JP4556613B2 - Anti-glare film and method for producing the same - Google Patents

Description

  The present invention relates to an antiglare film and a method for producing the same, and more particularly to an antiglare film suitable for a polarizing plate protective film for a liquid crystal display device and a method for producing the same.

In recent years, the outermost surface of a display device represented by a cathode ray tube (CRT), a liquid crystal display device (LCD), a plasma display panel (PDP), or the like is used to prevent a decrease in contrast and reflection of an image due to external light reflection. In addition, an antiglare film or an antireflection film is often disposed.
Fine irregularities are formed on the surface of such an antiglare film. As a method for forming such irregularities, a method is generally used in which a resin containing fine particles is applied to the film surface, and protrusions based on the shape of the particles are formed on the surface. In addition, sandblasting, etching, and a method for transferring shaped irregularities have been reported. The surface irregularities can diffuse and reflect external light to prevent image reflection. However, there is a problem that a so-called white blur phenomenon is likely to occur, in which black display is whitened due to the scattering of external light and the display quality is deteriorated. Furthermore, since the transmitted light from the pixels is also bent due to the unevenness of the surface, there is a problem that the clarity of the transmitted image is lowered.
For example, Patent Document 1 discloses an antiglare layer in which surface irregularities having a pitch of 30 to 300 μm and a ten-point average roughness of 0.3 to 3 μm are formed by forming transfer. However, depending on the method of forming by such transfer, it is necessary to introduce equipment, and it is difficult to form fine irregularities with a 10-point average roughness of 1 μm or less. The layer is insufficient in terms of transmitted image clarity.
Patent Document 2 discloses an antiglare layer characterized by having a fine concavo-convex structure with an average peak-valley interval of 40 μm or less and an average inclination angle of 5 degrees or more on the surface. According to this, it is described that even in a large-screen display device with a small pixel size, it is possible to effectively prevent occurrence of visual interference due to surface reflection of external light while preventing occurrence of a glare phenomenon. However, for high-definition display applications, it is insufficient in terms of improving the white blur phenomenon and sharpness of the transmitted image.
In Patent Document 3, in an antiglare film and an antiglare antireflection film having irregularities on the surface, a protrusion is cut along a plane including a normal vector at the apex of the protrusion, and straight to the right and left at right angles to the normal. When the length of the straight line is extended by 500 nm, the vertex formed by the angle formed by the three points of the point where the straight line that extends the line opposite to the point where the end point of the left or right line collides with the ridge line of the protrusion collides with the ridge line of the protrusion, An antiglare film and an antiglare antireflection film containing 50% or more of protrusions having an angle of 170 degrees or more are disclosed. According to this, it is described that it is possible to provide an antiglare film and an antiglare antireflection film that have good whiteness and good transmitted image clarity. As a method for forming such protrusions, it has been proposed to first form surface protrusions with fine particles or the like and then perform rubbing treatment, calendering treatment or the like on the apex portions of the protrusions to flatten the surface protrusions. However, such a method requires a new introduction of a rubbing processing apparatus, a calendar processing apparatus, etc., and at the same time, the processing process becomes more complicated.

Japanese Unexamined Patent Publication No. 64-19301 JP 2001-154006 A JP 2001-281402 A

  Accordingly, an object of the present invention is to provide an anti-glare film capable of realizing anti-glare properties, white blur improvement and resolution at a high level, and a method for efficiently and simply producing the same.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by containing specific fine particles in the coating liquid applied to the base film and reducing the surfactant. As a result, further research has been made based on this finding, and the present invention has been completed.

Thus, according to the present invention,
(1) An antiglare film characterized in that an antiglare layer having irregularities on the surface thereof is formed on a substrate film containing a transparent resin, and the irregularities satisfy the following requirements [1] to [3]. [1] The height of the unevenness is 0.1 to 0.8 μm. [2] The period of the unevenness is in the range of 4 to 100 μm. [3] The average inclination angle of the unevenness is 3 degrees or less;
(2) The antiglare film according to the above (1), which has a low refractive index layer having a refractive index of 1.25 to 1.37 on the antiglare layer;
(3) The antiglare film according to (1) or (2), wherein the refractive index of the antiglare layer is 1.55 or more;
(4) The antiglare layer according to any one of (1) to (3), wherein the antiglare layer comprises an active energy ray-curable resin or a thermosetting resin and fine particles having an average particle diameter of 5 to 100 nm. Antiglare film;
(5) The antiglare film according to any one of (1) to (4), wherein the total light transmittance is 90% or more and the haze is 10% or less;
(6) An antiglare layer is formed on a base film containing a transparent resin by applying a coating solution that satisfies the following requirements [4] to [6] directly or via another layer. The manufacturing method of the anti-glare film of any one of Claims 1-6 characterized by the above-mentioned;
[4] Content of volatile organic solvent is at least 20% by volume [5] Content of fine particles having an average particle diameter of 5 to 100 nm is at least 5% by volume [6] Content of surfactant The amount is at most 1000 ppm;
(7) A polarizing plate provided with the antiglare film according to any one of (1) to (5) on at least one surface of a polarizer. ;
And (8) A liquid crystal display device comprising the antiglare film according to any one of (1) to (5) or the polarizing plate according to (7);
Are provided respectively.

  ADVANTAGE OF THE INVENTION According to this invention, the anti-glare film suitable for the polarizing plate protective film in a liquid crystal display device which can implement | achieve anti-glare property, white blurring improvement, and a high resolution can be provided.

The antiglare film of the present invention has an antiglare layer having irregularities on its surface on a base film containing a transparent resin.
The transparent resin used for the base film used in the present invention is not particularly limited as long as it has a thickness of 1 mm and a total light transmittance of 80% or more. For example, a polymer resin or a polyester resin having an alicyclic structure , Cellulose resin, polycarbonate resin, polysulfone resin, polyethersulfone resin, polystyrene resin, chain polyolefin resin, polyvinyl alcohol resin, polyvinyl chloride resin, polymethyl methacrylate resin and the like. These transparent resins can be used alone or in combination of two or more. Among these, cellulose resins such as diacetyl cellulose, propionyl cellulose, triacetyl cellulose, and butyryl cellulose; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; A polymer resin having an alicyclic structure is preferable, and from the viewpoint of transparency and lightness, triacetyl cellulose, polyethylene terephthalate, and a polymer resin having an alicyclic structure are preferable, from the viewpoint of dimensional stability and thickness controllability. More preferred are polyethylene terephthalate and polymer resins having an alicyclic structure.

  The polymer resin having an alicyclic structure has an alicyclic structure in the main chain and / or side chain, and contains an alicyclic structure in the main chain from the viewpoint of mechanical strength, heat resistance and the like. Is preferred.

