to explain the mechanism of the aggregation state in the antiglare layer in the antiglare film of the present invention. It is a schematic explanatory drawing shown. In FIG. 6, (a) shows the state which applied the said coating liquid containing a solvent to a translucent base material, and formed the coating film, (b) removed the solvent from a coating film. The state which hardened the coating film and formed the glare-proof layer is shown.

Hereinafter, with reference to FIG. 6, a mechanism for forming the gentle convex portion as described above will be described. As shown in FIGS. 6A and 6B, the film thickness of the coating film shrinks (decreases) by removing the solvent contained in the coating film. Since the lower surface side (back surface side) of the coating film is stopped by the translucent substrate, the contraction of the coating film occurs from the upper surface side (front surface side) of the coating film. In FIG. 6 (a), particles (for example, particle 1, particle 4 and particle 5) existing in a portion where the film thickness of the coating film is reduced will move to the lower surface side of the coating film due to the film thickness reduction. And On the other hand, the particles (for example, particle 2, particle 3 and particle 6) present at a relatively low position near the lower surface which is not affected by the change in film thickness or hardly affected are thixotropy contained in the coating liquid. The movement to the lower surface side is suppressed by the anti-settling effect (thixotropic effect) of the imparting agent (for example, it does not move to the lower surface side from the two-dot chain line 10). For this reason, even if the coating film shrinks,
The particles on the lower surface side (particle 2, particle 3 and particle 6) are not pushed downward (back surface side) by the particles (particle 1, particle 4 and particle 5) trying to move from the surface side, and remain almost in that position. ing. Since the particles on the lower surface side (particles 2, particles 3 and particles 6) remain almost in their positions, the particles (particles 1, particles 4 and particles 5) to be moved from the surface side are the particles on the lower surface side. It moves next to the particle on the lower surface side (surface direction of the coating film) that does not exist. Thus, in the anti-glare film of this invention, it is guessed that in the said glare-proof layer, the said particle | grain exists in the state gathered in the surface direction of the said glare-proof layer.

As described above, in the antiglare layer, the particles agglomerate in the surface direction of the antiglare layer, so that the convex portion has a gentle shape as shown in FIG. Further, if the antiglare layer contains a thixotropy-imparting agent having an anti-settling effect, it is possible to avoid excessive aggregation of the particles in the thickness direction of the antiglare layer. Thereby, generation | occurrence | production of the protrusion-like object of the glare-proof layer surface used as an external appearance fault can be prevented.

The antiglare film of the present invention may be one in which the convex portion has a gentle shape as described above, and can prevent the occurrence of protrusions on the surface of the antiglare layer, which is an appearance defect. However, the present invention is not limited to this. In addition, in the antiglare film of the present invention, for example, the particles may be somewhat present at a position directly or indirectly overlapping in the thickness direction of the antiglare layer. When the overlap of the particles is represented by the number, the “thickness direction” of the antiglare layer is, for example, the surface of the translucent substrate, as shown in the schematic diagrams of FIGS. The angle formed by the direction (surface direction of the antiglare layer) is 4
Indicates a direction within a range of 5 to 135 degrees. For example, the thickness (d) of the antiglare layer is 3 to 1
2 μm and the particle diameter (D) of the particles is in the range of 2.5 to 10 μm, and the relationship between the thickness (d) and the particle diameter (D) is 0.3 When it is within the range of ≦ D / d ≦ 0.9, for example, the number of overlapping particles in the thickness direction of the antiglare layer is preferably 4 or less, more preferably 3 or less.

Next, a case where the above-described permeation layer is formed between the translucent substrate and the antiglare layer in the inferred mechanism will be described with reference to a schematic explanatory diagram of FIG. . FIG.
(A) shows the state in the middle of the formation of an antiglare layer by removing the solvent from the coating film,
b) shows the state where the solvent was removed from the coating film to form an antiglare layer. In FIG. 8, the permeation layer is marked with parallel diagonal lines. In addition, this invention is not restrict | limited and limited at all by the following description.

As shown in FIGS. 8A and 8B, by removing the solvent contained in the coating film, the film thickness of the coating film shrinks (decreases) to form an antiglare layer. Further, along with the formation of the antiglare layer, the resin contained in the coating liquid penetrates into the translucent substrate, so that a permeation layer is formed between the antiglare layer and the translucent substrate. . As shown in FIG. 8A, in the state before the osmotic layer is formed, the particles are separated from the translucent base material without contact with the translucent base material due to the anti-settling effect of the thixotropic agent. Tend to exist in a state. And when the said osmosis | permeation layer is formed, the resin located in the said translucent base material side, ie, the resin located under the said particle | grain (translucent base material side), is mainly in the said osmosis | permeation layer. It penetrates. Accordingly, in the present invention, following the penetration of the resin into the translucent substrate, the particle group aggregated in the surface direction of the antiglare layer and the resin covering the same are combined to form the transparent resin. Move to the light base material side. That is, the particles move to the translucent substrate side as shown in FIG. 8B while maintaining the aggregation state shown in FIG.
As a result, the particle group on the surface side of the antiglare layer and the resin covering it are in a state as if they fall to the translucent substrate side as a whole while maintaining the surface shape. This
In the anti-glare film of this invention, it is guessed that it is hard to receive the change of the surface shape of the said glare-proof layer.

Further, when the resin has thixotropy due to the thixotropy imparting agent, the resin constituting the convex portion covering the surface of the particle group, even when the permeation layer is formed thick, It is assumed that it is difficult to move to the transparent substrate side. Combined with these effects, it is presumed that the antiglare film of the present invention is less susceptible to changes in the surface shape of the antiglare layer.

In the antiglare film of the present invention, in the antiglare layer, the appearance defect having a maximum diameter of 200 μm or more is preferably 1 or less per 1 m ^{2 of the} antiglare layer. More preferably, there is no appearance defect.

The antiglare film of the present invention preferably has a haze value in the range of 0 to 10%. The haze value is a haze value (cloudiness) of the entire antiglare film according to JIS K 7136 (2000 version). The haze value is more preferably in the range of 0 to 5%, and still more preferably in the range of 0 to 3%. In order to set the haze value in the above range, it is preferable to select the particles and the resin so that the difference in refractive index between the particles and the resin is in the range of 0.001 to 0.02. When the haze value is in the above range, a clear image can be obtained and the contrast in a dark place can be improved.

