KR20130040840A - Anti-glare film, manufacturing method of same, polarizing plate and image dislay device - Google Patents

Abstract

Provided is an anti-glare film having excellent impact resistance and capable of appropriately suppressing the occurrence of cracks even when applied to a sheet-shaped display. It is an anti-glare film formed on the light transmissive base material and the at least one surface of the said light transmissive base material, and has a diffused layer which has an uneven | corrugated shape on the surface, The said diffused layer is a layered inorganic compound, organic fine particles (A), and (meth) acrylate The coating liquid containing the radiation curable binder containing a monomer as an essential component is formed by applying and drying the coating film on at least one surface of the light-transmitting base material to form a coating film, and curing the coating film. The layered inorganic material in the coating liquid Content of a compound is 2-40 mass parts with respect to 100 mass parts of said radiation curable binders, The said layered inorganic compound is contained in the said diffusion layer in the random orientation state, The anti-glare film characterized by the above-mentioned.

Description

Anti-glare film, manufacturing method of anti-glare film, polarizing plate and image display device {ANTI-GLARE FILM, MANUFACTURING METHOD OF SAME, POLARIZING PLATE AND IMAGE DISLAY DEVICE}

This invention relates to an anti-glare film, the manufacturing method of the said anti-glare film, a polarizing plate, and an image display apparatus.

In image display devices such as a cathode ray tube display device (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescent display (ELD), and an electronic paper, an optical laminate for preventing reflection is usually formed on the outermost surface. It is installed. Such an antireflection optical laminated body suppresses reflection of an image or reduces reflectance by light diffusion or interference.

As one of the optical laminated bodies for reflection prevention, the anti-glare film which provided the anti-glare layer which has an uneven | corrugated shape on the surface of a transparent base material is known. This anti-glare film can prevent the fall of visibility by diffusing external light by the uneven | corrugated shape of a surface.

As a conventional anti-glare film, what coated the resin containing fillers, such as a silicon dioxide (silica), on the surface of a transparent base film and formed the anti-glare layer is known, for example (patent document 1) , 2).

These anti-glare films are a type in which cohesive particles, inorganic and / or organic fillers are added to the resin to form an uneven shape on the surface of the layer, or a type of laminating a film having unevenness on the surface of the layer to transfer the uneven shape. There exist a type which forms an uneven | corrugated shape by phase-separating using the compatibility of the compounds which comprise a binder, such as the above polymer.

In such a conventional anti-glare film, light diffusion and anti-glare action is obtained by the action of the surface shape of the anti-glare layer, and in order to improve the anti-glare property, it is necessary to increase the uneven shape, but the unevenness If this becomes large, the cloud value (haze value) of a coating film rises and a color fading generate | occur | produces, and there existed a problem that transmission transparency fell along with this.

Moreover, the anti-glare film of the conventional type had the problem that what is called a scintillation glittering luster generate | occur | produced on the film surface, and the visibility of a display screen fell.

By the way, the high definition of a liquid crystal display is progressing in recent years, and when a conventional anti-glare film is applied to a high definition liquid crystal display, scintillation generation becomes a more serious problem.

Moreover, as binder resin which comprises an anti-glare layer, what consists of irradiating and hardening an ultraviolet curable binder resin by ultraviolet irradiation is used, but such an anti-glare layer was hard but it was weak to an impact.

In the manufacturing process of a polarizing plate and the bonding process of a polarizing plate and a liquid crystal element, although the curvature radius of an anti-glare film may be made small or a local weight may be added, the anti-glare film provided with the hard but impact-resistant anti-glare layer mentioned above When used, there existed a problem which a crack generate | occur | produced in an anti-glare layer. Furthermore, although a high damage prevention property is calculated | required as a liquid crystal display, since the flaw generate | occur | produces local microcracks generate | occur | produce by weighting, the anti-glare film was required to have crack resistance, ie, impact resistance.

Moreover, the anti-glare film manufactured by the polymerization shrinkage of the ultraviolet curable resin also had the problem that there exist curl.

Patent Document 3 describes an antiglare material obtained by mixing resin beads swelled by 70% or more in a solvent to a binder resin.

Since the anti-glare film provided with the anti-glare layer which uses the resin beads swelled previously by such a solvent can improve the interface adhesiveness of a resin beads and binder resin, since the impact resistance of an anti-glare layer can be improved, It is expected to be applied to high definition displays.

However, the anti-glare film provided with the anti-glare layer which uses the resin beads swelled previously in the solvent, the improvement of the adhesiveness of the interface of the swelled resin beads in a glare-proof layer and binder resin is only an anchor effect which arises in the said interface. Since it was by, there existed room to improve adhesiveness etc. further.

For this reason, the conventional anti-glare film is inadequate as the impact resistance of the whole anti-glare layer, and it was not able to fully prevent the generation of a crack in an anti-glare layer when applied to the polarizing plate manufacturing process etc. mentioned above, or a liquid crystal display.

Japanese Patent Application Laid-open No. Hei 6-18706 Japanese Patent Application Laid-open No. Hei 10-20103 Japanese Patent Application Publication No. 2005-281476

The present invention, in view of the above-described phenomenon, has no scintillation, has an excellent impact resistance, can be appropriately suppressed the generation of cracks and curls, an anti-glare film, a manufacturing method of the anti-glare film, the polarizing plate to which the anti-glare film is applied And an image display device.

The present invention is an anti-glare film formed on a light-transmissive substrate and at least one surface of the light-transmissive substrate, and having a diffused layer having a concave-convex shape on its surface, wherein the diffused layer is a layered inorganic compound, organic fine particles (A) and ( The coating liquid containing the radiation curable binder which contains a meta) acrylate monomer as an essential component is apply | coated on at least one surface of the said transparent base material, and it is made to form a coating film, and hardens the said coating film, The said coating liquid Content of the said layered inorganic compound in is 2-40 mass parts with respect to 100 mass parts of said radiation curable binders, and the said layered inorganic compound is contained in the said diffusion layer in the random orientation state, It is an anti-glare film characterized by the above-mentioned.

In the anti-glare film of the present invention, the layered inorganic compound is preferably talc.

Moreover, it is preferable that the said coating liquid contains the solvent which swells an organic fine particle (A).

In addition, the said coating liquid contains the microparticles | fine-particles (B), The organic microparticles | fine-particles (A) in a diffusion layer have an impregnation layer in which the radiation curable binder was impregnated, and is an average larger than the average particle diameter of the microparticles | fine-particles (B) in the said diffusion layer. It is preferable to have a particle diameter.

It is preferable that the said microparticles | fine-particles (B) are microparticles | fine-particles with higher lipophilic property than organic microparticles | fine-particles (A).

Further, the refractive index of the radiation-curable binder, organic fine particles (A) and the difference in the refractive index and the fine particle (B), when said respective △ _A and △ _B, the △ _A and △ _B is, Equation (1) It is desirable to be satisfied.

[Equation 1]

| △ _A | <| △ _B |

Moreover, this invention is a manufacturing method of the anti-glare film formed on the light transmissive base material and the at least one surface of the said light transmissive base material, and has a diffused layer which has an uneven | corrugated shape on the surface, and is layered on at least one side of the said light transmissive base material A coating liquid containing a radiation curable binder containing an inorganic compound, organic fine particles (A) and a (meth) acrylate monomer as essential components is applied, dried to form a coating film, and the coating film is cured to form the diffusion layer. It is also the manufacturing method of the anti-glare film which has a process and the said layered inorganic compound in the said diffusion layer is contained in the random orientation state.

Moreover, this invention is a polarizing plate provided with a polarizing element, It is also a polarizing plate characterized by including the anti-glare film of this invention on the surface of the said polarizing element.

Moreover, this invention is also an image display apparatus provided with the anti-glare film of this invention or the polarizing plate of this invention in the outermost surface.

Hereinafter, the present invention will be described in detail.

The anti-glare film of this invention is formed on the light transmissive base material and the at least one surface of the said light transmissive base material, and has a diffused layer which has an uneven shape on the surface.

It is preferable that the said light transmissive base material has smoothness and heat resistance, and is excellent in mechanical strength. Specific examples of the material for forming the light-transmitting substrate include polyester (polyethylene terephthalate, polyethylene naphthalate), cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, polyamide, polyimide, polyether sulfone, polysulfone, poly Thermoplastic resins such as propylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, methyl polymethacrylate, polycarbonate or polyurethane, cyclopolyolefin, and the like, and preferably polyester (polyethylene terephthalate) , Polyethylene naphthalate), and cellulose triacetate.

