KR20090119968A - Process for producing antiglare antireflection film, antiglare antireflection film, polarizer, and display - Google Patents

Abstract

A process for producing an antiglare antireflection film which is free from bright-spot defects and has excellent marring resistance. It has a low reflectance and is hence less apt to reflect or glitter. It is excellent in visibility including clearness. Also provided are: an antiglare antireflection film; and a polarizer and a display both employing the film. The process, which is for producing an antiglare antireflection film comprising a transparent support and, formed thereon, an antiglare layer and at least one layer having a low refractive index, is characterized by: applying an antiglare-layer-forming coating composition in a solution state to a transparent support to thereby form an antiglare layer which has a smooth surface shape in this state just after application and has the function of changing in surface shape from the smooth one to a rugged shape which brings about antiglare properties when treated with at least one means selected among drying, heating, light irradiation, microwave irradiation, and electron beam irradiation; applying a coating fluid for forming at least one low-refractive-index layer to the antiglare layer whose surface shape is in the smooth state; and then changing that surface shape of the antiglare layer into a rugged shape by that means after the coating fluid application for low-refractive-index layer formation.

Description

Production method of anti-glare anti-reflection film, anti-glare anti-reflection film, polarizing plate and display device {PROCESS FOR PRODUCING ANTIGLARE ANTIREFLECTION FILM, ANTIGLARE ANTIREFLECTION FILM, POLARIZER, AND DISPLAY}

The present invention relates to a method for producing an antiglare antireflection film, an antiglare antireflection film, a polarizing plate using the same, and a display device.

In a flat panel display display device, in order to improve visibility, an anti-glare antireflection film is required.

As an anti-glare antireflection film, it is known to form an optical antireflection layer, such as a low refractive index layer of 50-200 nm film thickness, on the surface of the anti-glare film whose surface is an uneven structure.

Although the antireflection layer is formed on the surface of the anti-glare film having a concave-convex structure by the deposition method, the sputtering method, or the atmospheric plasma film formation, it is possible to form the antireflection layer having a uniform film thickness, but it is inferior in mass productivity and very expensive. It is not suitable for producing a uniform large area anti-glare antireflection film. On the other hand, the manufacturing method of the anti-glare antireflection film by the coating method suitable for manufacturing the anti-glare antireflection film of the outstanding mass productivity, which can be manufactured by moderate cost, and a uniform large area is proposed.

However, forming an optical antireflection layer such as a low refractive index layer having a uniform film thickness on the uneven surface according to the coating method causes a bright point defect due to uneven coating due to unevenness, weak adhesion and poor scratch resistance. Is not uniform, the reflectance is not lowered than the theoretical value, and there is a problem that color unevenness occurs due to variation in the film thickness.

As a means of solving these problems, Patent Document 1 describes a manufacturing method for lowering the coated surface of the coating film of the surface irregularities film. In this specification, it is described that the purpose of suppressing the bright point by the elasticity in the convex part of an antireflection film is described. However, in the above production method, the effect is insufficient.

Further, in Patent Documents 2 and 3 below, adhesion of the hard coat layer and the antireflection layer can be improved by performing a surface treatment of the hard coat layer before applying the antireflection layer on the hard coat layer, thereby hard coat. Examples of the surface treatment of the layer include a high frequency discharge plasma method, an electron beam method, an ion beam method, an evaporation method, a sputtering method, an alkali treatment method, an acid treatment method, a corona treatment method, and an atmospheric glow discharge plasma method. have. However, when forming an optical antireflection layer, such as a low refractive index layer, on the anti-glare film which surface-treated, the effect was inadequate.

Patent Literature 4 below describes a technique of embossing an antireflection film having an optical antireflection layer such as a low refractive index layer on a smooth clear hard coat surface. However, the embossing is a mechanical means, and the breakage of the antireflection layer of the thin film occurs at 50 to 200 nm, such as cracking, which is insufficient to solve the above problem.