  Examples of the alicyclic structure of the polymer include a saturated alicyclic hydrocarbon (cycloalkane) structure and an unsaturated alicyclic hydrocarbon (cycloalkene) structure. From the viewpoint of mechanical strength and heat resistance, cycloalkane. A structure is preferred. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, more preferably 5 to 15 in the mechanical strength, The properties of heat resistance and film formability are highly balanced and suitable. The proportion of the repeating unit containing the alicyclic structure in the alicyclic structure-containing polymer used in the present invention may be appropriately selected according to the purpose of use, but is preferably 30% by weight or more, Preferably it is 50% by weight or more, particularly preferably 70% by weight or more, and most preferably 90% by weight or more. When the ratio of the repeating unit having an alicyclic structure in the polymer resin having an alicyclic structure is within this range, it is preferable from the viewpoint of the transparency and heat resistance of the base film.

Specifically, the polymer resin having an alicyclic structure includes (1) a norbornene polymer, (2) a monocyclic olefin polymer, (3) a cyclic conjugated diene polymer, and (4) vinyl. Examples include alicyclic hydrocarbon polymers and hydrogenated products thereof. Among these, norbornene-based polymers are more preferable from the viewpoints of transparency and moldability.
Specific examples of the norbornene-based polymer include ring-opening polymers of norbornene-based monomers, ring-opening copolymers of norbornene-based monomers and other monomers capable of ring-opening copolymerization, and hydrogenated products thereof, norbornene-based polymers Examples include addition polymers of monomers and addition copolymers with other monomers copolymerizable with norbornene monomers. Among these, from the viewpoint of transparency, a ring-opening (co) polymer hydrogenated product of a norbornene-based monomer is most preferable.
The polymer resin having the alicyclic structure is selected from known polymers disclosed in, for example, Japanese Patent Application Laid-Open No. 2002-321302.

  The glass transition temperature of the transparent resin used for this invention becomes like this. Preferably it is 80 degreeC or more, More preferably, it is 100-250 degreeC. A base film containing a transparent resin having a glass transition temperature in such a range is excellent in durability without causing deformation or stress in use at high temperatures.

  The base film used in the present invention may contain other compounding agents in addition to the transparent resin. The compounding agent is not particularly limited, but inorganic fine particles; antioxidants, heat stabilizers, light stabilizers, weathering stabilizers, ultraviolet absorbers, near infrared absorbers, and other stabilizers; resins such as lubricants and plasticizers Modifiers; coloring agents such as dyes and pigments; antistatic agents and the like. These compounding agents can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range not impairing the object of the present invention, and is usually 0 to 100 parts by weight of the transparent resin. 5 parts by weight, preferably 0 to 3 parts by weight.

The average thickness of the base film is preferably 30 to 300 μm, more preferably 40 to 200 μm from the viewpoint of mechanical strength and the like.
Moreover, it is preferable that the dispersion | variation in the thickness of a base film is less than 3% of the said average thickness over the base film full width. When the variation in the thickness of the base film is within the above range, the adhesion of the antiglare layer and the surface smoothness of other layers laminated thereon can be improved.
Examples of the method for forming the base film used in the present invention include a solution casting method and a melt extrusion method. Among these, the melt extrusion molding method is preferable because the content of volatile components in the base film and the thickness unevenness can be reduced. Further, examples of the melt extrusion molding method include a method using a die and an inflation method, but a method using a T die is preferable in terms of excellent productivity and thickness accuracy.
When adopting a method using a T die as a method for forming a base film, the melting temperature of the transparent resin in the extruder having the T die should be 80 to 180 ° C. higher than the glass transition temperature of the transparent resin. The temperature is preferably 100 to 150 ° C. higher than the glass transition temperature. If the melting temperature in the extruder is excessively low, the fluidity of the transparent resin may be insufficient. Conversely, if the melting temperature is excessively high, the resin may be deteriorated.

As the substrate film used in the present invention, one having one or both surfaces subjected to surface modification treatment may be used. By performing the surface modification treatment, the adhesion to the antiglare layer can be improved. Examples of the surface modification treatment include energy beam irradiation treatment and chemical treatment.
Examples of the energy ray irradiation treatment include corona discharge treatment, plasma treatment, electron beam irradiation treatment, ultraviolet ray irradiation treatment, and the like. From the viewpoint of treatment efficiency, corona discharge treatment and plasma treatment are preferred, and corona discharge treatment is particularly preferred.
Examples of the chemical treatment include a method of immersing in an aqueous solution of an oxidizing agent such as potassium dichromate solution or concentrated sulfuric acid and then thoroughly washing with water. It is effective to shake in the immersed state, but there is a problem that the surface will dissolve or the transparency will be lowered if treated for a long time. Depending on the reactivity and concentration of the chemical used, the treatment time etc. It needs to be adjusted.

In this invention, you may interpose another layer between a base film and the glare-proof layer mentioned later. Examples of the other layer include a primer layer.
The primer layer is formed for the purpose of imparting and improving the adhesion between the base film containing a transparent resin and the antiglare layer. Examples of the material constituting the primer layer include polyester urethane resins, polyether urethane resins, polyisocyanate resins, polyolefin resins, resins having a hydrocarbon skeleton in the main chain, polyamide resins, acrylic resins, and polyester resins. Examples thereof include resins, vinyl chloride / vinyl acetate copolymers, chlorinated rubber, cyclized rubber, and modified products obtained by introducing polar groups into these polymers. Among these, a modified product in which a polar group is introduced into a resin having a hydrocarbon skeleton in the main chain and a modified product in which a polar group is introduced into a cyclized rubber can be suitably used.

  Examples of the resin having a hydrocarbon skeleton in the main chain include a polybutadiene skeleton or a resin having a polybutadiene skeleton hydrogenated to at least a part thereof, specifically, polybutadiene resin, hydrogenated polybutadiene resin, styrene / butadiene / styrene. Examples thereof include a block copolymer (SBS copolymer), a hydrogenated product thereof (SEBS copolymer), and the like. Especially, the modified material which introduce | transduced the polar group into the hydrogenated product of a styrene-butadiene-styrene block copolymer can be used conveniently.

As a compound for introducing a polar group used for obtaining a modified product of a polymer, a carboxylic acid or a derivative thereof is preferable. For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid; halides, amides, imides, anhydrides and esters of unsaturated carboxylic acids such as maleyl chloride, maleimide, maleic anhydride and citraconic anhydride And the like; and the like. Among these, a modified product with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride is excellent in adhesion, and thus can be suitably used. Among the unsaturated carboxylic acids or anhydrides thereof, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are more preferable, and maleic acid and maleic anhydride are particularly preferable. These unsaturated carboxylic acids and the like can be modified by mixing two or more kinds.
The thickness of the primer layer is not particularly limited, but is usually 0.01 to 5 μm, preferably 0.1 to 2 μm.