Although it is preferable to use the said light-transmissive base material as the said film body with abundant flexibility, even if it is also possible to use the board | substrate of these thermoplastic resins according to the use form which sclerosis | hardenability is calculated | required, or even if it uses plate-shaped bodies, such as a glass plate, good.

As thickness of the said transparent base material, it is preferable that it is 20-300 micrometers, More preferably, an upper limit is 200 micrometers and a minimum is 30 micrometers. When the light transmissive base material is a plate-shaped body, a thickness exceeding these thicknesses may be used.

In addition, in forming the diffusion layer thereon, the light-transmitting substrate may be coated with an anchor or primer, in addition to physical treatments such as corona discharge treatment, plasma treatment, saponification treatment, and oxidation treatment, in order to improve adhesion. You may carry out beforehand.

In the anti-glare film of the present invention, the diffusion layer includes a coating liquid containing a radiation curable binder containing a layered inorganic compound, organic fine particles (A), and a (meth) acrylate monomer as an essential component, at least of the light-transmissive substrate. It is made by coating and drying on one surface, forming a coating film, and hardening the said coating film. In addition, in this invention, the said diffusion layer shows the hardened coating film layer unless there is particular notice.

It does not specifically limit as said layered inorganic compound, For example, montmorillonite, Weidelite, nontronite, saponite, hectorite, souconite, Stevensight, vermiculite, halosite, kaolinite, endelite, dickite, Talc, pyrophyllite, mica, pearl mica, white mica, gold mica, tetrasilic mica, teniolite, antigorite, chlorite, kutite, nanite and the like. These layered inorganic compounds may be natural or synthetic. Moreover, organic surface treatment may be given to the said layered inorganic compound.

The particle diameter of these layered inorganic compounds is represented by the average particle diameter D50 (median diameter of particle diameter distribution) by a laser diffraction scattering particle size distribution measuring method. Preferable particle diameter range is 0.1-9 micrometers, More preferably, it is 0.3-5 micrometers.

These layered inorganic compounds exist as a plate-shaped particle with a long diameter of about 0.3-5 micrometers when the cross section of an actual anti-glare film is observed by SEM etc. In order to solve the subject of this invention, even if the said particle diameter is too small, an effect cannot be exhibited, and even if too large, the transparency of the whole anti-glare film may be affected. In the particle diameter which can be measured by the result of SEM observation, the more preferable range is plate-shaped particle whose long diameter is about 0.3-2.5 micrometers. In addition, the measurement of a long diameter shall take the average value of ten long diameters of the plate-shaped particle shown by SEM cross section observation.

In the anti-glare film of the present invention, the layered inorganic compound is contained in a random orientation state in the diffusion layer. In addition, random means that in the cross section of the said diffusion layer, in the area | region formed by the direction (10 micrometers) perpendicular | vertical with respect to the thickness direction and the thickness direction of the said diffusion layer, the long diameter or long diameter extension line of a layered inorganic compound does not parallel with each other. It means not in state. At this time, it is preferable that it becomes less than 30%, and it is more preferable that it is less than 20% to become parallel.

By containing the said layered inorganic compound in a random orientation state in a diffusion layer, even if the said diffusion layer is stressed from various directions by deformation | transformation etc., it can prevent that it becomes a starting point of a crack. Moreover, even if irradiated with ultraviolet rays at the time of preparation of the said diffusion layer, the said layered inorganic compound contained in the random orientation state alleviates the damage by ultraviolet irradiation, and also prevents curling to generate in the produced anti-glare film suitably. can do.

This is because the layered inorganic compound has a multi-layer structure in which the layers are bonded by van der Waals attraction, and the bonding force between the layers is weak, so that the layers are displaced when an impact is applied, thereby absorbing the applied shear stress and thus impacting more. It is inferred that it becomes easy to absorb this. In addition, since such a layered inorganic compound is contained in the diffusion layer in a randomly oriented state, it is possible to exhibit the shock absorption effect described above with respect to the stress applied from all directions of the diffusion layer.

That is, the anti-glare film of this invention becomes the thing excellent in impact resistance by containing the said layered inorganic compound in the random orientation state in a diffusion layer.

As such a layered inorganic compound, the inorganic compound containing Si, Al, Mg, and O element is especially preferable, and a talc is suitable as a compound containing such an element. From the physical properties and the crystal structure, talc is easily dispersed and present in the radiation-curable binder of the coating liquid in a vertical and horizontal manner, and the effect of the anti-glare film of the present invention described above can be obtained very appropriately.

For example, when the said diffusion layer contains the microparticles | fine-particles (B) mentioned later, and the said organic microparticles | fine-particles (A) are crosslinked acrylic beads and the said microparticles | fine-particles (B) are polystyrene, when the said layered inorganic compound is talc, the said organic It becomes possible to appropriately control the aggregation of the fine particles (A) and the fine particles (B). As a result, the anti-glare property, color fading prevention property, and scintillation prevention property of the obtained anti-glare film can be achieved at a high level.

This assumes that the talc has a high lipophilic substance. That is, it is assumed that talc having high lipophilicity is adjusting that the organic fine particles (A) (crosslinked acrylic resin) have hydrophilic properties and that the fine particles (B) (polystyrene) have lipophilic properties, and that both fine particles are aggregated. have.

Moreover, as a form of the said talc, it is a layered structure and also includes what looks like acicular or fibrous shape in cross-sectional microscope observation.

Content of the said layered inorganic compound in the said coating liquid is 2-40 mass parts with respect to 100 mass parts of said radiation curable binders. If it is less than 2 mass parts, the impact resistance of the anti-glare film of this invention will become inadequate, and if it exceeds 40 mass parts, the viscosity of the said coating liquid for diffusion layers will become high and it will become impossible to apply | coat a coating, or to control the unevenness | corrugation of a coating film surface. It becomes impossible. In addition, when the content of the layered inorganic compound is out of the above range, if the addition amount is too small, it may not exist properly in a random alignment state in the whole of the diffusion layer, and the aggregation of organic fine particles (A) present together can be controlled appropriately. Since no scintillation occurs and, on the contrary, excessive scintillation, the decrease in contrast cannot be sufficiently prevented. The minimum with preferable content of the said layered inorganic compound is 2 mass parts, and a preferable upper limit is 30 mass parts. By being in this range, a shock resistance effect can be exhibited more, and control of surface asperity becomes easier.

The said organic fine particles (A) are microparticles which mainly form an unevenness | corrugation on the surface of the said diffusion layer, and express surface diffusion function, As a material which comprises such an organic fine particle (A), it is silicone resin, polyester, polystyrene, for example. And acrylic resins, polyacryl-styrene copolymer resins, and olefin resins. Especially, an acrylic resin is used suitably, Furthermore, when manufacturing microparticles | fine-particles, the crosslinked acrylic resin of the type which changed the grade of crosslinking, such as improving a crosslinking density, is preferable. In addition, in this specification, "resin" is the concept also containing resin components, such as a reactive or non-reactive polymer, a monomer, and an oligomer.

Moreover, in order to suppress the scintillation of the anti-glare film of this invention, it is more preferable that the said organic microparticles | fine-particles (A) have refractive index difference (DELTA) _A with respect to the radiation curable binder mentioned later, and give an internal diffusion function to the said diffusion layer. Do.

Specifically, when the microparticles | fine-particles (B) mentioned later are not used, it is preferable that the said refractive index difference (DELTA) _A is 0.1 or less, and when using the microparticles | fine-particles (B) mentioned later, it is preferable that the said refractive index difference (DELTA) _A is 0.04 or less.

As said crosslinked acrylic resin, For example, polymerization initiators, such as persulfate, ethylene glycol dimethacrylate, etc. to acrylic monomers, such as acrylic acid and acrylic acid ester, methacrylic acid and methacrylic acid ester, acrylamide, and acrylonitrile, etc. The homopolymer and copolymer obtained by superposing | polymerizing by suspension polymerization method etc. using the crosslinking agent of is suitable.

As said acryl-type monomer, the crosslinked acrylic resin obtained using methyl methacrylate is especially suitable.