The antiglare film of the present invention is JIS B 060 in the uneven shape on the surface of the antiglare layer.
1 (1994 version) is preferably in the range of 0.01 to 0.3 μm, more preferably in the range of 0.02 to 0.2 μm. In order to prevent external light and image reflection on the surface of the antiglare film, it is preferable that the surface is rough to some extent. However, when Ra is 0.01 μm or more, the reflection can be improved. When the Ra is in the above range, when used in an image display device or the like, scattering of reflected light when viewed from an oblique direction is suppressed, white blur is improved, and contrast in a bright place is also improved. be able to.

The concavo-convex shape preferably has a surface average concavo-convex distance Sm (mm) measured according to JIS B 0601 (1994 edition) in a range of 0.05 to 0.4, more preferably 0.08 to 0. .3 range. By setting it as the said range, it can be set as the anti-glare film which is more excellent in anti-glare property and can prevent white blurring, for example.

The antiglare film of the present invention has an average inclination angle θa (° in the uneven shape on the surface of the antiglare layer.
) Is preferably in the range of 0.1 to 1.5, more preferably in the range of 0.2 to 1.0. Here, the average inclination angle θa is a value defined by the following mathematical formula (1). The average inclination angle θa is, for example, a value measured by a method described in an example described later.

Average inclination angle θa = tan ⁻¹ Δa (1)

In the formula (1), Δa is JIS B 060 as shown in the following formula (2).
1 (1994 version), the sum (h1 + h2 + h3... + Hn) of the difference (height h) between the apex of the adjacent mountain and the lowest point of the valley in the reference length L of the roughness curve defined in 1 (1994 version) Reference length L
The value divided by. The roughness curve is a curve obtained by removing a surface waviness component longer than a predetermined wavelength from a cross-sectional curve with a phase difference compensation type high-pass filter. The cross-sectional curve is a contour that appears at the cut end when the target surface is cut along a plane perpendicular to the target surface.

Δa = (h1 + h2 + h3... + Hn) / L (2)

For example, when Ra, Sm, and θa are all within the above range, an antiglare film that is more excellent in antiglare property and can prevent white blurring can be obtained. As described above, the method for producing an antiglare film of the present invention can adjust the surface shape of the antiglare film by adjusting the shear distance of the coating film in the shearing step. Thus, for example, Ra,
It is also possible to freely adjust Sm and θa in a wide range. In addition, preferably, the surface shape of the antiglare film can be adjusted by adjusting the number of parts by weight of the particles with respect to 100 parts by weight of the resin in the coating solution. Thereby, for example, Ra, Sm, and θa can be freely adjusted in a wider range.

The graph of FIG. 10 schematically shows an example of the antiglare film surface shape control by the shear distance and the number of parts by weight of the particles in the production method of the present invention. As shown in the figure, when the shear distance is increased, both the average unevenness distance Sm and the average inclination angle θa increase. On the other hand, when the number of added particles (the number of parts by weight of the particles with respect to 100 parts by weight of the resin) is increased, the average unevenness distance Sm decreases and the average inclination angle θa increases. However, this figure is an example and does not limit the present invention.

The hardness of the antiglare film of the present invention is affected by the layer thickness in pencil hardness, but 2
It is preferable to have a hardness of H or higher.

As an example of the antiglare film of the present invention, one having an antiglare layer formed on one surface of a transparent plastic film substrate can be mentioned. The antiglare layer contains particles, whereby the surface of the antiglare layer has an uneven shape. In this example, an antiglare layer is formed on one side of the transparent plastic film substrate, but the present invention is not limited thereto,
It may be an antiglare film in which an antiglare layer is formed on both sides of a transparent plastic film substrate. The antiglare layer in this example is a single layer, but the present invention is not limited to this, and the antiglare layer may have a multilayer structure in which two or more layers are laminated.

In the antiglare film of the present invention, an antireflection layer (low refractive index layer) may be disposed on the antiglare layer. For example, when an antiglare film is attached to an image display device, one of the factors that lower the image visibility is the reflection of light at the interface between air and the antiglare layer. Antireflection layer
The surface reflection is reduced. In addition, you may form an anti-glare layer and an antireflection layer on both surfaces, such as a transparent plastic film base material. The antiglare layer and the antireflection layer may each have a multilayer structure in which two or more layers are laminated.

In the present invention, the antireflection layer is an optical thin film in which thickness and refractive index are strictly controlled, or a laminate of two or more optical thin films. The antireflection layer exhibits an antireflection function by canceling out the reversed phases of incident light and reflected light using the interference effect of light. The wavelength region of visible light that exhibits the antireflection function is, for example, 380 to 780 nm.
The wavelength region with particularly high visibility is in the range of 450 to 650 nm, and it is preferable to design the antireflection layer so as to minimize the reflectance at 550 nm, which is the center wavelength.

In designing the antireflection layer based on the light interference effect, as a means for improving the interference effect, for example, there is a method of increasing the refractive index difference between the antireflection layer and the antiglare layer. In general, in a multilayer antireflection layer having a structure in which two to five optical thin layers (thin films whose thickness and refractive index are strictly controlled) are laminated, a plurality of components having different refractive indexes are formed in a predetermined thickness. This increases the degree of freedom in the optical design of the antireflection layer, and can further improve the antireflection effect.
Spectral reflection characteristics can also be made uniform (flat) in the visible light region. Since the optical thin film requires high thickness accuracy, each layer is generally formed by a dry method such as vacuum evaporation, sputtering, or CVD.

Further, in order to prevent the adhesion of contaminants and improve the ease of removing the adhered contaminants, a contamination prevention layer formed of a fluorine group-containing silane compound or a fluorine group-containing organic compound is provided on the antireflection layer. It is preferable to laminate them.

In the antiglare film of the present invention, it is preferable to perform a surface treatment on at least one of the translucent substrate and the antiglare layer. If the surface of the translucent substrate is surface-treated, the adhesion with the antiglare layer, the polarizer or the polarizing plate is further improved. Further, if the surface of the antiglare layer is surface-treated, the adhesion with the antireflection layer, the polarizer or the polarizing plate is further improved.

In the antiglare film in which the antiglare layer is formed on one surface of the translucent substrate, a solvent treatment may be performed on the other surface in order to prevent curling. In addition, in the antiglare film in which the antiglare layer is formed on one surface of the translucent base material or the like, a transparent resin layer may be formed on the other surface in order to prevent curling. .

The antiglare film obtained in the present invention can usually be bonded to the optical member used in the LCD with the translucent substrate side through an adhesive or an adhesive. In this bonding, various surface treatments as described above may be performed on the surface of the translucent substrate.