In the present invention, the antiglare layer serves to prevent, for example, light from a fluorescent lamp from moving on the screen in order to improve the visibility of a display device such as a liquid crystal display device or a CRT. The layer containing the substance to be made contains an organic resin material as an essential component.
As the organic resin material constituting the antiglare layer, it has properties as a binder in the antiglare layer, has sufficient strength as a film after forming the antiglare layer, and can be used without particular limitation with transparency. . Examples of the resin include a thermosetting resin, a thermoplastic resin, and an active energy ray curable resin, and a thermosetting resin or an active energy ray curable resin is preferable in terms of the strength and workability of the film.
Thermosetting resins include phenolic resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea co-condensation resin, silicone resin, polysiloxane Among them, melamine resin, epoxy resin, silicone resin, and polysiloxane resin are preferable from the viewpoint of excellent surface hardness, resistance to repeated fatigue, and scratch resistance.
Further, these resins can be used by adding a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like, if necessary.

The active energy ray-curable resin is a resin obtained by curing a prepolymer, an oligomer and / or a monomer having a polymerizable unsaturated bond or an epoxy group in a molecule by irradiation with energy rays. An active energy ray refers to an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or crosslinking molecules, and usually an ultraviolet ray or an electron beam is used.
There is no restriction | limiting in particular as an ultraviolet-ray and an electron beam curable resin, It can select from what was used conventionally and can use it suitably. This ultraviolet curable resin contains a photopolymerizable prepolymer, a photopolymerizable monomer, a photopolymerization initiator or a photosensitizer. The electron beam curable resin contains a photopolymerizable prepolymer or a photopolymerizable monomer.

Examples of the photopolymerizable prepolymer include polyester acrylate, epoxy acrylate, urethane acrylate, and polyol acrylate. These photopolymerizable prepolymers may be used alone or in combination of two or more. Examples of the photopolymerizable monomer include polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples include dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate.
In the present invention, it is preferable to use urethane acrylate as the prepolymer and dipentaerythritol hexa (meth) acrylate as the monomer.

  Examples of the photopolymerization initiator include acetophenones, benzophenones, α-amyloxime esters, tetramethylchuram monosulfide, thioxanthones, and the like. Further, n-butylamine, triethylamine, poly-n-butylphosphine and the like can be mixed and used as a photosensitizer.

In the present invention, the antiglare layer is preferably composed of the thermosetting resin or active energy ray curable resin and fine particles. When the antiglare layer has the above-described configuration, the uneven surface shape in the present invention can be realized.
As the fine particles, those having an average particle diameter of 5 to 100 nm, preferably 10 to 50 nm are used. The average particle size is determined by visual observation from a secondary electron emission image photograph obtained by a scanning electron microscope (SEM) or the like, by image processing, or by dynamic light scattering, static It can be measured by a particle size distribution meter using an automatic light scattering method or the like. The average particle diameter here refers to the number average particle diameter. The same applies hereinafter.
More specifically, fine particles having the above particle diameter may be used, but conductive fine particles are preferable. By using conductive fine particles as the fine particles, an antiglare layer having excellent antistatic properties and mechanical strength can be obtained. In addition, the refractive index of the antiglare layer can be easily controlled.

  The conductive fine particles are not particularly limited as long as they are conductive fine particles, but metal oxide fine particles are preferable because of excellent transparency.

Examples of the conductive metal oxide include antimony pentoxide, tin oxide, tin oxide doped with phosphorus (PTO), tin oxide doped with antimony (ATO), and tin oxide doped with fluorine (FTO). Indium oxide doped with tin (ITO), indium oxide doped with zinc (IZO), zinc oxide doped with aluminum (AZO), zinc oxide / aluminum oxide, zinc antimonate and the like. These metal oxide fine particles can be used singly or in combination of two or more. Among these, the use of tin oxide doped with antimony pentoxide and / or phosphorus is preferable because of its excellent transparency.
Moreover, in this invention, what provided electroconductivity by coat | covering a conductive metal oxide to the metal oxide fine particle which does not have electroconductivity as a conductive metal oxide fine particle can also be used. For example, the surface of fine particles of titanium oxide, zirconium oxide, cerium oxide or the like having a high refractive index but no conductivity can be used by coating the conductive metal oxide to impart conductivity.

  In the present invention, the content of fine particles in the antiglare layer is preferably at least 30% by volume, and more preferably 40-60% by volume. When the content of the fine particles is less than the above range, the height of the surface unevenness of the antiglare layer is insufficient, and conversely when the content is large, the strength of the antiglare layer tends to be insufficient.

In the present invention, the height of the irregularities on the surface of the antiglare layer is 0.1 to 0.8 μm, preferably 0.2 to 0.7 μm, in terms of 10-point average roughness Rz. If the height of the unevenness is smaller than the above range, the antiglare property is insufficient. Conversely, if the height is large, the scattering becomes too large, and when used in an image display device, the haze increases or the image sharpness decreases. In addition, the whiteness when the image display is black is also enhanced.
The ten-point average roughness Rz expressed as the height of irregularities on the surface of the antiglare layer is, for example, 1 mm in diameter with a tip portion made of diamond having a conical shape with an apex angle of 55 degrees according to JIS B0601-1994. It is possible to obtain knowledge as a surface roughness curve by scanning the surface of the concavo-convex structure with a length of 3 mm in a certain direction via the measuring needle, measuring the movement change in the vertical direction of the measuring needle in that case, and recording it. it can. Alternatively, it can be measured by an optical interference type surface roughness measuring machine.

In the present invention, the range of the irregularities on the surface of the antiglare layer is usually 4 to 100 μm, preferably 10 to 80 μm. When the period of the unevenness is smaller than the above range, the antiglare property is insufficient, and conversely, when it is large, glare occurs when used in an image display device.
The period of the antiglare layer is assumed to be a reference line on which the unevenness change of the surface roughness curve can be evaluated as a protrusion based on a portion where the unevenness change in the surface roughness curve is minute, and the protrusion from the reference line Can be defined as the average of the distances between the intersection points based on the intersection points when the surface roughness curve passes from the bottom line to the top (or from the top to the bottom).

In the present invention, the average inclination angle of the antiglare layer is 3 degrees or less, preferably 2 degrees or less. If the average inclination angle of the antiglare layer is larger than the above range, the scattering becomes excessively large, and when used in an image display device, the haze increases or the image clarity decreases, and the image display is displayed in black. Whiteness becomes stronger when selected.
The average inclination angle can be defined as the average of the absolute values of the gradient based on the gradient of the portion where the unevenness change is minute in the surface roughness curve.

  In this invention, it is preferable that the shape when the convex part of an anti-glare layer is seen from the main surface side is the shape of polygonal close-packed packing. When the shape is a polygonal close-packed shape, it is possible to achieve both antiglare properties, white blurring prevention and transmitted image sharpness. Examples of the polygon include a pentagon, a hexagon, and an octagon. The shape may be a combination of two or more of these.

  In the present invention, the refractive index of the antiglare layer is preferably 1.55 or more, more preferably 1.60 or more. When the refractive index of the antiglare layer is within this range, when a low refractive index layer is provided on the antiglare layer, reflection of external light can be suppressed and reflection can be prevented. The refractive index can be obtained by measuring using a known spectroscopic ellipsometer, for example.