As an average particle diameter in the coating film of the said organic fine particle (A), the thing of the range of 0.5-15.0 micrometers is suitable, for example. In particular, the thing of the range of 1.0-10.0 micrometers is more suitable. When the said average particle diameter is less than 0.5 micrometer, the anti-glare property and scintillation prevention property of the anti-glare film of this invention may become inadequate, and when it exceeds 15.0 micrometer, the outline of the image of the display formed by applying the anti-glare film of this invention The roughness which lacks the denseness of an image, such as blur, may arise, and the image quality may fall.

In addition, the said average particle diameter means the arithmetic mean of the particle diameter if each particle | grain contained in a diffusion layer is a single particle, and if it is an amorphous particle which has a wide particle size distribution, the particle size distribution measurement will It means the particle size of many particles. In addition, the said particle diameter can be measured by the Coulter counter method etc., in the state of only microparticles | fine-particles. However, in addition to this method, as a fine particle measuring method in a cured film, SEM observation of the cross section of the actually produced anti-glare film is performed, and the measurement by the photographing and the surface of an anti-glare film are observed also by a transmission optical microscope. Can be.

In the anti-glare film of the present invention, the organic fine particles (A) preferably have an impregnation layer in which the radiation-curable binder described below is impregnated in the diffusion layer. The fine particles (A), that is, the organic fine particles (A) in the diffusion layer will be referred to as "organic fine particles (A2)".

By having the said impregnation layer, the said organic microparticles | fine-particles (A2) become what was excellent in adhesiveness with the hardened | cured material (henceforth a binder resin hereafter) of the radiation curable binder of a diffusion layer. In addition, since the said impregnation layer in organic fine particles (A2) was formed in the state which the radiation curable binder was mixed, the refractive index of the said impregnation layer is the refractive index between the refractive index of a radiation curable binder and the refractive index of organic fine particles (A). This becomes possible to appropriately reduce the reflection of the transmitted light of the said diffusion layer in the interface of the said organic fine particle A2 (impregnation layer) and binder resin. At the same time, since the impregnation layer has an appropriate layer thickness, and the central portion of the organic fine particles (A2) maintains the refractive index of the initial organic fine particles (A), it is appropriate to prevent scintillation without reducing internal diffusion. It becomes possible.

In addition, as mentioned later, since the said radiation hardening type binder and / or a solvent is a layer formed suitably by swelling an organic fine particle (A), the said organic fine particle (A2) is very rich in flexibility. It becomes fine particles. For this reason, although the surface of the said diffusion layer is formed in the position corresponding to the organic fine particles (A2) in the said diffusion layer, the shape of the said convex part can be made smooth. In addition, this point is demonstrated in detail later.

The impregnation layer is a layer formed by impregnating the radiation curable binder from the outer surface of the organic fine particles (A2) in the diffusion layer toward the center thereof. The impregnated layer is a layer formed by impregnating a low molecular weight component, that is, a monomer, in a radiation curable binder, and a polymer or oligomer, which is a polymer of a radiation curable binder that is a high molecular weight component, is difficult to be impregnated. However, even if it is an oligomer or a polymer, when molecular weight is comparatively small or when a monomer is impregnated, it may be impregnated together.

The said impregnated layer can be discriminated by observing the cross section of the said diffusion layer with SEM etc., for example, and observing the cross section of the organic fine particle (A2) in it. As a detailed method, the diffusion layer is cut in the thickness direction, and SEM observation is performed at a magnification of 3000 times to 50,000 times on a cross section containing at least one organic fine particle (A2), and the radiation curable binder is impregnated with the organic fine particle (A2). In the part where the boundary between the organic fine particles (A2) and the surrounding radiation curable binder is relatively clear, and the radiation curable binder is most impregnated in the organic fine particles (A2), the thickness of the two points is shown by SEM photograph or the like. The measurement is carried out in the same manner, and the total of five organic fine particles (A2) is measured in the same manner, and the average value of the measurement results of ten points is calculated. For example, when it contains other microparticles | fine-particles etc. other than organic microparticles | fine-particles (A2), the thickness of the impregnation layer with respect to the microparticles | fine-particles can be measured similarly to the above.

In addition, the radiation curable binder impregnated in the impregnation layer may be impregnated with all the components constituting it, or may be impregnated with a part of the constituent components.

Moreover, it is preferable that the said impregnation layer is 0.01-1.0 micrometer in average thickness. If it is less than 0.01 micrometer, the effect obtained by forming an impregnation layer mentioned above may not be fully acquired, and when it exceeds 1.0 micrometer, the internal diffusion function of organic microparticles | fine-particles (A2) will not fully be exhibited, and the scintillation prevention effect is fully exhibited. You may not get it. The minimum with more preferable average thickness of the said impregnation layer is 0.1 micrometer, and a more preferable upper limit is 0.8 micrometer. By being in this range, the above-mentioned effect can be exhibited more. In addition, it is preferable that the diameter of the center part in which the impregnation layer of organic fine particles (A2) is not formed is more than the wavelength of light from a viewpoint of ensuring an internal diffusion function and preventing scintillation.

In addition, the average thickness of the said impregnation layer means the average value of the thickness of the impregnation layer in the cross section of the organic fine particle (A) observed by the cross-sectional SEM photograph of an anti-glare film.

Here, although the organic fine particles generally have a crosslinked structure, the degree of swelling by the radiation curable binder and / or the solvent varies depending on the degree of crosslinking. Usually, when the degree of crosslinking is high, the organic fine particles have a low swelling degree. When the degree of crosslinking is low, the degree of swelling is high. For this reason, when the material which comprises the said organic microparticles | fine-particles (A2) is the crosslinked acrylic resin mentioned above, for example, the thickness of the said impregnation layer is controlled to a desired range by adjusting the grade of crosslinking of the said crosslinked acrylic resin suitably. can do. From the viewpoint of antireflection and scintillation prevention, it is more preferable that the organic fine particles (A2) have a higher degree of crosslinking as much as the center portion, and a crosslinking degree in which impregnability does not occur inside the thickness of the impregnated layer of the organic fine particles (A2). It is also most preferred that the degree of crosslinking is lower toward the surface.

Further, when the average particle diameter of the organic fine particles (A2) of the average particle diameter of the organic fine particles (A) and that D _A 1, diffusion layers have called D _A 2, wherein the D _A 1, D _A 2 are the following, equation (2) It is desirable to satisfy.

&Quot; (2) &quot;

0.01 μm <D _A 2-D _A 1 <1.0 μm

In Equation 2, when the "2-D _A D _A 1" is less than 0.01㎛, thinner the thickness of the impregnated layer too, may not be obtained the effect obtained by forming the above-described impregnation layer. When "D _A 2-D _A 1" is 1.0 micrometer or more, an internal diffusion function may not fully be exhibited and the prevention effect of scintillation may not fully be acquired.

The minimum with said more preferable "D _A 2-D _A 1" is 0.1 micrometer, and a more preferable upper limit is 0.5 micrometer. When "D _A 2-D _A1 " exists in this range, the above-mentioned effect can be exhibited more. .

Moreover, it is preferable that the said organic fine particle (A) does not aggregate in the thickness direction (vertical direction) of the said diffusion layer in the said diffusion layer. When the organic fine particles (A) in the diffusion layer are aggregated so as to be laminated in the thickness direction of the diffusion layer, a large convex portion is formed on the surface of the diffusion layer at a position corresponding to the aggregated organic fine particles (A), and the anti-glare film of the present invention Color fading or scintillation may occur. In addition, aggregation of the organic fine particles (A) in the diffusion layer can be appropriately prevented, for example, by containing the above-mentioned layered inorganic compound, and when talc is used as the layered inorganic compound, the organic fine particles (A) Aggregation can be prevented particularly appropriately. In addition, in the case where the aggregation of the organic fine particles (A) is perpendicular to the thickness direction of the diffusion layer (the transverse direction), the above problem is less likely to occur than in the longitudinal direction, but when the aggregated mass becomes too large, the same problem occurs. Therefore, addition of a layered inorganic compound is suitable similarly to the case of longitudinal aggregation.

In the anti-glare film of the present invention, when the organic fine particles (A) have an impregnation layer in the diffusion layer, as such organic fine particles (A), for example, a coating liquid using organic fine particles having a different crosslinking degree in advance is used. It is good to produce an anti-glare film, and to select and use the organic fine particle which conforms to a preferable impregnation degree. The selection of the organic fine particles affects the composition other than the organic fine particles forming the diffusion layer, that is, all resin compounds contained in the matrix binder, various additives, solvents, and the like, and therefore, the preferred degree of crosslinking cannot be determined uniformly. Therefore, the fine particles of various crosslinking degrees are previously added to the matrix composition selected at that time, the diffusion layer is cured and produced once, and the particles are selected by measuring the thickness of the impregnated layer by the method described above.