Examples of the optical member include a polarizer and a polarizing plate. Generally, the polarizing plate has a transparent protective film on one side or both sides of the polarizer. When providing a transparent protective film on both surfaces of a polarizer, the same material may be sufficient as the transparent protective film of front and back, and a different material may be sufficient as it. The polarizing plates are usually disposed on both sides of the liquid crystal cell. Further, the polarizing plates are arranged so that the absorption axes of the two polarizing plates are substantially orthogonal to each other.

(6) Polarizing plate Next, the optical member which laminated | stacked the said anti-glare film is demonstrated taking a polarizing plate as an example. As described above, according to the method for producing an antiglare film of the present invention, the surface shape of the antiglare film can be freely controlled in a wide range. For this reason, the optical characteristics that can be obtained by laminating the antiglare film with a polarizer or a polarizing plate using an adhesive, a pressure sensitive adhesive, or the like are in a wide range corresponding to the surface shape of the antiglare film. Over. Further, for example, by laminating the antiglare film produced by the production method of the present invention under predetermined conditions with a polarizer or a polarizing plate using an adhesive or a pressure sensitive adhesive, antiglare property and white It is also possible to obtain a polarizing plate that has excellent display characteristics that achieve both prevention of blurring and prevents appearance defects.

The polarizer is not particularly limited, and various types can be used. Examples of the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film, and iodine and dichroic dyes. Examples thereof include a polyene-based oriented film such as a film obtained by adsorbing a chromatic substance and uniaxially stretched, a dehydrated polyvinyl alcohol product or a dehydrochlorinated polyvinyl chloride product.

As the transparent protective film provided on one side or both sides of the polarizer, those having excellent transparency, mechanical strength, thermal stability, moisture shielding property, retardation value stability and the like are preferable. Examples of the material for forming the transparent protective film include the same materials as those for the transparent plastic film substrate.

As the transparent protective film, JP-A-2001-343529 (WO01 / 3)
7007). The polymer film can be produced by extruding the resin composition into a film. The polymer film has a small phase difference and a small photoelastic coefficient, and therefore, when applied to a protective film such as a polarizing plate, it can eliminate problems such as unevenness due to distortion and has a low moisture permeability. Excellent in humidification durability.

The transparent protective film is preferably a film made of a cellulose resin such as triacetyl cellulose or a film made of a norbornene resin from the viewpoints of polarization characteristics and durability. Examples of the commercial product of the transparent protective film include trade name “Fujitac” (manufactured by FUJIFILM Corporation), trade name “ZEONOR” (manufactured by ZEON Corporation), trade name “ARTON” (manufactured by JSR Corporation), and the like. . The thickness of the transparent protective film is not particularly limited, but is, for example, in the range of 1 to 500 μm from the viewpoints of workability such as strength, handleability, and thin layer properties.

The configuration of the polarizing plate in which the antiglare film is laminated is not particularly limited. For example, the transparent protective film, the polarizer and the transparent protective film are laminated in this order on the antiglare film. Or the structure which laminated | stacked the said polarizer and the said transparent protective film in this order on the said glare-proof film may be sufficient.

(7) Image display apparatus The image display apparatus of this invention is the structure similar to the conventional image display apparatus except using the anti-glare film of this invention. For example, in the case of LCD, it can be manufactured by appropriately assembling each component such as a liquid crystal cell, an optical member such as a polarizing plate, and an illumination system (backlight etc.), a black matrix pattern, etc. .

In the image display device of the present invention, as described above, the antiglare film of the present invention is disposed so that one direction in which a plurality of the particles are collected and the long side direction of the black matrix pattern coincide. Is preferred. The antiglare film of the present invention arranged as described above preferably has anisotropy. In this way, despite the fact that the irregular shape of the antiglare film surface is simply formed by the aggregation of particles, it has excellent antiglare properties, small glare, and little reduction in contrast. An image display device can be obtained.

The image display device of the present invention is used for any appropriate application. Applications include, for example, OA devices such as personal computer monitors, laptop computers, and copy machines, mobile phones, watches, digital cameras, personal digital assistants (PDAs), portable devices such as portable game machines, video cameras, televisions, microwave ovens, etc. Household electrical equipment, back monitor, car navigation system monitor,
In-vehicle equipment such as car audio, display equipment such as information monitors for commercial stores, security equipment such as monitoring monitors, nursing care and medical equipment such as nursing monitors and medical monitors.

Next, examples of the present invention will be described together with reference examples. However, the present invention is not limited by the following examples and reference examples. Various characteristics in the following examples and reference examples were evaluated or measured by the following methods.

(Coating specific gravity k (kg / m ³ ))
100 ml of the coating solution was prepared, and the weight was measured to obtain the specific gravity of the coating film.

(Acceleration a (m / s ² ))
The inclination angle was θ, and the calculation was performed using the following formula.
a = gravity acceleration (9.8 m / s ² ) × sin θ

(Coating thickness h (m))
Using “MCPD3750” manufactured by Otsuka Electronics Co., Ltd., non-contact interference film thickness measurement was performed. The coating film refractive index was 1.5.

(Coating viscosity η (Pa · s))
The viscosity measured under the condition of a shear rate of 200 (1 / s) was measured using a HAAKE RheoStress RS6000.

(Surface shape measurement)
A glass plate (thickness 1.3 mm) manufactured by Matsunami Glass Industry Co., Ltd. is bonded to the surface of the antiglare film on which the antiglare layer is not formed. Coda ET4000, manufactured by Kosaka Laboratory Co., Ltd.), the surface shape of the antiglare layer was measured under the condition of a cut-off value of 0.8 mm, arithmetic average surface roughness Ra, average inter-protrusion distance Sm, and average inclination The angle θa was determined. The high-precision fine shape measuring instrument automatically calculates the arithmetic average surface roughness Ra and the average inclination angle θa. The arithmetic average surface roughness Ra and the average inclination angle θ
a is based on JIS B 0601 (1994 edition). The average irregularity distance Sm is the average irregularity distance (mm) of the surface measured according to JIS B 0601 (1994 edition).

(Anti-glare evaluation)
(1) A sample in which a black acrylic plate (Mitsubishi Rayon Co., Ltd., thickness 2.0 mm) is bonded to the surface of the antiglare film on which the antiglare layer is not formed, and the reflection on the back surface is eliminated. Produced.
(2) In an office environment where a display is generally used (about 1000 Lx), the sample was illuminated with a fluorescent lamp (three-wavelength light source), and the antiglare property of the sample prepared above was visually determined according to the following criteria. .
Criteria G: Excellent anti-glare property and does not leave an outline image of the fluorescent lamp.
NG: Inferior in antiglare property, and an outline image of a fluorescent lamp is reflected.