Patent Document 1: Japanese Patent Laid-Open No. 2004-24967

Patent Document 2: Japanese Patent Laid-Open No. 2002-317152

Patent Document 3: Japanese Patent Laid-Open No. 2003-292831

Patent Document 4: Japanese Patent Laid-Open No. 2004-29240

This invention is made | formed in view of the said subject, Comprising: It is the objective of the anti-glare antireflection film which has no bright spot defect, is excellent in abrasion resistance, has low reflectance, little reflection and glitter, and is excellent in visibility, such as sharpness. It is providing the manufacturing method, and also providing the anti-glare antireflection film manufactured by the said manufacturing method, the polarizing plate using the anti-glare antireflection film, and a display apparatus.

The said subject of this invention is achieved by the following structures.

1.A method for producing an antiglare antireflection film having an antiglare layer and at least one low refractive index layer on a transparent support,

The anti-glare layer is applied to the transparent support in a solution state of the anti-glare layer-forming coating composition, the surface of the anti-glare layer in the applied state is smooth, by one or more means of drying, heating, light irradiation, microwave irradiation or electron beam irradiation The smooth surface shape has a function of changing into an uneven shape showing anti-glare property,

In the state where the surface of the antiglare layer is smooth, one or more layers of the low refractive index layer are applied on the smooth surface, and after the application of the low refractive index layer,

The said antiglare layer surface shape is changed to an uneven | corrugated shape by the said means, The manufacturing method of the anti-glare antireflection film characterized by the above-mentioned.

2. After the said anti-glare layer forming coating composition is apply | coated on a transparent support body in a solution state, the said means of the extent that surface shape does not change into uneven | corrugated shape is performed, and after that, application of a low refractive index layer is performed, The said 1 characterized by the above-mentioned. The manufacturing method of the anti-glare antireflection film of description.

3. The anti-glare layer-forming coating composition is formed of a coating composition containing a first resin and a second resin, wherein the first resin and the second resin are resins having functional groups that react with each other, and the surface tension of the first resin. Anti-glare antireflection according to 1 or 2, wherein the difference? Of the surface tension between the second resin and the second resin is two or more resins of 2 dyne / cm or more, the means is light irradiation, and the light irradiation is ultraviolet irradiation. Method for producing a film.

4. Said low refractive index layer contains component hardened | cured by ultraviolet irradiation, The manufacturing method of anti-glare antireflection film in any one of said 1-3 characterized by the above-mentioned.

5. Arithmetic mean roughness Ra of the surface of anti-glare layer before apply | coating the said low refractive index layer is 100 nm or less, The manufacturing method of the anti-glare antireflection film in any one of said 1-4 characterized by the above-mentioned.

6. A high refractive index layer containing conductive metal oxide fine particles is formed between said anti-glare layer and low refractive index layer, The manufacturing method of the anti-glare antireflection film in any one of said 1-5 characterized by the above-mentioned.

7. Said transparent support body contains cellulose ester resin, The manufacturing method of anti-glare antireflection film in any one of said 1-6 characterized by the above-mentioned.

8. Said transparent support body contains cellulose ester resin and acrylic resin, The manufacturing method of anti-glare antireflection film in any one of said 1-6 characterized by the above-mentioned.

9. Said transparent support body contains cellulose ester resin, acrylic resin, and acrylic particle, The manufacturing method of anti-glare antireflection film in any one of said 1-6 characterized by the above-mentioned.

10. The anti-glare antireflection film manufactured by the manufacturing method of the anti-glare antireflection film in any one of said 1-9.

11. The anti-glare antireflection film described in 10 above was formed on at least one side thereof.

12. The display device characterized by using the anti-glare antireflection film according to 10 or the polarizing plate according to 11 above.

Effect of the Invention

According to the present invention, there is provided a method for producing an anti-glare antireflection film having no bright spot defects, excellent scratch resistance, low reflectance, little reflection and glare, and excellent visibility such as sharpness. The produced anti-glare antireflection film, the polarizing plate using the anti-glare antireflection film, and a display apparatus can be provided.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, although the best form for implementing this invention is demonstrated in detail, this invention is not limited to these.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining about the said subject, in the manufacturing method of the anti-glare antireflection film which has an anti-glare layer and at least 1 low refractive index layer on a transparent support body,

The anti-glare layer is applied to the anti-glare layer-forming coating composition on a transparent support in a solution state, the anti-glare layer surface shape of the applied state is smooth, at least one of drying, heating, light irradiation, microwave irradiation or electron beam irradiation Has a function of changing the smooth surface shape into an uneven shape showing anti-glare property,

In the state where the antiglare layer surface shape is smooth, at least one low refractive index layer is applied on the smooth surface, and after the low refractive index layer is applied,

By the above means, the antiglare antireflection film is produced by changing the surface of the antiglare layer into a concave-convex shape, and there is no bright spot defect, excellent scratch resistance, low reflectance, low reflection and no glare. It was discovered that the anti-glare antireflection film excellent in visibility, such as sharpness, is obtained.