Moreover, it is although it does not specifically limit as content of the organic fine particle (A) in the said coating liquid, It is preferable that it is 0.5-30 mass parts with respect to 100 mass parts of radiation curable binders mentioned later. If it is less than 0.5 mass part, sufficient uneven | corrugated shape may not be formed in the surface of a diffusion layer, and the anti-glare performance of the anti-glare film of this invention may become inadequate. On the other hand, when it exceeds 30 mass parts, aggregation of organic microparticles | fine-particles (A) will generate | occur | produce easily in the said coating liquid, aggregation in the longitudinal or horizontal direction mentioned above occurs in the said diffusion layer, and a big convex part is formed in the surface of a diffusion layer. This can cause color fading or scintillation. The minimum with more preferable content of the said organic fine particle (A) is 1.0 mass part, and a more preferable upper limit is 20 mass parts. By being in this range, the above-mentioned effect can be ensured more reliably.

It is preferable that the said coating liquid contains further microparticles | fine-particles (B). The fine particles (B) are mainly fine particles for obtaining internal diffusion, and by containing the fine particles (B), it is possible to more appropriately prevent scintillation from occurring in the diffusion layer to be formed. Specifically, the refractive index difference △ _B of the radiation curable binder of fine particles (B) is larger than the refractive index difference △ _A of the above organic fine particles (A) and the radiation-curable binder is preferably 0.2 or less. When it is more than 0.2, excessive interdiffusion stronger, it is apprehended by a fade occurs lead to contrast degradation, is less than the refractive-index difference △ _A, weakened over the interdiffusion, there is a case where the suppression of scintillation becomes insufficient . In order to achieve the above effect, the refractive index difference? _B is more preferably 0.01 or more and 0.1 or less.

As such microparticles | fine-particles (B), it is preferable that they are particle | grains which do not swell by the radiation curable binder and / or the solvent in the said coating liquid. This is because when the fine particles (B) have an impregnation layer, diffusion at the interface between the fine particles (B) and the binder is reduced.

Here, the &quot; non-swollen particles &quot; include a case where the particles are not swelled at all by the radiation curable binder and / or the solvent, and the particles are slightly swollen. In the case of “swelling slightly”, in the diffusion layer, an impregnation layer similar to the organic fine particles (A2) is formed in the fine particles (B), and the average thickness of the impregnated layer is an impregnated layer of the organic fine particles (A). Smaller and less than 0.1 μm.

The determination of whether or not the impregnation layer is formed in the fine particles (B) in the diffusion layer can be performed by observing, for example, a cross section of the fine particles (B) in the diffusion layer with a microscope (SEM or the like).

In addition, in the following description, the microparticles | fine-particles (B) in the said diffusion layer are called "particulates (B2)."

As microparticles | fine-particles (B) which are not swollen by the said radiation-curable binder and / or a solvent, For example, inorganic microparticles | fine-particles, such as a silica microparticle, polystyrene, melamine resin, polyester, an acrylic resin, an olefin resin, these copolymers, etc. Examples of the organic fine particles of the present invention include those having an increased degree of crosslinking, but are preferably organic fine particles with easy control of the refractive index and the particle diameter. These microparticles | fine-particles (B) may be used independently and 2 or more types may be used together.

Among them, the polystyrene fine particles and / or the acrylic-styrene copolymer fine particles have a high refractive index, which is easy to provide a difference in refractive index with the binder (the refractive index of the normal radiation curable binder is about 1.48 to 1.54), and the internal diffusion can be easily obtained. It is used properly. In addition, below, it demonstrates that microparticles | fine-particles (B) are organic particle | grains.

Here, when the organic fine particles by acrylic resin and styrene resin are manufactured by a generally known manufacturing method, all of them use acrylic-styrene copolymer resin as the material, or fine particles of core-shell-type. In the polystyrene microparticles | fine-particles which used the microparticles | fine-particles which consist of acrylic resin for a core, and the polyacryl microparticles | fine-particles which used the microparticles | fine-particles which consist of styrene resin on the contrary are present. In the present specification, the distinction between the acrylic fine particles, the styrene fine particles, and the acrylic-styrene copolymerized fine particles is determined depending on which resin has the closest characteristic of the fine particles. For example, when the refractive index of the fine particles is less than 1.50, the fine particles are acrylic fine particles. If it is 1.50 or more and less than 1.59, it can be called acryl-styrene copolymer microparticles | fine-particles, and if it is 1.59 or more, it can be called styrene microparticles | fine-particles.

Although it does not specifically limit as an average particle diameter of the said microparticles | fine-particles (B), It may be equivalent to the average particle diameter of the organic microparticles | fine-particles (A) mentioned above. However, when the organic fine particles (A) are swollen by the radiation curable binder and / or solvent to form an impregnated layer, the organic fine particles (A) are diffusion layers in order to sufficiently obtain the effect of adding the fine particles (B). It is preferable that an average particle diameter is larger than the microparticles | fine-particles (B) in it, and also the average particle diameter of the said organic microparticles (A) and the microparticles | fine-particles (B), ie, the average particle diameter of the organic microparticles (A) and microparticles (B) of a material state, , it called respectively D _a 1 and D _B 1, and when the average particle diameter of the organic fine particles (A2) and fine particles (B2) of the diffusion layer, called respectively D _a 2 and D _B 2, wherein the D _a 1, D _B 1, It is preferable that D _A 2 and D _B 2 satisfy the following expression (3).

&Quot; (3) &quot;

1.0 μm> D _A 2-D _A 1> D _B 2-D _B 1≥0

By satisfying the above expression (3), the uneven shape of the surface of the diffusion layer is smooth, and the change of the refractive index of the particles due to impregnation of the binder or the like with respect to the particles contributing to the internal diffusion is suppressed, so that the internal diffusion can be easily maintained. In addition, since the reflection of the particle surface is suppressed by the decrease in the refractive index difference with the binder due to impregnation, it is possible to more reliably prevent color fading and scintillation of the anti-glare film of the present invention.

Further, when the diffusion layer of the fine particles (B) and radiation-curing the refractive-index difference △ _B 2 of the binder is large (e.g., △ _B when divalent gateul 0.02 or more refractive-index difference) is, the D _A 2 is a D _B 2 Larger is more preferred. This is because the average particle diameter of the fine particles (B) having a higher internal diffusibility than the organic fine particles (A) is smaller, so that they can be widely distributed in the diffusion layer, and the occurrence of scintillation and roughness in the anti-glare film of the present invention is reduced. Because it becomes.

In the anti-glare film of the present invention, as the fine particles (B), for example, an anti-glare film is produced with a coating liquid using organic fine particles having different crosslinking degrees in advance, and organic fine particles matching the desired degree of impregnation are selected and used. good.

Although it does not specifically limit as content of the microparticles | fine-particles (B) in the said coating liquid, It is preferable that it is 0.5-30 mass parts with respect to 100 mass parts of radiation curable binders mentioned later. If it is less than 0.5 mass part, scintillation will generate | occur | produce easily in the anti-glare film of this invention, and if it exceeds 30 mass parts, the contrast of the image display layer using the anti-glare film of this invention may fall. The minimum with more preferable content of the said microparticles | fine-particles (B) is 1.0 mass part, and a more preferable upper limit is 20 mass parts. By being in this range, the above-mentioned effect can be ensured more reliably.

In the anti-glare film of the present invention, the radiation curable binder includes a (meth) acrylate monomer as an essential component.

As such a radiation-curable binder, it is said that it is suitable to swell the above-mentioned organic microparticles | fine-particles (A), It is preferable that it is transparent, For example, the ionizing radiation curable resin hardened | cured by an ultraviolet-ray or an electron beam is mentioned. In addition, in this specification, "(meth) acrylate" refers to a methacrylate and an acrylate. In addition, in this specification, since a monomer is ionizing radiation hardening and becomes a polymer film, it contains all the molecules which can be a structural unit of the basic structure of this polymer film, and has an unsaturated bond. That is, an oligomer and a prepolymer are also included if an oligomer and a prepolymer are a basic unit of a cured film. In this invention, it is preferable that the said monomer has a molecular weight of 5000 or less.