(White blur evaluation and appearance)
(1) A sample in which a black acrylic plate (manufactured by Nitto Resin Co., Ltd., thickness 1.0 mm) is bonded to the surface of the antiglare film on which the antiglare layer is not formed, and reflection on the back surface is eliminated. Was made.
(2) Generally, in an office environment using a display (about 1000 Lx), the white blur phenomenon is visually observed when viewed from a direction of 60 ° with the vertical direction as a reference (0 °) with respect to the plane of the sample prepared above. And evaluated according to the following criteria.
Judgment criteria (white blur evaluation)
AA: Almost no white blur.
A: There is white blur but the effect on visibility is small.
B: There is white blur, but there is no practical problem.
-: Not appraisal (because it has no anti-glare property and is almost clear)
(3) Further, the appearance of the comprehensive antiglare film including prevention of white blur was visually determined as follows. In addition, the anti-glare film, which had a particularly high white blur suppression (prevention) effect, had an appearance that black (Jet Black) was narrowed while being uneven. This was determined as “J” below.
Judgment criteria (appearance)
J: Appearance with white blur prevention (black is squeezed) and anti-glare properties M: Appearance with matte and anti-glare properties *: Due to large unevenness and very strong anti-glare properties Not applicable to either J or M-: Not appraisal (because there is no anti-glare property and it is almost clear)

(Weight average particle diameter of fine particles)
The weight average particle diameter of the fine particles was measured by a Coulter counting method. Specifically, using a particle size distribution measuring device (trade name: Coulter Multisizer, manufactured by Beckman Coulter, Inc.) using the pore electrical resistance method, electrolysis corresponding to the volume of the particulates when the particulates pass through the pores. By measuring the electrical resistance of the liquid, the number and volume of fine particles were measured, and the weight average particle diameter was calculated.

(Thickness of anti-glare layer)
The total thickness of the antiglare film was measured using a micro gauge thickness meter manufactured by Mitutoyo Corporation, and the thickness of the antiglare layer was calculated by subtracting the thickness of the translucent substrate from the overall thickness. .

(Example 1-1)
As a resin contained in the coating liquid, UV curable urethane acrylate resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “UV1700B”, solid content: 100%) 70 parts by weight and pentaerythritol triacrylate as main components 30 parts by weight of polyfunctional acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “Biscoat # 300”, solid content 100%) was prepared. Copolymer particles of acryl and styrene (made by Sekisui Plastics Co., Ltd., trade name “Techpolymer”, weight average particle size: 3.0 μm, refractive index: 100 parts by weight of resin solid content of the resin. 1.52), 2 parts by weight, synthetic clay smectite (trade name “Lucentite SAN” manufactured by Co-op Chemical Co., Ltd.) as an organic clay as the thixotropy imparting agent, 0.4 part by weight, photopolymerization initiator (BASF) 3 parts by weight of a product name “Irgacure 907” and 0.5 parts by weight of a leveling agent (manufactured by DIC Corporation, trade name “PC4100”, solid content 10%). The organoclay was used after diluting with toluene to a solid content of 6%. This mixture was dissolved in toluene / cyclopentanone (CPN) so that the solid concentration was 50% by weight.
It diluted with the mixed solvent (weight ratio 80/20), and prepared the coating liquid using the ultrasonic disperser.

As a translucent substrate, a transparent plastic film substrate (triacetyl cellulose film, manufactured by Fuji Film Co., Ltd., trade name “Fujitac”, thickness: 60 μm, refractive index: 1.49)
Prepared. The said coating liquid was apply | coated to the single side | surface of the said transparent plastic film base material using a wire bar, and the coating film was formed. At this time, as shown in FIG. 2A, the transparent plastic film substrate is tilted, and the shear rate V of the coating film is 0.18 × 10 6 for 30 seconds.
^-9 m / s (shear distance S = 5.34 × 10 ⁻⁹ m). Subsequently, the said coating film was dried by heating at 90 degreeC for 2 minute (s). After that, accumulated light quantity 300m with high pressure mercury lamp
The coating film was cured by irradiating J / cm ² ultraviolet rays to form an antiglare layer having a thickness of 7 μm to obtain an antiglare film of this example. The shear distance S was calculated based on the formula (I ′), and the shear rate V was calculated based on the formula (II). Further, the above numerical values in the shear distance S and the shear rate V are values obtained by rounding off the calculated values based on the formula (I ′) or the formula (II), respectively. Since the numerical value of the shear rate V in the formula (I ′) is the value before rounding off, the numerical value of the shear distance S (5.34 × 10 ⁻⁹ m) is the above numerical value of the shear rate V (0. 18 × 10 ⁻⁹ m / s) ^multiplied by 30 seconds (5.4 × 1)
0 ^-9 m / s) and do not match. The same applies to the following examples and comparative examples.

(Example 1-2)
The coating film has a shear rate V of 0.09 × 10 ⁻⁹ m / s (shear distance S = 2) for 30 seconds.
. 67 × 10 ⁻⁹ m) The antiglare film of this example was obtained in the same manner as in Example 1-1.

(Example 1-3)
The coating film has a shear rate V of 0.04 × 10 ⁻⁹ m / s for 30 seconds (shear distance S = 1).
. The antiglare film of the present example was obtained in the same manner as in Example 1-1 except that it was set to 09 × 10 ⁻⁹ m).

(Example 2-1)
The solid content concentration is 40% by weight, and the shear rate V of the coating film is 0.11 × for 30 seconds.
Example 1 except that 10 ⁻⁹ m / s (shear distance S = 3.24 × 10 ⁻⁹ m) was used.
1 was used to obtain an antiglare film of this example.

(Example 2-2)
The shear rate V of the coating film was 0.27 × 10 ⁻⁹ m / s for 30 seconds (shear distance S = 8
. The anti-glare film of the present example was obtained in the same manner as in Example 2-1, except that 10 × 10 ⁻⁹ m).

(Example 2-3)
The coating film has a shear rate V of 0.53 × 10 ⁻⁹ m / s (shear distance S = 1) for 30 seconds.
An antiglare film of this example was obtained in the same manner as in Example 2-1, except that 5.88 × 10 ⁻⁹ m).

(Example 3-1)
The solid content concentration is 33% by weight, and the shear rate V of the coating film is 0.23 × 30 seconds.
This embodiment was carried out in the same manner as in Example 1-1, except that an antiglare layer having a thickness of 6.5 μm was formed as 10 ⁻⁹ m / s (shear distance S = 6.84 × 10 ⁻⁹ m). An antiglare film of an example was obtained.

(Example 3-2)
The coating film has a shear rate V of 0.56 × 10 ⁻⁹ m / s for 30 seconds (shear distance S = 1).
6. An antiglare film of this example was obtained in the same manner as in Example 3-1, except that 6.76 × 10 ⁻⁹ m).