Although the size of the unevenness | corrugation which generate | occur | produces anti-glare property is generally about 40 nm-20 micrometers in the arithmetic mean roughness Ra of the outermost surface, on the other hand, the thickness of an antireflection layer is 50-200 nm, and it is a thin film compared with uneven | corrugated size. Conventionally, when the antireflection layer is applied as a liquid on the unevenness of the substrate having anti-glare property, the coating liquid causes leveling and does not follow fine unevenness, resulting in non-uniform thickness of the antireflection layer, resulting in bright spot defects, Scratches, glitters, etc. were often generated.

The present invention is applied to at least one low refractive index layer on a smooth surface in a state where the antiglare layer surface shape is smooth, and after application of the low refractive index layer, the surface of the antiglare layer is dried, heated, irradiated with light, Since at least one of microwave irradiation or electron beam irradiation is used to change the irregular shape, it is possible to form a thin film of a very uniform low refractive index layer. Therefore, there are few defects, such as bright spot defects, scratch resistance, reflection, or glitter resulting from the non-uniformity of the low refractive index layer, and a low reflection and clear image are obtained.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

[Antiglare layer]

The anti-glare antireflection film of this invention forms the hard-coat layer which has anti-glare property, and the anti-glare layer mentioned in this invention between a transparent support body and a low refractive index layer or antireflection layers, such as a high refractive index layer and a low refractive index layer.

(Anti-glare)

The anti-glare property is to reduce the visibility of the reflective image by applying the contour of the image reflected on the surface so that the reflection of the reflective image is not bothered when using an image display device such as a liquid crystal display, an organic EL display, or a plasma display. By providing an appropriate unevenness | corrugation on a surface, this property can be made.

As a method of forming such an unevenness | corrugation, processing to a transparent support body, formation of an anti-glare layer, processing to the antireflection film after forming an antireflection layer, etc. can be selected, but the direct processing to an antireflection film is an uneven | corrugated shape Since the convex structure of R may tear the antireflective layer or deform the antireflective layer to impair the antireflective effect, it is preferable to process or form an antiglare layer on the transparent support, from the viewpoint of antiglare effect and production efficiency. Formation of an antiglare layer is particularly preferable.

The concave-convex shape referred to in the present invention includes a structure selected from a staff pyramid, an inclined cone, a pyramid, a square pyramid, a wedge (wedge), a convex polygon, a hemispherical shape, and a structure having those partial shapes. In addition, the hemispherical shape does not necessarily need to be a spherical shape, but may be an ellipsoid shape or a more convex curved shape. Moreover, the prism shape, the lenticular lens shape, and the Fresnel lens shape in which the uneven | corrugated ridgeline extended linearly are mentioned. The inclined surface that extends from the ridge line to the curve may be a planar shape, a curved shape, or a combination of both.

The anti-glare layer of this invention apply | coats an anti-glare layer forming coating composition on a transparent support body in a solution state, The surface shape of the anti-glare layer in the apply | coated state is smooth, and at least 1 of drying, heating, light irradiation, microwave irradiation, or electron beam irradiation is carried out. Although it is a characteristic that the smooth surface shape has a function to change into the uneven | corrugated shape which shows anti-glare property by a means, the said means of the extent that a surface shape does not change to uneven | corrugated shape is performed, and after that, the application of a low refractive index layer is performed It is also preferable.

That is, after apply | coating the said anti-glare layer forming coating composition on a transparent support body in a solution state, it is preferable to solidify and gelatinize an anti-glare layer so that surface shape may not change into an uneven | corrugated shape, and apply | coat a low refractive index layer after that.