As said (meth) acrylate monomer, the compound which has 1 or 2 or more unsaturated bonds, such as a compound which has a (meth) acrylate type functional group, is mentioned, for example.

As a compound which has an unsaturated bond of 1, ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methyl styrene, N-vinylpyrrolidone, etc. are mentioned, for example. As a compound which has a 2 or more unsaturated bond, For example, polymethylol propane tri (meth) acrylate, hexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, diethylene glycol di (meth) Acrylate, polyethylene glycol di (meth) acrylate, bisphenol F EO modified di (meth) acrylate, bisphenol A EO modified di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth ) Acrylate, isocyanuric acid EO modified di (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, trimethylolpropane PO modified tri (meth) acrylate, trimethylolpropane EO modified tri (meth) ) Acrylic acid, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol penta (meth) arc Reaction products such as polyfunctional compounds such as latex, dipentaerythritol hexa (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, neopentylglycoldi (meth) acrylate and (meth) acrylate ( For example, poly (meth) acrylate ester of polyhydric alcohol) etc. are mentioned. Moreover, urethane (meth) acrylate and polyester (meth) acrylate which have two or more unsaturated bonds are also mentioned.

Especially, when the hard coat property of the said diffusion layer is considered important, it is preferable that the said radiation curable binder is an acrylate which 50% (mass ratio) or more of all monomer components have a trifunctional or more reactive reactor.

As said ionizing radiation curable resin, in addition to the (meth) acrylate monomer, a relatively low molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin and poly having an unsaturated double bond Butadiene resin, polythiol polyene resin, etc. can also be used as said ionizing radiation curable resin.

When using the said ionizing radiation curable resin as an ultraviolet curable resin, it is preferable that the said coating liquid contains a photoinitiator.

Specific examples of the photopolymerization initiator include acetophenones, benzophenones, Michler's benzoyl benzoate, α-amyl oxime esters, thioxanthones, propiophenones, benzyls, benzoins, and acylphosphine oxides. Can be mentioned. Moreover, it is preferable to mix and use a photosensitizer, and, as the specific example, n-butylamine, triethylamine, poly-n-butylphosphine, etc. are mentioned, for example.

As said photoinitiator, when the said ultraviolet curable resin is resin type which has a radically polymerizable unsaturated group, it is preferable to use acetophenone, benzophenone, thioxanthones, benzoin, benzoin methyl ether, etc. individually or in mixture. Do. In addition, when the said ultraviolet curable resin is resin system which has a cationically polymerizable functional group, as said photoinitiator, aromatic diazonium salt, aromatic sulfonium salt, aromatic iodonium salt, a metallocene compound, benzoin sulfonic acid ester, etc. are single or a mixture. It is preferable to use as.

It is preferable that the addition amount of the said photoinitiator is 0.1-10 mass parts with respect to 100 mass parts of ultraviolet curable resins.

Moreover, the said ionizing radiation curable resin can also be used in combination with solvent-drying resin (resin which becomes a film only if the solvent added in order to adjust solid content at the time of application | coating, such as a thermoplastic resin, will be dried). In this case, the said solvent drying type resin plays an additive role, and mainly uses ionizing radiation hardening type resin. As addition amount of the said solvent drying type resin, it is preferable that it is 40 mass% or less with respect to the total solid of the resin component contained in the said coating liquid.

As the solvent drying type resin, mainly a thermoplastic resin can be mentioned. As the thermoplastic resin, those generally used may be used. By the addition of the above-mentioned solvent-drying type resin, coating film defects on the coated surface can be effectively prevented.

As a specific example of a preferable thermoplastic resin, For example, styrene resin, (meth) acrylic resin, vinyl acetate resin, vinyl ether resin, halogen-containing resin, alicyclic olefin resin, polycarbonate resin, polyester resin And polyamide resins, cellulose derivatives, silicone resins and rubbers or elastomers.

As said thermoplastic resin, it is usual to use resin which is amorphous and is soluble in the organic solvent (especially the common solvent which can melt | dissolve a some polymer and curable compound). In particular, resins having high moldability or film forming property, transparency and weather resistance, such as styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (cellulose esters, etc.) desirable. Especially (meth) acrylic-type resin is especially preferable at the balance of affinity with an acrylate monomer, hardness, and an optical characteristic.

According to a preferred embodiment of the present invention, when the material of the light-transmitting base material is a cellulose resin such as triacetyl cellulose "TAC", as a specific example of the thermoplastic resin, a cellulose resin such as nitrocellulose, acetyl cellulose , Cellulose acetate propionate, ethyl hydroxyethyl cellulose, and the like. By using the said cellulose resin, adhesiveness and transparency with a light transmissive base material and the base uneven | corrugated layer formed as desired can be improved.

The coating liquid may further contain a thermosetting resin. Examples of the thermosetting resins include phenol resins, urea resins, diaryl phthalate resins, melanin resins, guanamine resins, unsaturated polyester resins, polyurethane resins, epoxy resins, amino alkyd resins, melamine-urea co-condensation resins, Silicon resin, polysiloxane resin, etc. are mentioned. When using a thermosetting resin, you may use together a hardening | curing agent, such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, etc. as needed.

When the refractive index and the difference between the refractive index and the organic fine particles (A) and fine particles (B) at room overt film of the present invention, the radiation curable binder, after curing, that each △ _A and △ _B, the △ _A and △ It is preferable that _B satisfy | fills following formula (1).

[Equation 1]

| △ _A | <| △ _B |

By satisfying Equation 1 above, an anti-glare film having excellent uniformity in screen luminance without scintillation having a small internal diffusion of the diffusion angle by the organic fine particles (A) and a large internal diffusion of the diffusion angle by the fine particles (B) is obtained. You can get it.

Moreover, although the arbitrary methods can be mentioned as a measuring method of the refractive index of the said radiation curable binder, organic microparticles | fine-particles (A), and microparticles | fine-particles (B), For example, the Becke method, the minimum polarization method, the polarization analysis, the mode line It can measure by a method, an elliptical polarization reflection method, etc. In addition to measuring the material itself, each method can be similarly used for the coating film itself depending on what kind of microparticles | fine-particles were taken out in the film | membrane of the produced anti-glare film, and a measuring method.

In addition, when the said radiation curable binder contains the said (meth) acrylate and other resin and additive, the refractive index of the said radiation curable binder means the refractive index by all the resin components and additives containing except the fine particle after hardening. Say.

As a preferable measuring method of the said refractive index, if it is a radiation curable binder, the method of cutting out only a binder part from a cured film and measuring by a Becke method is mentioned. In addition, the difference in refractive index between the organic fine particles and the resin component can be measured by measuring the phase difference using a transmission type phase shift laser microscopic interference measurement device PLM-OPT manufactured by NTT Advanced Technology. Therefore, about the refractive index of organic microparticles | fine-particles, the method calculated | required in the form of refractive index + refractive index difference of the resin component calculated | required previously is mentioned.

It is preferable that the said coating liquid contains a solvent further.

It does not specifically limit as said solvent, For example, alcohol (for example, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentane On), esters (e.g. methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (e.g. hexane, cyclohexane), halogenated hydrocarbons (e.g. methylene chloride , Chloroform, carbon tetrachloride, aromatic hydrocarbons (e.g. benzene, toluene, xylene), amides (e.g. dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (e.g. diethyl ether, dioxane , Tetrahydrofuran), ether alcohols (eg, 1-methoxy-2-propanol), and the like.

Although the said radiation-curable binder and the solvent may all select and use the thing of the property which swells the said organic microparticles | fine-particles (A), only one may select and use the thing of the property which swells the said organic microparticles (A).

The formation of the impregnated layer of the organic fine particles (A) can be performed more reliably regardless of the degree of swelling of the radiation curable binder because a solvent having a property of swelling the organic fine particles (A) exists. More preferably, the solvent has a property of swelling the organic fine particles (A). This is inferred that first, the solvent acts on the organic fine particles (A), the organic fine particles (A) swell, and then the low molecular weight component contained in the radiation cured binder is impregnated.

In the anti-glare film of this invention, as a combination of the said radiation curable binder and a solvent, the molecular weight is small and it is easy to be impregnated as a radiation curable binder especially, The said organic fine particle (A) as a (meth) acrylate monomer and a solvent It is preferable to use a combination of ketones and / or esters having a strong property of swelling).