In the present invention, the antiglare layer preferably exhibits a hardness of “HB” or higher in a pencil hardness test (test plate is a glass plate) shown in JIS K5600-5-4. When the pencil hardness of the antiglare layer is in the above range, the antiglare layer can also serve as the hard coat layer, and the member can be thinned.
The thickness of the antiglare layer is preferably in the range of 1 to 30 μm.

  In the present invention, it is preferable to have a low refractive index layer having a refractive index of 1.25 to 1.37 on the antiglare layer. By having a low refractive index layer, the antiglare film of the present invention can have antireflection properties.

In the present invention, the material constituting the low refractive index layer is not particularly limited as long as it is a material constituting the layer having a refractive index in the above range, but the refractive index can be easily controlled and the water resistance is excellent. Airgel is preferable.
The airgel is a transparent porous body in which minute bubbles are dispersed in a matrix. Most of the size of the bubbles is 200 nm or less, and the content of the bubbles is usually 10% by volume or more and 60% by volume or less, preferably 20% by volume or more and 40% by volume or less.
Specific examples of the airgel in which minute bubbles are dispersed include silica aerogel and a porous body in which hollow particles are dispersed in a matrix.
Silica airgel is a wet state composed of a silica skeleton obtained by hydrolysis polymerization reaction of alkoxysilane as disclosed in US Pat. No. 4,402,927, US Pat. No. 4,432,956, US Pat. No. 4,610,863 and the like. The gel-like compound can be produced by drying in a supercritical state above the critical point of the solvent in the presence of a solvent (dispersion medium) such as alcohol or carbon dioxide. In supercritical drying, for example, a gel compound is immersed in liquefied carbon dioxide, and all or part of the solvent contained in the gel compound is replaced with liquefied carbon dioxide having a critical point lower than that of the solvent. It can be carried out by drying under supercritical conditions of a single system of or a mixed system of carbon dioxide and a solvent. Silica airgel may be produced in the same manner as described above using sodium silicate as a raw material as disclosed in US Pat. No. 5,137,279, US Pat. No. 5,124,364, and the like. The refractive index of silica airgel can be freely changed by the raw material compounding ratio of silica airgel.
When silica aerogel is used, it is preferable to impart hydrophobicity to the silica airgel by hydrophobizing the gel-like compound obtained by hydrolysis and polymerization reaction of alkoxysilane as described above. Hydrophobic silica airgel imparted with hydrophobicity as described above can prevent moisture, water, and the like from entering, and prevent the performance of the silica airgel from being degraded in refractive index, light transmittance, and the like.
This hydrophobizing treatment can be performed before or during supercritical drying of the gel compound. The hydrophobization treatment is performed to make the hydrophobization by reacting the hydroxyl group of the silanol group present on the surface of the gel compound with the functional group of the hydrophobization treatment agent and replacing it with the hydrophobic group of the hydrophobization treatment agent. . As a method of performing the hydrophobization treatment, the gel is immersed in a hydrophobization treatment solution in which the hydrophobization treatment agent is dissolved in a solvent, mixed, and so on. There is a method in which the hydrophobization reaction is performed by heating accordingly.

Examples of the solvent used for the hydrophobic treatment include methanol, ethanol, isopropanol, xylene, toluene, benzene, N, N-dimethylformamide, hexamethyldisiloxane, and the like, but the hydrophobic treatment agent can be easily dissolved. And what is necessary is just to be able to substitute for the solvent which the gel before hydrophobization treatment contains, and it is not limited to these. Further, when supercritical drying is performed in a later step, a medium that can be easily supercritically dried, such as methanol, ethanol, isopropanol, liquefied carbon dioxide, or the like, is preferable. Examples of the hydrophobizing agent include hexamethyldisilazane, hexamethyldisiloxane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, and methyltriethoxysilane. Etc.
For the hydrophobization treatment, methods disclosed in JP-A-5-279011 and JP-A-7-138375 can also be used.

As a porous material in which hollow particles are dispersed in a matrix, hollow fine particles having voids inside fine particles as disclosed in JP-A Nos. 2001-233611 and 2003-149642 are used as binder resins. And a porous material dispersed in the substrate.
The binder resin can be selected from resins suitable for conditions such as dispersibility of hollow fine particles, transparency of the porous body, and strength of the porous body. For example, conventionally used polyester resins and acrylic resins Resin, urethane resin, vinyl chloride resin, epoxy resin, melamine resin, fluorine resin, silicon resin, butyral resin, phenol resin, vinyl acetate resin, UV curable resin, electron beam curable resin, emulsion resin, water-soluble resin, hydrophilic resin Further, a mixture of these resins, a coating resin such as a copolymer or a modified product of these resins, a hydrolyzable organosilicon compound such as alkoxysilane, and a hydrolyzate thereof can be used.
Among these, hydrolyzable organosilicon compounds such as acrylic resins, epoxy resins, urethane resins, silicon resins, alkoxysilanes, and hydrolysates thereof are preferable from the viewpoint of the dispersibility of the fine particles and the strength of the porous body.
When a porous body in which hollow particles are dispersed in a matrix is used as the low refractive index layer, it is possible to improve the reflection characteristics and antifouling properties of the low refractive index layer. Good.

The hollow fine particles are not particularly limited as long as they are fine particles of an inorganic compound, but inorganic hollow fine particles in which cavities are formed inside the outer shell are preferable, and use of silica-based hollow fine particles is particularly preferable.
As the inorganic compound, an inorganic oxide is common. As the inorganic _{oxide, SiO 2, Al 2 O 3} , B 2 O 3, TiO 2, ZrO 2, SnO 2, Ce 2 O 3, P 2 O 5, Sb 2 O 3, MoO 3, ZnO 2, WO One or two or more of ₃ or the like can be mentioned. Examples of the two or more inorganic oxides include TiO ₂ —Al ₂ O ₃ , TiO ₂ —ZrO ₂ , In ₂ O ₃ —SnO ₂ , and Sb ₂ O ₃ —SnO ₂ . These can be used alone or in combination of two or more.

  As the inorganic hollow fine particles, (A) an inorganic oxide single layer, (B) a single layer of a composite oxide composed of different kinds of inorganic oxides, and (C) a double layer of (A) and (B) above What is included can be used.