(Example 3-3)
The shear rate V of the coating film was 1.12 × 10 ⁻⁹ m / s for 30 seconds (shear distance S = 3
An antiglare film of this example was obtained in the same manner as in Example 3-1, except that it was 3.53 × 10 ⁻⁹ m).

(Example 4-1)
The blending amount of the particles is 7 parts by weight, the thixotropic agent is not added, and the shear rate V of the coating film is 0.25 × 10 ⁻⁹ m / s for 60 seconds (shear distance S = 14.96). × 1
0 ^-9 m) and the fact that, as the solvent of the coating liquid, toluene / cyclopentanone (CPN)
Propylene glycol monomethyl ether (PM) instead of mixed solvent (weight ratio 80/20)
) / CPN mixed solvent (weight ratio 80/20) was used, and the antiglare film of this example was obtained in the same manner as in Example 2-1.

(Example 4-2)
The shear rate V of the coating film was set to 0.50 × 10 ⁻⁹ m / s (shear distance S = 2) for 60 seconds.
An antiglare film of this example was obtained in the same manner as in Example 4-1, except that 9.92 × 10 ⁻⁹ m).

(Example 4-3)
The coating film has a shear rate V of 0.10 × 10 ⁻⁹ m / s (shear distance S = 6) for 60 seconds.
. The anti-glare film of this example was obtained in the same manner as in Example 4-1, except that 11 × 10 ⁻⁹ m).

(Example 5-1)
The solid content concentration is 33% by weight, and the shear rate V of the coating film is 0.17 × for 60 seconds.
This embodiment was carried out in the same manner as in Example 4-1, except that an antiglare layer having a thickness of 6.5 μm was formed as 10 ⁻⁹ m / s (shear distance S = 10.45 × 10 ⁻⁹ m). An antiglare film of an example was obtained.

(Example 5-2)
The shear rate V of the coating film was 0.43 × 10 ⁻⁹ m / s (shear distance S = 2) for 60 seconds.
An antiglare film of this example was obtained in the same manner as in Example 5-1, except that 5.60 × 10 ⁻⁹ m).

(Example 5-3)
The coating film has a shear rate V of 0.85 × 10 ⁻⁹ m / s for 60 seconds (shear distance S = 5
An antiglare film of this example was obtained in the same manner as in Example 5-1, except that 1.20 × 10 ⁻⁹ m).

(Example 6-1)
The solid content concentration is 50% by weight, and the shear rate V of the coating film is 0.20 × for 60 seconds.
Example 4 with the exception of 10 ⁻⁹ m / s (shear distance S = 12.22 × 10 ⁻⁹ m).
The antiglare film of this example was obtained by the same method as -1.

(Example 6-2)
The coating film has a shear rate V of 0.04 × 10 ⁻⁹ m / s (shear distance S = 2) for 60 seconds.
. 49 × 10 ⁻⁹ m) The antiglare film of this example was obtained by the same method as in Example 6-1.

(Example 6-3)
The coating film has a shear rate V of 0.10 × 10 ⁻⁹ m / s (shear distance S = 6) for 60 seconds.
. The antiglare film of the present example was obtained in the same manner as in Example 6-1 except that 11 × 10 ⁻⁹ m).

(Example 7-1)
The shear rate V of the coating film was 0.27 × 10 ⁻⁹ m / s for 3 seconds (shear distance S = 0.
The anti-glare film of the present example was obtained in the same manner as in Example 2-1, except that 81 × 10 ⁻⁹ m).

(Example 7-2)
The shear rate V of the coating film was 0.27 × 10 ⁻⁹ m / s for 5 seconds (shear distance S = 1.
The antiglare film of the present example was obtained in the same manner as in Example 7-1 except that it was 35 × 10 ⁻⁹ m).

(Example 7-3)
The shear rate V of the coating film was 0.27 × 10 ⁻⁹ m / s (shear distance S = 2) for 10 seconds.
. The anti-glare film of the present example was obtained in the same manner as in Example 7-1 except that 70 × 10 ⁻⁹ m).

(Example 7-4)
The shear rate V of the coating film was 0.27 × 10 ⁻⁹ m / s for 30 seconds (shear distance S = 8
. An antiglare film of this example was obtained in the same manner as in Example 7-1 except that 10 × 10 ⁻⁹ m).
(Example 7-5)
An antiglare film of this example was obtained in the same manner as in Example 7-3 except that the blending amount of the particles was 5 parts by weight.

(Example 8-1)
The shear rate V of the coating film was 0.25 × 10 ⁻⁹ m / s for 30 seconds (shear distance S = 7
. The anti-glare film of this example was obtained in the same manner as in Example 4-1, except that it was set to 48 × 10 ⁻⁹ m).

(Example 8-2)
The coating film has a shear rate V of 0.25 × 10 ⁻⁹ m / s (shear distance S = 120 seconds).
29.92 × 10 ⁻⁹ m) The antiglare film of this example was obtained in the same manner as in Example 8-1.

(Example 9-1)
The blending amount of the particles was 6 parts by weight, the solid content concentration was 45% by weight, and the shear rate V of the coating film was 0.17 × 10 ⁻⁹ m / s (3 seconds). Shear distance S =
An antiglare film of this example was obtained in the same manner as in Example 1-1, except that 0.51 × 10 ⁻⁹ m).

(Example 9-2)
The shear rate V of the coating film was 0.17 × 10 ⁻⁹ m / s for 5 seconds (shear distance S = 0.
An antiglare film of this example was obtained in the same manner as in Example 9-1 except that 85 × 10 ⁻⁹ m).

(Example 9-3)
The blending amount of the particles was 8 parts by weight, and the shear rate V of the coating film was set to 0.
An antiglare film of this example was obtained in the same manner as in Example 9-1 except that the film was set to 07 × 10 ⁻⁹ m / s (shear distance S = 0.21 × 10 ⁻⁹ m). It was.

(Example 9-4)
The coating film has a shear rate V of 0.07 × 10 ⁻⁹ m / s for 5 seconds (shear distance S = 0.
An antiglare film of this example was obtained in the same manner as in Example 9-3, except that 35 × 10 ⁻⁹ m).

(Example 9-5)
An antiglare film of this example was obtained in the same manner as in Example 9-3 except that the blending amount of the particles was 10 parts by weight.

(Example 9-6)
The coating film has a shear rate V of 0.07 × 10 ⁻⁹ m / s for 5 seconds (shear distance S = 0.
An antiglare film of this example was obtained in the same manner as in Example 9-5, except that 35 × 10 ⁻⁹ m).