Moreover, the impregnation amount of the low molecular weight component contained in the said radiation curable binder can be controlled by adjusting the swelling degree of organic microparticles | fine-particles (A) by mixing and using the said solvent.

In the case of using a cellulose triacetate (hereinafter also referred to as a TAC substrate) as the light transmissive substrate, the TAC substrate is swelled for interfacial adhesion of the diffusion layer to the light transmissive substrate and prevention of interference fringes occurring at the interface. Moreover, it is preferable to use the solvent which can impregnate the solvent and the low molecular weight component in a resin component in a TAC base material. The solvent used for the swelling of the organic fine particles (A) and the solvent such as those impregnated in the TAC base material may be more common. That is, when the solvent for a TAC base material and the solvent used when preparing the organic fine particles (A) having an impregnation layer in advance are almost the same, the compound balance contained in the coating liquid is in a very stable state and is anti-glare for a long time. Even when processing a film, it can be set as the outstanding coating liquid which can be processed stable.

Preferable examples of such a solvent are methyl isobutyl ketone and the like. Moreover, what is preferable as a low molecular weight component in a resin component is pentaerythritol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. to be.

The said coating liquid can be prepared by mixing each above-mentioned material.

It does not specifically limit as a method of mixing each said material and preparing a coating liquid, For example, a paint shaker, a bead mill, etc. may be used.

The said diffusion layer can be formed by apply | coating and drying the said coating liquid on the at least one surface of the said transparent base material, forming a coating film, and hardening the said coating film.

It does not specifically limit as a coating method of the said coating liquid, For example, the roll coating method, the Meyer Bar coating method, the gravure coating method, the die coating method, etc. are mentioned.

It does not specifically limit as thickness of the coating film which apply | coats and forms the said coating liquid, It determines suitably in consideration of the uneven shape formed on the surface, the material to be used, etc .. If it is 1 micrometer or more, it is excellent in hard coat property, and if it is 20 micrometers or less, since curling hardly arises, it is about 1-20 micrometers preferably. 2-15 micrometers is more preferable, and 2-10 micrometers is more preferable.

The thickness of the said diffusion layer can be measured by SEM observation etc. of the cross section of a diffusion layer. In the case of measurement, 5 or more points | pieces of the thickness from the diffused layer surface position where organic microparticles | fine-particles (A2) do not exist to a light-transmissive base material interface are measured, and the average value is calculated | required.

As described above, the organic fine particles (A2) are appropriately prepared by swelling the organic fine particles (A) with the radiation curable binder and / or solvent to impregnate the radiation curable binder to form an impregnation layer. Preparation of organic microparticles | fine-particles (A2) may be performed in the said coating liquid, and may be performed in the coating film apply | coated and formed in the said light transmissive base material.

A diffusion layer can be formed by hardening the coating film formed on the said transparent base material.

Although it does not specifically limit as a hardening method of the said coating film, It is preferable to carry out by ultraviolet irradiation. When hardening with an ultraviolet-ray, it is preferable to use the ultraviolet-ray of the wavelength range of 190-380 nm. Curing by ultraviolet rays can be performed by, for example, a metal halide lamp, a high pressure mercury lamp, a low pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or the like. As a specific example of an electron beam source, various electron beam accelerators, such as a cokecroft Walton type, a van degraf type, a resonant transformer type, an insulation core transformer type, a straight type, a dynamtron type, and a high frequency type, are mentioned.

In addition, in order to make the said layered inorganic compound into a random orientation state in a diffusion layer, at the time of preparation of the said coating liquid, the layered inorganic compound with few lattice defects electrically neutral, such as talc, is organically produced using ultrasonic waves etc., for example. It is preferable to disperse | distribute uniformly to microparticles | fine-particles (A), a radiation curable binder, a solvent, etc., and to prevent a share from apply | coating when apply | coating a coating liquid with the said light transmissive base material, and to form a coating film by reducing convection at the time of drying. By forming a coating film in this way, it can prevent an orientation of a layered inorganic compound in the said coating film, and a layered inorganic compound is contained in a random orientation state in the diffused layer formed by hardening a coating film after that.

Moreover, it is more preferable to add 0.0002-2.0 mass% of surfactants, such as a fluorine system and a siloxane system, to a coating liquid in order to acquire a random orientation state. It is because the orientation by convection can be prevented by suppressing convection at the time of drying more effectively. If the added amount is less than 0.0002% by mass, the effect of suppressing convection is insufficient. If the amount is more than 2.0% by mass, a decrease in hardness, scratchiness, or the like of the diffusion layer to be formed may occur.

In the anti-glare film of the present invention, the diffusion layer has a concave-convex shape on the surface.

It is preferable that the said diffusion layer has a convex part (henceforth a convex part A) in the position corresponding to at least the organic fine particle A in the said diffusion layer.

In addition, when the organic fine particles (A) are organic fine particles (A2) having the above-mentioned impregnation layer, the height and / or average inclination angle of the convex portion (A) is the following requirements (1), (2) and ( 3) the height and / or height of convex portions (hereinafter also referred to as convex portions C) at positions corresponding to the organic fine particles C on the surface of the diffusion layer C including organic fine particles C satisfying all of them. It is preferred to be lower than the average tilt angle.

Requirement (1): A diffusion layer (C) is formed under the same conditions as the diffusion layer containing the organic fine particles (A) except that organic fine particles (C) are used instead of the organic fine particles (A).

Requirement (2): The organic fine particles (C) in the diffusion layer (C) have the same average particle diameter as the organic fine particles (A) in the diffusion layer.

Requirement (3): The organic fine particles (C) do not have an impregnation layer formed in the diffusion layer (C).

The convex part A of the position corresponding to the said organic fine particle A2 is low in height and / or average inclination angle compared with the said convex part C, and is smooth shape. The anti-glare film of this invention which has a diffused layer with such a convex part A can be made excellent in anti-glare property and color fading prevention property.

This is considered to be because the said organic fine particle (A2) is a fine particle with very flexibility compared with the said organic fine particle (C). That is, when the coating film is cured, the radiation curable binder causes curing shrinkage, but the curing shrinkage of the surface where the organic fine particles (A2) are located is compared with the curing shrinkage of the surface where the organic fine particles (A2) are not located. Since the amount of radiation curable binders is small, it becomes small. In addition, since the said organic microparticles | fine-particles (A2) are microparticles | fine-particles which are very flexible, organic microparticles | fine-particles (A2) deform | transform by hardening shrinkage of the said coating film. As a result, the height and / or average inclination angle of the convex part A formed are low and smooth compared with the said convex part C formed in the surface of the diffusion layer C containing harder organic microparticles C. It is assumed to be losing.

In addition, the height of the said convex part means that the surface of an anti-glare film is observed by AFM, and the difference of the convex part between the convex part which exists in the surface, and the other convex part adjacent to the said convex part is the height of the convex part n It is measured as (n is 1-10). And the arbitrary heights of ten convex parts calculated | required in this way were calculated | required.

Since the anti-glare film of this invention contains the layered inorganic compound mentioned above in a random orientation state in a diffusion layer, even if the said diffusion layer is stressed from various directions by deformation | transformation etc., it can prevent that it becomes a starting point of a crack. have. In addition, even when irradiated with ultraviolet rays during the preparation of the diffusion layer, the layered inorganic compound contained in a random orientation state can alleviate damage caused by ultraviolet irradiation and also prevent curling from occurring in the produced anti-glare film. Can be.

That is, the anti-glare film of this invention becomes the thing excellent in impact resistance by containing the said layered inorganic compound in the random orientation state in a diffusion layer.

Moreover, since the anti-glare film of this invention provided with the diffusion layer containing the said organic microparticles | fine-particles (A2) is hard to tolerate distortion by the stress from various directions by a deformation | transformation etc., the organic fine particles (A2) and radiation in the said diffusion layer The adhesiveness with the hardened | cured material of a curable binder becomes very excellent. In the anti-glare film of the present invention, in the mandrel test, cracking does not occur in a condition in which the diameter of the mandrel is 10 mm, more preferably in a condition of 8 mm, even more preferably in a condition of 6 mm. It is preferable.