  The outer shell may be porous with pores, or the pores may be closed and the cavity sealed with respect to the outside of the outer shell. The outer shell is preferably a plurality of inorganic oxide coating layers comprising an inner first inorganic oxide coating layer and an outer second inorganic oxide coating layer. By providing the second inorganic oxide coating layer on the outer side, the fine pores of the outer shell are closed to make the outer shell dense, and furthermore, the inorganic hollow fine particles in which the inner cavity is sealed can be obtained. In particular, when a fluorine-containing organosilicon compound is used for forming the second inorganic oxide coating layer, the coating layer containing fluorine atoms is formed, so that the resulting particles have a lower refractive index and are reduced to an organic solvent. The dispersibility is good, and it is also effective for imparting antifouling properties to the low refractive index layer, which is preferable. Such fluorine-containing organic silicon compounds include 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, heptadecafluorodecyl. Examples thereof include trichlorosilane, heptadecafluorodecyltrimethoxysilane, trifluoropropyltrimethoxysilane, and tridecafluorooctyltrimethoxysilane.

  The average particle size of the inorganic hollow fine particles is not particularly limited, but is preferably 5 to 2000 nm, and more preferably 20 to 100 nm. If it is smaller than 5 nm, the effect of lowering the refractive index due to hollowness is small. Conversely, if it is larger than 2000 nm, the transparency is extremely deteriorated, and the contribution due to diffuse reflection increases. Here, the average particle diameter is a number average particle diameter by observation with a transmission electron microscope.

  The method for producing inorganic hollow fine particles as described above is described in detail, for example, in JP-A-2001-233611, and the inorganic hollow fine particles that can be used in the present invention are produced based on the method described therein. In addition, commercially available inorganic hollow fine particles can also be used.

  The blending amount of the inorganic fine particles is not particularly limited, but is preferably 10 to 30% by weight with respect to the entire low refractive index layer. When the blending amount of the inorganic fine particles is within this range, an optical laminated film having both low refractive index properties and scratch resistance can be obtained.

The refractive index of the low refractive index layer is preferably 1.25 to 1.37, more preferably 1.30 to 1.37. By setting the refractive index of the low refractive index layer in the above range, in addition to antireflection properties, scratch resistance can be imparted to the antiglare film.
The refractive index of the low refractive index layer can be measured by the same method as the refractive index of the antiglare layer.
The thickness of the low refractive index layer is 10 to 1000 nm, preferably 30 to 500 nm, in order to improve the absorption of visible light.

In the present invention, an antifouling layer may be provided on the low refractive index layer. The antifouling layer is provided for protecting the low refractive index layer and enhancing the antifouling performance.
The material for forming the antifouling layer is not particularly limited as long as the function of the low refractive index layer is not inhibited and the required performance as the antifouling layer is satisfied. Usually, a compound having a hydrophobic group can be preferably used.
As specific examples, a perfluoroalkylsilane compound, a perfluoropolyethersilane compound, or a fluorine-containing silicone compound can be used. As a method for forming the antifouling layer, for example, a physical vapor deposition method such as vapor deposition or sputtering; a chemical vapor deposition (CVD) method; a wet coating method; The thickness of the antifouling layer is not particularly limited, but is usually preferably 20 nm or less, and more preferably 1 to 10 nm.

The manufacturing method of the anti-glare film of this invention apply | coats the coating liquid which satisfy | fills the requirements of following [4]-[6] on the base film containing transparent resin directly or through another layer. Thus, an antiglare layer is formed.
[4] The content of the volatile organic solvent is at least 20% by volume.
[5] The content of fine particles having an average particle diameter of 5 to 100 nm is at least 5% by volume.
[6] The surfactant content is at most 1000 ppm.

The base film used in the production method of the present invention is as described in the antiglare film of the present invention.
In the case where another layer is interposed between the base film and the antiglare layer, the other layer includes a primer layer. The material for forming the primer layer is as described in the antiglare film of the present invention. The method for forming the primer layer is not particularly limited, and examples thereof include a method in which a primer layer forming coating solution is formed on a base film by a known coating method.

In the production method of the present invention, the volatile organic solvent contained in the coating solution for forming the antiglare layer includes alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol, ethylene glycol mono Glycols such as butyl ether and ethylene glycol monoethyl ether; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane and n-heptane; esters such as ethyl acetate and butyl acetate; methyl ethyl ketone; Ketones such as methyl isobutyl ketone; and combinations of two or more thereof; and the like.
Among these, in order to generate convection of the coating liquid and form surface irregularities, ASTM. The relative evaporation rate when the evaporation rate of n-butyl acetate measured according to D3539.76 is 1 is preferably 0.7 or more, and more preferably 0.9 or more. Examples of such an organic solvent include methanol, ethanol, toluene, n-hexane, ethyl acetate, butyl acetate, methyl ethyl ketone, and methyl isobutyl ketone.
Content of the organic solvent in a coating liquid is 20 volume% or more, and it is preferable that it is 40 volume% or more. If the amount is less than the above range, the convection of the coating solution does not occur sufficiently, and the surface unevenness becomes insufficient.

In the production method of the present invention, the fine particles having an average particle size of 5 to 100 nm contained in the coating solution for forming the antiglare layer are as described in the antiglare film of the present invention.
The particle diameter of the fine particles is an average particle diameter of 5 to 100 nm, preferably 10 to 50 nm. If the particle diameter is smaller than the above range, the coating solution is not imparted with thixotropy and tends to make it difficult to form irregularities on the surface of the antiglare layer after coating. When the antiglare film obtained is used in an image display device, the image clarity is reduced.
The content of fine particles in the coating solution is at least 5% by volume, preferably 7-30% by volume. If the content of the fine particles is less than the above range, the coating solution is not imparted with thixotropy, and irregularities that serve as an antiglare layer are not formed on the surface.

In the production method of the present invention, the content of the surfactant contained in the coating solution for forming the antiglare layer is at most 1000 ppm, preferably at most 500 ppm, and most preferably 0 ppm. When the content of the surfactant is larger than the above range, sufficient convection of the coating liquid does not occur, and irregularities are not formed on the surface of the antiglare layer.
Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant. Examples of fluorine-based surfactants include perfluoroalkylsulfonic acid amide group-containing nonions such as 3M's Fluorard FC-431, Daifuku Ink's Megafac F-171, F-172, F-173, F Perfluoroalkyl group-containing oligomers such as -176PF, F-470, and F-471. Examples of the silicone surfactant include polydimethylsiloxane in which the side chain or the end of the main chain is modified with various substituents such as oligomers such as ethylene glycol and propylene glycol.

  The antiglare layer of the present invention preferably contains no particles having a particle diameter of 500 nm or more. When particles having an average particle size in the above range are contained, the haze of the antiglare layer is increased, and when the obtained antiglare film is used for an image display device, the image clarity is deteriorated.

  Examples of the coating solution for forming the antiglare layer include organic resin materials constituting the antiglare layer, in addition to the fine particles and the surfactant. The organic resin material is as described in the antiglare film of the present invention.

The viscosity of the coating solution for forming the antiglare layer is preferably 50 mPa · s or less, and more preferably 30 mPa · s or less.
When the viscosity is larger than the above range, the convection of the coating solution is not sufficiently generated, and the surface unevenness becomes insufficient.
The viscosity of the coating solution can be measured with a single cylindrical rotational viscometer according to JIS Z 8803. The coating solution temperature at the time of measurement is the actual coating environment temperature.