(Example 9-7)
An antiglare film of this example was obtained in the same manner as in Example 9-3 except that the blending amount of the particles was 12 parts by weight.

(Reference Example 1-1)
Without tilting the transparent plastic film substrate, the coating film had a shear rate V of 0.00 × 10 ⁻⁹ m / s (shear distance S = 0.00 × 10 ⁻⁹ m) for 30 seconds. Except for this, an antiglare film of this reference example was obtained in the same manner as in Example 1-1.

(Reference Example 2-1)
Other than the shear rate V of the coating film being 0.00 × 10 ⁻⁹ m / s (shear distance S = 0 × 10 ⁻⁹ m) for 30 seconds without inclining the transparent plastic film substrate. Obtained the anti-glare film of this reference example by the method similar to Example 2-1.

(Reference Example 3-1)
Other than the shear rate V of the coating film being 0.00 × 10 ⁻⁹ m / s (shear distance S = 0 × 10 ⁻⁹ m) for 30 seconds without inclining the transparent plastic film substrate. Obtained the anti-glare film of this reference example by the method similar to Example 3-1.

(Reference Example 4-1)
Other than the shear rate V of the coating film being 0.00 × 10 ⁻⁹ m / s (shear distance S = 0 × 10 ⁻⁹ m) for 60 seconds without tilting the transparent plastic film substrate. Obtained the anti-glare film of this reference example by the method similar to Example 4-1.

(Reference Example 5-1)
Other than the shear rate V of the coating film being 0.00 × 10 ⁻⁹ m / s (shear distance S = 0 × 10 ⁻⁹ m) for 60 seconds without tilting the transparent plastic film substrate. Obtained the anti-glare film of this reference example by the method similar to Example 5-1.

(Reference Example 6-1)
Other than the shear rate V of the coating film being 0.00 × 10 ⁻⁹ m / s (shear distance S = 0 × 10 ⁻⁹ m) for 60 seconds without tilting the transparent plastic film substrate. Obtained the anti-glare film of this reference example by the method similar to Example 6-1.

(Reference Example 7-1)
The shear rate V of the coating film was 0.27 × 10 ⁻⁹ m / s for 0 second (shear distance S = 0 ×
The antiglare film of the present reference example was obtained in the same manner as in Example 2-1, except that 10 ⁻⁹ m).

(Reference Example 8-1)
The coating film has a shear rate V of 0.25 × 10 ⁻⁹ m / s for 0 second (shear distance S = 0 ×
The antiglare film of this reference example was obtained in the same manner as in Example 4-1, except that 10 ⁻⁹ m).

Various properties were measured or evaluated for the antiglare films of Examples and Reference Examples thus obtained. The results are shown in Table 1 below.

As shown in Table 1, in all examples, using the same type of resin and particles, the arithmetic average surface roughness Ra is 0.020 to 0.490, and the average inter-protrusion distance Sm is 0.061 to
The surface shape could be freely controlled in a wide range with 0.356 and average inclination angle θa of 0.195 to 0.880. Example 4 in which no thixotropy-imparting agent is mixed in the coating solution
5, 6 and 8, the arithmetic average surface roughness Ra is 0.020 to 0.280, the average unevenness distance Sm is 0.061 to 0.244, and the average inclination angle θa is 0.248 to 0.618. there were.
On the other hand, in Examples 1-3, 7 and 9 in which the thixotropy-imparting agent was mixed, the arithmetic average surface roughness Ra was 0.027 to 0.490, and the average inter-protrusion distance Sm was 0.082 to 0.356.
The average inclination angle θa was 0.195 to 0.880. That is, if the coating liquid contains a thixotropy imparting agent, the surface shape of the antiglare film can be easily controlled in a wide range,
It was easy to increase the upper limit values of the arithmetic average surface roughness Ra, the average inter-concave distance Sm, and the average inclination angle θa. In many examples, good results were obtained for both antiglare properties and white blurring. In addition, as described above, the example of the white blur determination “B” has no practical problem, and can obtain a matte feeling (matte, calm appearance, appearance evaluation M) or extremely strong antiglare property. did it. In addition, all the anti-glare films whose visual appearance was judged to be “*” (very high anti-glare property) had an anti-glare property of “G” and Ra exceeded 0.20 μm. Thus, according to the Example of this application, the surface shape of the anti-glare film could be freely controlled in a wide range. In the embodiment, the predetermined time can be shortened and white blur can be further prevented by mixing the thixotropy-imparting agent with the coating liquid. Further, in the above case of mixing the thixotropy-imparting agent to the coating solution, the shear rate V is 0.05 or more, the shear distance S of ^{0.5 × 10 -9 m~8.0 × 10 -9} m
And Example 1-1, Example 1-2, Example 2-1, wherein the number of added parts was 2 parts,
In Example 3-1, Example 7-1, Example 7-2 and Example 7-3, white blur can be further prevented (white blur evaluation: AA), and black (jet black: The appearance that (Jet Black) was narrowed was obtained (appearance: J). On the other hand, in Reference Examples 1-1 to 8-1 in which the shear distance S of the coating film is 0 (that is, no shear is generated), the arithmetic average surface roughness Ra is 0.019-0. 034, the average irregularity distance Sm is 0.066 to 0.1
67. The average inclination angle θa was 0.160 to 0.248, and the range of the surface shape was extremely narrow compared to the examples. In addition, the film of these reference examples 1-1 to 8-1 was inferior in anti-glare property. Moreover, since there was almost no unevenness | corrugation in the surface of the said glare-proof layer and white blurring did not generate | occur | produce, white blurring evaluation was not possible (evaluation: "-").

In addition, in the graph of FIG. 11, the surface shape of the anti-glare film of an Example (average uneven | corrugated distance Sm and average inclination-angle (theta) a shown in Table 1) is shown. In the figure, the ● (black circle) mark is data of the antiglare film of the example, and the ■ (black square) mark (two points) is data of the conventional antiglare film. As shown in the figure, the antiglare film at the two points marked with ■ has a surface shape (average irregularity distance S).
m and the average inclination angle θa) are greatly different. Conventionally, in order to greatly vary the surface shape of the antiglare film as described above, it is necessary to use different types of resins, types of particles (particle diameter), and the like. On the other hand, according to the present embodiment, as shown in the figure, the resin is used only by controlling the shear distance S and the weight part of the particle (the weight part of the particle with respect to 100 parts by weight of the resin) using the same resin and the same particle. In addition, the surface shape could be controlled over a wide range equivalent to or better than that of conventional products with different types of particles.