In addition, since the above-mentioned impregnation layer is formed in the organic fine particle (A2) in the said diffusion layer, and the said impregnation layer was formed in the state which the radiation curable binder was mixed, the said diffusion layer is the organic fine particle (A) in the said diffusion layer (impregnation Layer) and the difference in refractive index between the cured product of the radiation curable binder can be reduced, and the reflection at the interface can be appropriately reduced. At the same time, the impregnated layer has an appropriate layer thickness, and since the center of the organic fine particles (A) maintains the refractive index of the initial organic fine particles (A), it can exhibit appropriate internal diffusibility and appropriately scintillation. It can prevent.

Moreover, the height of the convex part formed in the position corresponding to the organic fine particle (A) of the said diffusion layer is low, and can be made into a gentle shape.

Therefore, the anti-glare property, color fading prevention property, and scintillation prevention property of the anti-glare film of this invention can be achieved at a high level.

It is preferable that haze value is 30% or less of the anti-glare film of this invention. When it exceeds 30%, color fading may occur in the anti-glare film of this invention, and the image quality of an image display apparatus may fall.

In addition, the said haze value is the value measured using the haze meter HR100 (Murakami Color Research Institute, product, brand name) based on the haze (dodo) prescribed | regulated to JIS-K7136. In addition, all the haze value in this invention was the value measured by this method.

The method of manufacturing such an anti-glare film of this invention is also one of this invention.

That is, the manufacturing method of the anti-glare film of this invention is a manufacturing method of the anti-glare film formed on the light transmissive base material and the at least one surface of the said light transmissive base material, and has a diffused layer which has an uneven shape on the surface, The said light transmissive property On at least one side of the substrate, a coating liquid containing a radiation curable binder containing a layered inorganic compound, organic fine particles (A) and a (meth) acrylate monomer as essential components is applied and dried to form a coating film. It has a process of hardening and forming the said diffusion layer, The said layered inorganic compound in the said diffusion layer is contained in the random orientation state, It is characterized by the above-mentioned.

In the manufacturing method of the anti-glare film of this invention, the material etc. which comprise the said coating liquid are the same as what was demonstrated by the anti-glare film of this invention mentioned above.

Moreover, the process similar to the method demonstrated by the anti-glare film of this invention mentioned above also the process of forming the said diffusion layer is mentioned.

Moreover, it is a polarizing plate provided with a polarizing element, The polarizing plate characterized by including the anti-glare film of this invention by bonding a light transmissive base material to the surface of the said polarizing element is also one of this invention.

It does not specifically limit as said polarizing element, For example, the polyvinyl alcohol film, the polyvinyl formal film, the polyvinyl acetal film, the ethylene-vinyl acetate copolymer type saponification film etc. which were dyed and extended with iodine etc. can be used. . In the lamination process of the said polarizing element and the anti-glare film of this invention, it is preferable to perform a saponification process to a light transmissive base material. By the saponification treatment, adhesiveness is improved and an antistatic effect can be obtained.

This invention is also an image display apparatus provided with the said anti-glare film or the said polarizing plate in the outermost surface. Examples of the image display apparatus include LCD, PDP, FED, ELD (organic EL, inorganic EL), CRT, touch panel, electronic paper, and the like.

The LCD includes a transmissive display and a light source device for irradiating the transmissive display from the back side. When the image display apparatus of this invention is LCD, the anti-glare film of this invention or the polarizing plate of this invention is formed in the surface of this transmissive display body.

When this invention is a liquid crystal display device which has the said anti-glare film, the light source of a light source device is irradiated from the lower side of an anti-glare film. In the STN type liquid crystal display device, a retardation plate may be inserted between the liquid crystal display element and the polarizing plate. An adhesive bond layer may be provided between each layer of this liquid crystal display device as needed.

The said PDP is provided with the back glass substrate by which the discharge gas was enclosed and arrange | positioned facing the surface glass substrate and the said surface glass substrate. When the image display apparatus of this invention is a PDP, it may also provide the anti-glare film mentioned above in the surface of the said surface glass substrate, or its front plate (glass substrate or film substrate).

As other image display apparatuses, zinc sulfide which emits light when a voltage is applied, and diamines: a light-emitting body is deposited on a glass substrate, and an ELD apparatus or electric signal which displays by controlling the voltage applied to the substrate is converted to light and visually An image display device such as a CRT that generates a visible image may be used. In this case, the above-mentioned anti-glare film is provided on the outermost surface of each display device as described above or the surface of the front plate.

In any case, the anti-glare film of this invention can be used for display displays, such as a television and a computer. In particular, it can use suitably for the surface of high definition image displays, such as a liquid crystal panel, PDP, ELD, a touch panel, and an electronic paper.

Since the anti-glare film of the present invention contains the layered inorganic compound in a random orientation state in the diffusion layer, even when the diffusion layer is stressed from various directions due to deformation or the like, it is possible to prevent the crack from originating. Moreover, even if irradiated with ultraviolet rays at the time of preparation of the said diffusion layer, the said layered inorganic compound contained in the random orientation state alleviates the damage by ultraviolet irradiation, and also prevents curling to generate in the produced anti-glare film suitably. can do.

1 is a cross-sectional SEM photograph of the diffusion layer of the anti-glare film obtained in Example 1. FIG.

Although the content of this invention is demonstrated by the following Example, the content of this invention is limited to these Examples and is not interpreted.

(First embodiment)

First, triacetyl cellulose (manufactured by Fuji Film Co., Ltd., thickness of 80 μm) was prepared as a light transmissive substrate.

Next, as a radiation curable binder, a mixture (mass ratio; PETA / DPHA / SAP = 82/7 /) of pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA) and cellulose acetate propionate (SAP) 11) (refractive index 1.51), using 1-hydroxycyclohexyl-phenyl-ketone: Igacure 184 (manufactured by BASF Corporation) as a photopolymerization initiator (3 parts by mass based on 100 parts by mass of the binder solids), thereby organic fine particles As (A), low-crosslinked acrylic particles (refractive index 1.49, average particle diameter 5.0 μm) were polystyrene particles (refractive index 1.59, average particle diameter 3.5 μm) as 6.0 parts by mass and fine particles (B) with respect to 100 parts by mass of the radiation curable binder. The talc particle (refractive index 1.57, average particle diameter 0.8 micrometer) was contained 8.0 mass part with respect to 100 mass parts of radiation curable binders with respect to 100 mass parts of radiation curable binders as a 5.0 mass part and layered inorganic compound. In addition, 0.003 mass parts of non-reactive fluorochemical surfactant was added with respect to 100 mass parts of radiation curable binders as surfactant. Thus, the coating liquid which mix | blended 190 mass parts of mixtures of a toluene and methyl isobutyl ketone (mass ratio 8: 2) with respect to 100 mass parts of radiation curable binders was prepared as a solvent.

By adjusting the obtained coating liquid so that the coating liquid supply amount and the coating amount correspond (coating liquid supply amount / coating amount = 1.0), the share is removed and applied to the light transmissive substrate by gravure method, and the drying air at 70 ° C. at a flow rate of 1.2 m / s. Was passed through, and dried for 1 minute to form a coating film.

Thereafter, the coating film was irradiated with ultraviolet rays (200 mJ / cm 2 under a nitrogen atmosphere) to cure the radiation curable binder to form a diffusion layer to prepare an anti-glare film. In addition, the film thickness of the diffusion layer was 6.0 micrometers.

(Examples 2 to 11, Comparative Examples 1 to 5)

Except having made the kind of organic microparticles | fine-particles (A) and microparticles | fine-particles (B) added to the coating liquid, the kind and content of a layered inorganic compound, presence or absence of surfactant, and ratio of (coating liquid supply amount / coating amount) to Table 1, An anti-glare film was produced in the same manner as in Example 1.

[Table 1]

The detail of the symbol shown by the organic fine particle (A), microparticles | fine-particles (B), a layered inorganic compound, and a solvent which were shown in Table 1 is as follows. In addition, in Table 1, content of a layered inorganic compound shows content (mass part) with respect to 100 mass parts of radiation curable binders.

(Organic Fine Particles A)

A: High crosslinked acrylic particle (refractive index 1.49, average particle diameter 5.0 micrometers, the Soken Kagaku company make)

B: low-cost bridge | crosslinking acrylic particle (refractive index 1.49, average particle diameter 5.0 micrometers, the Soken Kagaku company make)

(Particulates B)

C: Polystyrene particle (refractive index 1.59, average particle diameter 3.5 micrometers, the Soken Kagaku company make)

(Layered Inorganic Compound)

M: Talc (refractive index 1.57, average particle diameter 0.8 micrometer, a nano talc Nihon Talc company)

N: bentonite (refractive index 1.52, average particle diameter 0.1-0.5 micrometer, the Knipia F Kunimine Kogyo make)

In addition, the particle diameter of a layered inorganic compound is average particle diameter D50 by a laser diffraction scattering type particle size distribution measuring method.