  The coating method of the coating liquid for forming the antiglare layer is not particularly limited, and a known coating method can be employed. Examples of the coating method include a wire bar coating method, a dip method, a spray method, a spin coating method, and a roll coating method. The thickness after application is preferably 10 μm or more in terms of the average thickness, more preferably 30 μm to 100 μm in terms of the average thickness in the state of the solution immediately after application and before solvent drying. When the thickness after application is thinner than the above range, the height of the surface irregularities becomes insufficient. On the other hand, if the thickness after coating is larger than the above range, the surface unevenness height and period increase, white blurring increases, and the transmitted image sharpness deteriorates, which is not preferable.

In the production method of the present invention, an antiglare layer having irregularities on the surface can be formed by applying a coating solution constituting the antiglare layer and then drying and curing the coating solution. In the present invention, by applying the coating liquid constituting the above-described antiglare layer, convection occurs in the coating liquid during coating, and irregularities can be easily formed on the surface of the coating layer.
The drying temperature and drying time are appropriately set according to the solvent of the coating solution constituting the antiglare layer, the type of organic resin material, and the type of substrate film. The drying temperature is usually in the range from room temperature to the glass transition temperature of the substrate film. Surface irregularities are formed by the convection of the coating liquid during coating. Furthermore, the surface unevenness is fixed by increasing the viscosity of the remaining coating liquid component by reducing the solvent by drying.

After obtaining the coating film of the antiglare layer and drying it, by heating when containing a thermosetting resin, irradiating active energy rays when containing an active energy ray curable resin Can be cured to form an antiglare layer. The conditions for curing vary depending on the type of organic resin material constituting the antiglare layer.
When the organic resin material is a thermosetting resin, it may be cured by heating under curing conditions suitable for the thermosetting resin to be used.
When the organic resin material is an active energy ray-curable resin, it can be cured by irradiation with an electron beam or ultraviolet rays. In the case of electron beam curing, energy of 50 to 1000 KeV emitted from various electron beam accelerators such as Cockrowalton type, bandegraph type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type is used. An electron beam is used. In the case of ultraviolet curing, ultraviolet rays emitted from rays of ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, xenon arc, metal halide lamp and the like can be mentioned.

In the production method of the present invention, when a low refractive index layer is formed on the antiglare layer, the coating liquid constituting the low refractive index layer is applied on the antiglare layer and then dried. .
Examples of the coating method include known coating methods such as a wire bar coating method, a dip method, a spray method, a spin coating method, and a roll coating method.

  The formation method when the material constituting the low refractive index layer is a porous body in which hollow particles are dispersed in a matrix is not particularly limited. For example, at least fine particles have voids on the antiglare layer. Examples of the method include coating a hollow fine particle-containing coating solution containing a binder resin by a known coating method, and performing drying / heating treatment as necessary. The temperature of the heating performed as necessary is usually 50 to 200 ° C, preferably 80 to 150 ° C.

  In the production method of the present invention, when the antifouling layer is formed on the low refractive index layer, the antifouling layer is formed by a physical vapor deposition method such as vapor deposition or sputtering depending on the material to be formed; A chemical vapor deposition (CVD) method; a wet coating method.

  The antiglare film of the present invention has a total light transmittance of 90% or more, preferably a haze of 10% or less, a total light transmittance of 92% or more, and a haze of 5% or less. More preferably it is. If it is out of the range, the image clarity tends to be lowered when the antiglare film is used in an image display device.

The anti-glare film of the present invention is excellent in anti-glare property, and further has excellent anti-reflection properties by providing a low refractive index layer. Therefore, a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display It can be applied to display devices such as (ELD) and cathode ray tube display devices (CRT).
The antiglare film of the present invention is preferably used for a liquid crystal display device among the above display devices, and more preferably used for a polarizer protective film.

The polarizing plate of the present invention includes the antiglare film of the present invention on at least one surface of a polarizer.
As a polarizer, for example, a film made of a suitable vinyl alcohol-based polymer according to the prior art such as polyvinyl alcohol or partially formalized polyvinyl alcohol, a dyeing treatment with a dichroic substance made of iodine or a dichroic dye, a stretching treatment In addition, an appropriate treatment such as a crosslinking treatment can be performed in an appropriate order and method, and an appropriate material that transmits linearly polarized light when natural light is incident can be used. In particular, those excellent in light transmittance and degree of polarization are preferable. The thickness of the polarizer is generally 5 to 80 μm, but is not limited thereto.
In the polarizing plate of the present invention, the antiglare film of the present invention may be provided on at least one surface of the polarizer, and is usually provided on only one side. In the case where the antiglare film of the present invention is provided on only one side of the polarizer, it is preferable that the antiglare film of the present invention is provided on the viewing side of the display device.
In the polarizing plate of the present invention, when the antiglare film of the present invention is provided on only one side of the polarizer, it is preferable to provide a protective film on the other surface of the polarizer. In this case, examples of the protective film include a film made of a cellulose resin such as triacetyl cellulose or a polymer resin having an alicyclic structure, and is excellent in transparency, low birefringence, dimensional stability, and the like. From the viewpoint, a polymer resin having an alicyclic structure is preferable. Examples of the polymer resin having an alicyclic structure are the same as those described for the base film used in the antiglare film of the present invention.

In the polarizing plate of the present invention, the protective film used may be isotropic or birefringent. When the protective film has birefringence, the protective film can also serve as a retardation plate to be laminated when forming the liquid crystal display device, and the thickness of the member can be reduced. Examples of the method for obtaining the protective film having birefringence include a method of stretching a base film and a method of laminating an optical anisotropic layer made of a liquid crystalline compound on the base film.
In the polarizing plate of the present invention, an adhesive layer or a pressure-sensitive adhesive layer may be interposed between the antiglare film and the polarizer and between the polarizer and the protective film. Examples of the adhesive or pressure-sensitive adhesive used for the adhesive layer include acrylic, silicone, polyester, polyurethane, polyether, rubber, and the like. Among these, an acrylic type is preferable from the viewpoint of heat resistance and transparency.
The thickness of the polarizing plate of the present invention is not particularly limited, but is usually in the range of 60 μm to 2 mm.