Next, in the antiglare film of the present invention (the following Example 10-1 and Example 10-2), the one direction in which a plurality of the particles are collected coincides with the long side direction of the black matrix pattern of the image display device. An image display device arranged as described above was manufactured and the characteristics thereof were evaluated (Example 11-1 and Example 11-2 described later).

(Example 10-1 [Anti-glare film])
As a resin contained in the antiglare layer forming material, an ultraviolet curable urethane acrylate resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “UV1700B”, solid content 100%) 80 parts by weight, and pentaerythritol triacrylate 20 parts by weight of a polyfunctional acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “Biscoat # 300”, solid content 100%) as a main component was prepared. Crosslinked polymethyl methacrylate particles (manufactured by Sekisui Plastics Co., Ltd., trade name “Techpolymer”, weight average particle size: 5 μm per 100 parts by weight of the resin solid content of the resin.
2 parts by weight of refractive index: 1.51), 0.4 part by weight of synthetic smectite (trade name “Lucentite SAN” manufactured by Co-op Chemical Co., Ltd.), an organic clay, as the thixotropy imparting agent, and photopolymerization started. 3 parts by weight of an agent (trade name “Irgacure 907” manufactured by BASF Corporation) and 0.5 part of a leveling agent (trade name “PC4100” manufactured by DIC Corporation, solid content 10%) were mixed. The organoclay was used after diluting with toluene to a solid content of 6%. This mixture was dissolved in toluene / cyclopentanone (CPN) so that the solid concentration was 40% by weight.
It diluted with the mixed solvent (weight ratio 80/20), and prepared the glare-proof layer forming material (coating liquid) using the ultrasonic disperser.

As a translucent substrate, a transparent plastic film substrate (triacetyl cellulose film, manufactured by Fuji Film Co., Ltd., trade name “Fujitac”, thickness: 60 μm, refractive index: 1.49)
Prepared. The antiglare layer-forming material (coating liquid) was applied to one side of the transparent plastic film substrate using a wire bar to form a coating film. At this time, as shown in FIG. 2A, the transparent plastic film substrate was tilted, and the surface slip velocity V of the coating film was set to 0.127 × 10 ⁻⁹ m / s for 5 seconds. For convenience of explanation, the direction of the film with the transparent plastic film substrate tilted is referred to as “MD (Machine of anti-glare film)” described later.
Direction) ”. In the case of an actual machine that manufactures an antiglare film while transporting a long film by roll-to-roll, it is only necessary to incline the film with respect to the film transport direction. This is the same as the film transport direction in the actual machine. Moreover, let the direction of the film orthogonal to this MD direction be "TD (Transverse Direction) direction of an anti-glare film". Next, 9
The coating film was dried by heating at 0 ° C. for 2 minutes. Thereafter, ultraviolet light having an integrated light quantity of 300 mJ / cm ² was irradiated with a high-pressure mercury lamp, and the coating film was cured to form an antiglare layer having a thickness of 7.5 μm, thereby obtaining an antiglare film of this example. .

(Example 10-2 [Anti-glare film])
As the particles, crosslinked polystyrene particles (manufactured by Soken Chemical Co., Ltd., trade name “SX500”,
An antiglare film of this example was obtained in the same manner as in Example 10-1, except that a weight average particle size: 5 μm and a refractive index: 1.59) were used. The antiglare layer had a thickness of 7.5 μm.

Various properties were measured or evaluated for the antiglare films of Example 10-1 and Example 10-2 thus obtained. The results are shown in Table 2 below. In addition, although the surface shape measuring method is as above-mentioned, the surface shape was measured about MD direction and TD direction with respect to the anti-glare film of Example 10-1 and Example 10-2, respectively. Also,
Anisotropy evaluation and haze value measurement were performed as follows.

(Anisotropic evaluation)
The anisotropy evaluation of the unevenness on the surface of the antiglare film was determined according to the following criteria.
Judgment criteria Existence: The value obtained by dividing the difference in Ra value between the MD direction and the TD direction by the larger Ra value in the MD direction and the TD direction is 0.03 (3%) or more.
None: The value obtained by dividing the difference in Ra value between the MD direction and the TD direction by the larger Ra value in the MD direction and the TD direction is less than 0.03 (3%).

In addition, in this judgment criterion, since the antiglare film that becomes “present” can be visually confirmed that transmitted scattered light has anisotropy as follows when irradiated with a laser pointer,
Simple judgment by visual observation is also possible. That is, using a laser pointer having a circular light source, a laser is irradiated perpendicularly to the anti-glare film from a position 5 cm from the anti-glare film, and projected onto a white wall 5 m away from the anti-glare film. Check the shape of the transmitted light image. If it is an ellipse, it can be said that it has anisotropic scattering, and it can be interpreted that aggregates are formed in a direction perpendicular to the long direction of the ellipse.

(Haze value)
The haze value was measured using a haze meter (trade name “HM-150”, manufactured by Murakami Color Research Laboratory Co., Ltd.) according to JIS K 7136 (2000 version) haze (cloudiness). .

As shown in Table 2, in the antiglare films of Example 10-1 and Example 10-2, the MD direction of the antiglare film (the direction of the film in which the transparent plastic film substrate after coating is inclined) ) And the TD direction (the direction of the film perpendicular to the MD direction). That is, the antiglare films of Example 10-1 and Example 10-2 have on the surface an agglomerated part in which particles aggregate to form a convex part, and in the aggregated part, the particles are ,
A plurality of antiglare films existed in the TD direction (direction perpendicular to the MD direction).

(Example 11-1 [Image display device])
The antiglare film 1 was disposed on the viewing side surface of the liquid crystal display panel so that the MD direction of the antiglare film of Example 10-1 and the long side direction of the black matrix pattern of the liquid crystal display panel were orthogonal to each other. . The definition of the black matrix pattern of the liquid crystal display panel is 1
20 ppi.
(Example 11-2 [Image display device])
The antiglare film 2 was disposed on the viewing side surface of the liquid crystal display panel so that the MD direction of the antiglare film of Example 10-2 and the long side direction of the black matrix pattern of the liquid crystal display panel were orthogonal to each other. . The definition of the black matrix pattern of the liquid crystal display panel is 2
00ppi.

Various characteristics were measured or evaluated for the image display devices of Example 11-1 and Example 11-2 obtained in this way. The results are shown in Table 3 below. The evaluation of contrast (panel contrast) and glare was performed by the following method.