(solvent)

Y: mixture of toluene and methyl isobutyl ketone (mass ratio 8: 2)

Z: mixture of toluene and isopropyl alcohol (mass ratio 7: 3)

The following evaluation was performed about the anti-glare film obtained by the Example and the comparative example.

The results are shown in Table 2.

(Random Orientation State of Layered Inorganic Compounds)

The anti-glare film obtained in Examples and Comparative Examples was cut in the thickness direction, and SEM observation of the region where the thickness of the diffusion layer and the vertical direction (10 μm) were formed with respect to the thickness direction in the cross section of the diffusion layer was applied to the layered inorganic compound. The orientation state was evaluated. 1 is a cross-sectional SEM photograph of the diffusion layer of the anti-glare film according to Example 1. FIG.

(Double-circle): In the layered inorganic compound observed, the presence of the long or long diameter extension line parallel to the long or long diameter extension line of another layered inorganic compound is less than 20%.

(Circle): In the layered inorganic compound observed, the presence or the extension line of the long diameter or the long diameter of the layered inorganic compound parallels the long diameter or the long diameter extension line of another layered inorganic compound is 20% or more and less than 30%.

X: 30% or more of the observed layered inorganic compound whose long diameter or long diameter extension line is parallel with the long diameter or long diameter extension line of another layered inorganic compound.

(Hayes)

Haze value of the anti-glare film obtained by the Example and the comparative example was measured using the haze meter HR100 (made by Murakamishikisai Kijutsu Genkyu Sho Co., Ltd.) according to the haze (dominance) prescribed | regulated to JIS-K7136.

(Mandrel test)

According to JIS K5600, the mandrel test of the anti-glare film obtained by the Example and comparative example in mandrel phi 6mm, phi 8mm, and phi 10mm was performed, and it evaluated according to the following criteria.

(Double-circle): A crack does not arise at 6 mm.

(Circle): A crack does not generate in φ8 mm.

(Triangle | delta): A crack does not generate in φ10 mm.

X: A crack occurs at φ10 mm.

(Contrast)

The anti-glare film obtained by the Example and the comparative example was bonded to the black acrylic board using the transparent adhesive film for optical films, and 20 subjects showed the surface state of an anti-glare film from various directions on the condition of 1000 Lx clear room. Sensory evaluation was performed. It was judged whether or not the glossy black could be reproduced and evaluated according to the following criteria.

◎: 15 or more people answered good

○: 10 to 14 people answered good

△: 5 to 9 people who answered good

X: 4 or less people answered good

(Scintillation)

The polarizing plate of the outermost surface of the liquid crystal television "KDL-40X2500" by Sony Corporation was peeled off, and the polarizing plate without surface coating was attached.

Subsequently, the anti-glare film obtained by the Example and the comparative example on it has a transparent adhesive film for optical films (91% or more of total light transmittance, 0.3% or less of haze, 20-50 micrometers of film thicknesses) so that a diffusion surface side may become an outermost surface. A product, for example, MHM series: Nichei Kako Corp. make, etc.).

The liquid crystal television was installed indoors under an illuminance of about 1,000 Lx, a white screen was displayed, and 20 subjects evaluated visual sensory evaluation from various angles up, down, left, and right from a place spaced 1.5 to 2.0 m away from the liquid crystal television. Done. It was judged whether scintillation was seen on the white screen display, and the evaluation was made according to the following criteria.

◎: 15 or more people answered good

○: 10 to 14 people answered good

△: 5 to 9 people who answered good

X: 4 or less people answered good

(Thickness of Impregnated Layer of Organic Fine Particles (A))

The anti-glare film was cut | disconnected in the thickness direction, and the thickness of the impregnation layer formed in the cross section of five organic microparticles | fine-particles (A) was measured 10 pieces in total, respectively, and the average value was computed by SEM observation of the cross section of a diffusion layer.

[Table 2]

As shown in Table 2, in the anti-glare film according to the examples, SEM cross sections were observed, and the layered inorganic compound was contained in the diffusion layer in a random orientation state, and in the cross section, the talc particles had a long diameter of about 0.5 to 1.5 m. It was observed as a linear material of degree, and bentonite particles were observed as a linear material of about 0.1 to 0.8 mu m, and each evaluation of haze value, mandrel test, contrast, and scintillation was good.

 Since the anti-glare film which concerns on the comparative example 1 does not contain a layered inorganic compound in a diffusion layer, it was inferior to each evaluation of a mandrel test, contrast, and scintillation. The anti-glare film according to Comparative Example 2 has a small content of the layered inorganic compound added at the time of preparing the coating liquid, is poor in each evaluation of the mandrel test, contrast, and scintillation, and the layered inorganic compound is also in an unaligned orientation state. There existed a lot. In addition, the anti-glare film which concerns on the comparative example 3 had many content of the layered inorganic compound added at the time of preparation of coating liquid, and was not able to apply | coat uniformly to a transparent base material. In addition, in the anti-glare film which concerns on Comparative Examples 4 and 5, most of the layered inorganic compounds in a diffusion layer did not become in a random orientation state, and each evaluation of a mandrel test, contrast, and scintillation was inferior.

Industrial availability

The anti-glare film of the present invention is a display such as a cathode ray tube display device (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescent display (ELD), a touch panel, an electronic paper, and the like, in particular, high definition. It can be used suitably for display.

Claims (9)

As an anti-glare film formed on a light-transmissive base material and at least one surface of the said light-transmissive base material, and having a diffused layer which has an uneven shape on the surface,
The said diffusion layer apply | coats and dries the coating liquid containing the radiation curable binder which contains a layered inorganic compound, organic microparticles | fine-particles (A), and a (meth) acrylate monomer as an essential component on at least one surface of the said transparent base material, and coats (V) is formed and the coating film is cured.
Content of the said layered inorganic compound in the said coating liquid is 2-40 mass parts with respect to 100 mass parts of said radiation curable binders,
The said layered inorganic compound is contained in the said diffusion layer in the random orientation state, The anti-glare film characterized by the above-mentioned. The method of claim 1,
The layered inorganic compound is talc. Antiglare film. The method according to claim 1 or 2,
A coating liquid contains the solvent which swells an organic fine particle (A), The anti-glare film characterized by the above-mentioned. 4. The method according to any one of claims 1 to 3,
The coating liquid further contains fine particles (B), and the organic fine particles (A) in the diffusion layer have an impregnation layer impregnated with a radiation curable binder, and have an average particle diameter larger than the average particle diameter of the fine particles (B) in the diffusion layer. Anti-glare film, characterized in that. 5. The method of claim 4,
Microparticles | fine-particles (B) are microparticles | fine-particles which are higher in lipophilic property than organic microparticles | fine-particles (A), The anti-glare film characterized by the above-mentioned. The method according to claim 4 or 5,
When the refractive index of the radiation-curable binder and, the difference in refractive index of the organic fine particles (A) and fine particles (B), when said respective △ _A and △ _B, the △ _A and △ _B is to, by satisfying the expression (1) Anti-glare film characterized by the above-mentioned.
[Equation 1]
| △ _A | <| △ _B | As a manufacturing method of the anti-glare film formed on the at least one surface of a transparent base material and the said transparent base material, and having a diffused layer which has an uneven shape on the surface,
A coating liquid containing a radiation curable binder containing a layered inorganic compound, organic fine particles (A) and a (meth) acrylate monomer as essential components is applied on at least one surface of the light-transmissive substrate, dried to form a coating film, Curing the coating film to form the diffusion layer,
The said layered inorganic compound in the said diffusion layer is contained in the random orientation state, The manufacturing method of the anti-glare film characterized by the above-mentioned. A polarizing plate comprising a polarizing element,
The anti-glare film of any one of Claims 1-6 is provided on the surface of the said polarizing element, The polarizing plate characterized by the above-mentioned. The anti-glare film of any one of Claims 1-6 or the polarizing plate of Claim 8 is provided in the outermost surface, The image display apparatus characterized by the above-mentioned.

Images