  When the antiglare film or polarizing plate of the present invention is used in a liquid crystal display device, a TN (Twisted Nematic) type, a STN (Super Twisted Nematic) type, a HAN (Hybrid Alignment Nematic) type, a VA (Vertical Alignment), It can be preferably used for any liquid crystal cell such as a transflective type such as an MVA (Multiple Vertical Alignment) type, an IPS (In Plane Switching) type, an OCB (Optical Compensated Bend) type, or the like.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. Parts and% are based on weight unless otherwise specified.
Evaluation in this example is performed by the following method.
(1) Concave and convex height Based on JIS B0601-1994, the ten-point average roughness Rz was measured, and this was regarded as the concave and convex height. Specifically, the surface of the concavo-convex structure is scanned with a length of 2.5 mm in a certain direction via a measuring needle having a diameter of 1 mm with a tip portion made of diamond having a conical shape with an apex angle of 55 degrees, and measurement in that case A change in the vertical direction of the needle was measured to obtain a recorded surface roughness curve, and a ten-point average roughness Rz was obtained from the surface roughness curve with a reference length of 0.8 mm.
(2) Period of unevenness Assuming a reference line on which the unevenness change of the surface roughness curve can be evaluated as a convex portion based on a portion where the unevenness change in the surface roughness curve obtained in the above (1) is minute, the reference The average of the distances between the intersections is calculated based on the intersection of the surface roughness curve passing from the bottom to the top (or from the top to the bottom). The period of unevenness was taken.
(3) Average inclination angle of unevenness Based on the gradient of the portion where the unevenness change in (2) above in the surface roughness curve obtained in the above (1) is small, the average absolute value of the gradient is calculated as the average inclination of the unevenness. It was a corner.
(4) Refractive index Using a high-speed spectroscopic ellipsometer (manufactured by JA Woollam, M-2000U), measured at a measurement wavelength of 245 to 1000 nm, incident angles of 55 degrees, 60 degrees and 65 degrees. The originally calculated value was taken as the refractive index.

(5) Total light transmittance and haze Based on JIS K7136, it measured using the haze meter (the Nippon Denshoku Industries make, haze meter NDH2000). The greater the total light transmittance, the better the haze.
(6) Whiteness Using a spectrophotometer (manufactured by JASCO Corp., spectrophotometer V550), the antiglare film was irradiated with light from the 5 degree direction, and the 45 degree direction shifted by 40 degrees from the opposite 5 degree direction. The amount of scattered light was measured. The measurement was performed in a wavelength range of 350 nm to 700 nm, and a measured value at a wavelength having the highest reflectance was used as a whiteness index. The whiteness is better as the measured value is smaller.
(7) Image sharpness Based on JIS K7105, the image clarity of transmitted light was measured using the image clarity measuring device ICM-1T manufactured by Suga Test Instruments Co., Ltd. The optical comb width was 2.0 mm. The larger the image sharpness, the better.
(8) Anti-glare property An exposed anti-louver fluorescent lamp (8000 cd / m ² ) was projected on the anti-glare film prepared, and the degree of blur of the reflected image was evaluated according to the following criteria.
○: The outline of the fluorescent lamp is not known Δ: The fluorescent lamp is blurred, but the outline can be identified ×: The fluorescent lamp is hardly blurred (9) Viscosity of coating solution According to JIS Z8803, using a single cylindrical rotational viscometer It was measured. The coating solution temperature at the time of measurement was 20 ° C., the cylinder outer diameter was 20 mm, and the cylinder rotation speed was 60 rpm.

(Production Example 1) Preparation of anti-glare layer forming coating solution 1 To 100 parts of methyl isobutyl ketone sol (solid content concentration 40%, manufactured by Catalyst Kasei Co., Ltd.) of antimony pentoxide fine particles (average particle diameter 20 nm), ultraviolet curable urethane Mixing 12 parts of acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd., purple light UV7000B) and 0.5 part of photoinitiator (manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure 184), a UV curable coating solution for forming an antiglare layer 1 was prepared.
The content of the organic solvent in coating solution 1 was 77% by volume, the content of antimony pentoxide fine particles was 11% by volume, the content of surfactant was 0 ppm, and the viscosity of coating solution 1 was 10 mPa · s.

(Production Example 2) Preparation of antiglare layer-forming coating solution 2 To 100 parts of ethanol sol (solid content concentration 40%, manufactured by Catalyst Kasei Co., Ltd.) of antimony pentoxide fine particles (average particle diameter 20 nm), a silicone hard coating agent ( A thermosetting anti-glare layer-forming coating solution 2 was prepared by mixing 40 parts of a solid content concentration of 28%, Nippon Dacro Shamrock Co., Ltd., Solguard NP720).
The content of the organic solvent in the coating liquid 2 was 83% by volume, the content of the antimony pentoxide fine particles was 8% by volume, the content of the surfactant was 0 ppm, and the viscosity of the coating liquid 2 was 7 mPa · s.

(Production Example 3) Preparation of anti-glare layer-forming coating solution 3 To 100 parts of methyl isobutyl ketone sol (solid content concentration 40%, manufactured by Catalyst Kasei Co., Ltd.) of antimony pentoxide fine particles (average particle size 20 nm), ultraviolet curable urethane 12 parts of acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd., Violet UV7000B), 0.5 part of photoinitiator (manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure 184), and fluorosurfactant (manufactured by Neos, Footage 250) 0.2 part was mixed and the coating liquid 3 for anti-glare layer formation of an ultraviolet curable type was prepared.
The coating solution 3 had an organic solvent content of 77% by volume, an antimony pentoxide fine particle content of 11% by volume, a surfactant content of 1775 ppm, and the coating solution 3 had a viscosity of 10 mPa · s.

(Production Example 4) Preparation of anti-glare layer forming coating solution 4 To 100 parts of methyl isobutyl ketone sol (solid content concentration 40%, produced by Catalyst Kasei Co., Ltd.) of antimony pentoxide fine particles (average particle size 20 nm), UV curable urethane Mixing 50 parts of acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd., purple light UV7000B), 2 parts of photoinitiator (manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure 184) and 140 parts of methyl isobutyl ketone, UV curable antiglare layer A forming coating solution 4 was prepared.
The coating solution 4 had an organic solvent content of 83% by volume, an antimony pentoxide fine particle content of 3% by volume, a surfactant content of 0 ppm, and the coating solution 4 had a viscosity of 15 mPa · s.

(Production Example 5) Preparation of coating solution for forming low refractive index layer Tetramethoxysilane oligomer (trade name: methyl silicate 511, manufactured by Colcoat Co.) and methanol were mixed at a weight ratio of 47:75. A liquid A was prepared. Then, water B was prepared by mixing water, aqueous ammonia (ammonia 28 wt%), and methanol in a weight ratio of 60: 1.2: 97.2. And A liquid and B liquid were mixed so that it might become 16:17 by weight ratio, and the coating liquid for low-refractive-index layer formation was obtained.

(Production Example 6) Surface Modification Treatment of Base Film A A high-frequency oscillator (corona generator) is formed on both surfaces of a base film A made of norbornene-based polymer (manufactured by Nippon Zeon Co., Ltd., ZEONOR film ZF14-100, average thickness 100 μm). HV05-2 (manufactured by Tamtec Co., Ltd.), using a wire electrode with a diameter of 1.2 mm, an output voltage of 100%, an output of 250 W, and a corona discharge treatment for 3 seconds under the conditions of an electrode length of 240 mm and a workpiece electrode of 1.5 mm A base film a having a surface tension of 0.072 N / m was obtained.