(Panel contrast evaluation)
A polarizing plate on the viewing side of a liquid crystal cell taken out from a liquid crystal television (manufactured by SHARP, 32 type, product name “LC-32DX3”) is a commercially available polarizing plate without an antiglare film (manufactured by Nitto Denko Corporation)
Product name “NPF-TEG1465DU”). On the replaced polarizing plate,
The surface on which the antiglare layer of the antiglare film was not formed was bonded using an adhesive. In the dark room, the front luminance at the time of black display and white display of the liquid crystal television was measured using a color luminance meter (trade name “BM-5”, manufactured by Topcon Techno House Co., Ltd.). The contrast was determined from (brightness during white display / brightness during black display), and the rate of decrease from the contrast when no antiglare film was bonded was determined.
The panel contrast evaluation was determined according to the following criteria.
Judgment criteria A: Decreasing rate of less than 5% B: Decreasing rate of 5% or more

(Glare evaluation)
(1) An antiglare film having an antiglare layer on which a 185 μm polarizing plate is bonded is bonded to a glass substrate.
(2) The glass substrate was placed on a black matrix pattern fixed on a light table, and the degree of glare was visually evaluated.
Judgment criteria A: There is almost no glare.
B: There is glare, but there is no practical problem.
C: There is glare.

As shown in Table 3, in the image display device, the anti-glare film was arranged such that one direction (MD direction) in which a plurality of the particles gathered and the long side direction of the black matrix pattern coincided with each other. In Example 11-1 and Example 11-2, good results were obtained in glare and antiglare properties. In addition, Example 1 using the anti-glare film of Example 10-1
In 1-1, since the haze value of the anti-glare film was as low as 1%, the contrast was good and the glare was also well prevented. In Example 11-2 using the antiglare film of Example 10-2, since the haze value of the antiglare film is as high as 9%, the contrast is slightly impaired, but there is no practical problem, and the glare is It was well prevented and could handle high-definition panels.

The antiglare film obtained by the method for producing an antiglare film of the present invention is, for example, an optical member such as a polarizing plate, a liquid crystal panel, and an image display such as an LCD (liquid crystal display) or an OLED (organic EL display). It can be suitably used for an apparatus, and its application is not limited and can be applied to a wide range of fields.

1-6, 12 Particles 10 Double-dot chain line 11 Antiglare layer 13 Thixotropic agent 14 Convex part 20 Translucent substrate 21 Coating film 22 Coating solution

Claims (20)

It is a method for producing an antiglare film in which a coating liquid is applied to at least one surface of a translucent substrate and the coating liquid is cured to form an antiglare layer,
The coating liquid contains a resin, particles, and a solvent,
Including a shearing step for causing shearing in the coating solution applied to the translucent substrate,
The manufacturing method of the anti-glare film characterized by adjusting the surface shape of the said anti-glare film by adjusting the shear distance of the coating film defined by following formula (I) in the said shearing process.

S = ∫Vdt (I)

In the formula (I),
S: Shear distance (m)
V: Shear rate (m / s)
t: Shear retention time (s)
And
The shear rate V is defined by the following formula (II):

V = kah ² / η (II)

In the formula (II),
k: Specific gravity of coating film (kg / m ³ )
a: Acceleration (m / s ² )
h: Coating thickness (m)
η: coating film viscosity (Pa · s)
It is. However, the acceleration a may change with time or may be constant. In the shearing step, the coating film has a shear distance S of 0.005 × 10 ⁻⁹ m to 120.
The method for producing an antiglare film according to claim 1, wherein the range is within a range of × 10 ⁻⁹ m. 3. The antiglare film according to claim 1, wherein the shear rate V is in a range of 0.05 × 10 ⁻⁹ m / s to 2.0 × 10 ⁻⁹ m / s. Production method. The method for producing an antiglare film according to claim 3, wherein the shear rate V is in a range of 0.05 × 10 ⁻⁹ m / s to 1.0 × 10 ⁻⁹ m / s. . The method for producing an antiglare film according to any one of claims 1 to 4, wherein the shear holding time is in a range of 0.1 to 60 s. The method for producing an antiglare film according to any one of claims 1 to 5, wherein a coating solution containing a thixotropic agent is used as the coating solution. The method for producing an antiglare film according to claim 6, wherein the thixotropy-imparting agent is at least one selected from the group consisting of organic clay, oxidized polyolefin, and modified urea. The thickness (d) of the antiglare layer is in the range of 3 to 12 μm, and the particle diameter (D) of the particles
The method for producing an antiglare film according to any one of claims 1 to 7, wherein is in the range of 2.5 to 10 µm. 9. The production of an antiglare film according to claim 8, wherein the relationship between the thickness (d) and the particle diameter (D) is in a range of 0.3 ≦ D / d ≦ 0.9. Method. Furthermore, the surface shape of the said anti-glare film is adjusted by adjusting the weight part of the said particle with respect to 100 weight part of said resin in the said coating liquid, The any one of Claim 1 to 9 characterized by the above-mentioned. The manufacturing method of the anti-glare film as described in a term. The said coating liquid WHEREIN: The said particle | grain is contained in 0.2-12 weight part with respect to 100 weight part of said resin, It is characterized by the above-mentioned. A method for producing an antiglare film. The anti-glare film manufactured by the manufacturing method as described in any one of Claim 1 to 11. The anti-glare layer has an agglomerated part that forms a convex part on the surface of the anti-glare layer as the particles aggregate.
13. The antiglare film according to claim 12, wherein a plurality of the particles are present in a gathered state in the surface direction of the antiglare layer in the agglomerated part forming the convex part. The antiglare property according to claim 12 or 13, wherein the height of the convex portion from the roughness average line of the antiglare layer is less than 0.4 times the thickness of the antiglare layer. the film. In the antiglare layer, the appearance defect having a maximum diameter of 200 μm or more is 1 per 1 m ^{2 of the} antiglare layer.
The antiglare film according to claim 12, wherein the antiglare film is one or less. 16. The penetration layer formed by the said resin osmose | permeating the said translucent base material between the said translucent base material and the said glare-proof layer is characterized by the above-mentioned. The anti-glare film as described in any one of these. A polarizing plate comprising a polarizer and the antiglare film according to any one of claims 12 to 16. An image display device comprising the antiglare film according to any one of claims 12 to 16. An image display device comprising the polarizing plate according to claim 17. Having the antiglare film on the viewing side surface,
In addition, it has a black matrix pattern,
The antiglare layer of the antiglare film has an agglomerated portion that forms a convex portion on the surface of the antiglare layer by the aggregation of the particles,
In the agglomerated part forming the convex part, the particles exist in a state of being gathered in the surface direction of the antiglare layer,
The anti-glare film is disposed so that one direction in which a plurality of the particles are collected and the long side direction of the black matrix pattern coincide with each other.
The image display device described.

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