(Example 1) Manufacture of anti-glare film 1 The coating liquid 1 for forming the anti-glare layer obtained in Production Example 1 is dried on one side of the base film a obtained in Production Example 6 using a wire bar. The coating was applied so that the previous thickness was 50 μm in average thickness, and this coating film was dried at 20 ° C. for 1 minute and at 100 ° C. for 1 minute, followed by ultraviolet irradiation (accumulated light amount: 500 mW / cm ² ). A dazzling film 1 was obtained.
About the obtained anti-glare film 1, the above-mentioned evaluation was performed. The results are shown in Table 1.

(Example 2) Manufacture of anti-glare film 2 As the anti-glare layer-forming coating solution, the anti-glare layer-forming coating solution 2 obtained in Production Example 2 was used, and the coating film was dried at 20 ° C for 1 minute. Anti-glare film 2 was obtained by performing the same operation as in Example 1 except that it was performed at 100 ° C. for 2 minutes and subsequently heated at 80 ° C. for 2 hours.
The obtained antiglare film 2 was evaluated as described above. The results are shown in Table 1.

(Example 3) Production of antiglare film 3 Instead of the base film a, a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., Cosmo Shine 4300, thickness 100 μm, hereinafter referred to as “base film b”) was used. By performing the same operation as in Example 1, an antiglare film 3 was obtained.
The obtained antiglare film 3 was evaluated as described above. The results are shown in Table 1.

(Example 4) Manufacture of antiglare film 4 The antiglare film 1 obtained in Example 1 was put in a rotating chamber of a spin coater, and the low refractive index layer obtained in Production Example 5 was formed on the film 1. The forming coating solution was spin-coated for 10 seconds under the condition of a rotation speed of 700 rpm to form a gel-like thin film. The rotating chamber of the spin coater was previously set in a methanol atmosphere.
Next, this gel-like thin film is immersed for 5 minutes in a curing solution having a composition in which water, 28% aqueous ammonia, and methanol are mixed at a weight ratio of 162: 4: 640. Cured day and night. Further, the gel-like thin film thus cured was immersed in a 10% isopropanol solution of hexamethyldisilazane to perform a hydrophobic treatment.
This hydrophobized gel-like thin film is immersed in isopropanol for cleaning, and then placed in a high-pressure vessel. The inside of the high-pressure vessel is filled with liquefied carbon dioxide, and supercritical under conditions of 80 ° C., 16 MPa, 2 hours. By performing drying, an antiglare film 4 in which a low refractive index layer composed of a silica airgel thin film (low refractive index layer) having a thickness of 100 nm was formed on the antiglare layer of the antiglare film 1 was obtained.
The obtained antiglare film 4 was evaluated as described above. The results are shown in Table 1.

(Example 5) Manufacture of anti-glare film 5 Anti-glare film 5 is obtained by performing the same operation as Example 4 except using anti-glare film 3 instead of anti-glare film 1. It was.
The obtained antiglare film 5 was evaluated as described above. The results are shown in Table 1.

(Comparative example 1) Manufacture of anti-glare film 6 It was the same as that of Example 1 except having used coating liquid 3 for anti-glare layer formation obtained in manufacture example 3 instead of coating liquid 1 for anti-glare layer formation. By performing the operation, an antiglare film 6 was obtained.
The obtained antiglare film 6 was evaluated as described above. The results are shown in Table 1.

(Comparative example 2) Manufacture of anti-glare film 7 By using operation similar to Example 4 except having used anti-glare film 6 obtained by comparative example 1 instead of anti-glare film 1, An antiglare film 7 was obtained.
The obtained antiglare film 7 was evaluated as described above. The results are shown in Table 1.

(Comparative example 3) Manufacture of anti-glare film 8 It is the same as that of Example 1 except having used the coating liquid 4 for anti-glare layer formation obtained by manufacture example 4 instead of the coating liquid 1 for anti-glare layer formation. The antiglare film 8 was obtained by performing this operation.
The obtained antiglare film 8 was evaluated as described above. The results are shown in Table 1.

(Comparative example 4) Manufacture of the anti-glare film 9 The coating liquid 1 for anti-glare layer formation obtained by the manufacture example 1 was dried on the single side | surface of the base film a obtained by manufacture example 6 using the wire bar. The antiglare film 9 was obtained by applying the film so that the subsequent thickness was 150 μm, drying at 100 ° C. for 1 minute, and then irradiating with ultraviolet rays (integrated light amount 500 mW / cm ² ).
The obtained antiglare film 9 was evaluated as described above. The results are shown in Table 1.

From the results in Table 1, the following can be understood. According to the present invention, as shown in Examples, it is excellent in whiteness, image sharpness and antiglare property.
On the other hand, when the surface unevenness height is smaller than 0.1 μm and the uneven period is unknown (Comparative Examples 1 to 3), the antiglare property is inferior. In addition, when the height of the unevenness on the surface is larger than 0.8 μm, the period of the unevenness is larger than 100 μm, and the average inclination angle of the unevenness is larger than 3 degrees (Comparative Example 4), the haze is large and the image clarity is high. Inferior.

Claims (10)

There is an antiglare layer with irregularities on the surface on a substrate film containing a transparent resin,
The antiglare layer is composed of an active energy ray curable resin or a thermosetting resin and fine particles having an average particle diameter of 5 to 100 nm,
The anti-glare film, wherein the unevenness satisfies the following requirements [1] to [3].
[1] The height of the unevenness is 0.1 to 0.8 μm.
[2] The period of unevenness is in the range of 4 to 100 μm.
[3] The average inclination angle of the unevenness is 2.8 degrees or less.   The antiglare film according to claim 1, further comprising a low refractive index layer having a refractive index of 1.25 to 1.37 on the antiglare layer.   The antiglare film according to claim 1 or 2, wherein the antiglare layer has a refractive index of 1.55 or more. The antiglare film according to any one of claims 1 to 3 , wherein the total light transmittance is 90% or more and the haze is 10% or less. The antiglare film according to any one of claims 1 to 4, wherein the antiglare layer does not contain particles having a particle diameter of 500 nm or more. An anti-glare layer is formed on a base film containing a transparent resin by applying a coating solution that satisfies the following requirements [4] to [6] directly or via another layer. The method for producing an antiglare film according to any one of claims 1 to 5;
[4] Content of volatile organic solvent is at least 20% by volume [5] Content of fine particles having an average particle diameter of 5 to 100 nm is at least 5% by volume [6] Content of surfactant The amount is at most 1000ppm The method for producing an antiglare film according to claim 6, wherein the coating solution has a viscosity of 50 mPa · s or less. The anti-glare film manufactured with the manufacturing method of Claim 6 or 7. A polarizing plate comprising the antiglare film according to any one of claims 1 to 5 and 8 on at least one surface of a polarizer. The liquid crystal display device which mounts the anti-glare film of any one of Claims 1-5 and 8 , or the polarizing plate of Claim 9 .