When this applies an antireflection layer such as a low refractive index layer immediately after applying the antiglare layer-forming coating composition in a solution state, or at the same time, both of them are in a solution state, and thus they differ in viscosity and surface tension. This is because the components of each layer need to be kept separate without mixing.

Therefore, when applying antireflection layers, such as a low refractive index layer, in order to avoid mixing with the anti-glare layer component of a smooth surface, the anti-glare layer of a smooth surface is dry, heating, light irradiation, microwave irradiation, or electron beam irradiation in the range which does not uneven | corrugate. It is preferable to solidify and gelatinize by.

The degree of solidification and gelation is preferably such that the interfaces between the antiglare layer and the antireflection layer are slightly mixed with each other for adhesion between the layers.

Specifically, in the case of drying, it is preferable to adjust the appropriate time so as to be in a desired curing state in the range of 40 ° C to 70 ° C and in the case of ultraviolet irradiation, in the range of 5mJ / cm 2 to 100mJ / cm 2. As drying time and an ultraviolet irradiation time, it is preferable that it is the range of 1 second-10 minutes, It is more preferable that it is 30 second-7 minutes, It is still more preferable that it is 1 minute-5 minutes.

The state where the surface of the antiglare layer before applying the low refractive index layer is smooth means that the arithmetic mean roughness Ra specified in JIS B 0601: 2001 on the surface of the antiglare layer is 100 nm or less. In obtaining the effect of this invention, 100 nm or less is preferable, It is more preferable that it is 70 nm or less, It is especially preferable that it is 60 nm or less.

It is preferable that it is 40-500 nm, and, as for arithmetic mean roughness Ra prescribed | regulated by JIS B 0601: 2001 of the outermost surface of the anti-glare antireflection film after forming a low refractive index layer, it is more preferable that it is 80-400 nm. . When Ra is less than 40 nm, the effect of anti-glare is weak, and when it exceeds 500 nm, the impression is too rough with the naked eye. Arithmetic mean roughness Ra is preferably measured by an optical coherence surface roughness measuring instrument, and can be measured using, for example, an optical interference surface roughness meter RST / PLUS (manufactured by WYKO).

(Antiglare Layer Forming Coating Composition)

The anti-glare layer-forming coating composition of the present invention is a resin layer having an uneven shape on its surface by at least one of drying, heating, light irradiation, microwave irradiation, or electron beam irradiation of the coating film obtained by coating on a transparent support. Composition to be formed. As a technique which can be applied to this anti-glare layer forming coating composition, a plurality of resins which are easy to phase-separate from each other, such as epoxy resins and acrylate resins, for example, in which fluorine groups have been introduced, described in JP-A-2000-267086 are used. 1st resin and 2nd resin which have the same kind of skeletal structure as described in Unexamined-Japanese-Patent No. 2004-69753, and have different functional groups which mutually react, and crosslinked resin particle are mixed, and apply | coated and dried Later, as the resin in which the first resin and the second resin are phase separated, the difference in the SP value of the first resin and the second resin is at least one, and the same skeleton structure in the first resin and the second resin is a (meth) acrylic resin, The technique which uses resin which is skeletal structure of a polyester resin, a polyether resin, or a urethane resin, Furthermore, the 1st resin and 2nd resin of Unexamined-Japanese-Patent No. 2006-3647 are mutually reacting. As a resin having a functional group, the first resin is a difference Δγ of the surface tension and surface tension of the second resin 2dyne / ㎝ least a resin of at least two of, it discloses a technique such as curing by drying, to heat.

In the present invention, the antiglare layer-forming coating composition contains a first resin and a second resin, and the resin is a resin having functional groups that react with each other, and the difference Δγ between the surface tension of the first resin and the surface tension of the second resin. The first resin having a value of 2 dyne / cm or more is selected from the group consisting of acrylic resins, olefin resins, polyether resins, polyester resins, epoxy resins, polycarbonate resins, polyamide resins and polyurethane resins. And a second resin is a melamine resin (b-1), the first resin is a carboxyl group-containing acrylic resin (a-2), and a second resin. It is preferable that resin contains some resin which is an epoxy resin (b-2).

After apply | coating a coating composition, the said 1st resin and a 2nd resin localize a 1st resin and a 2nd resin based on the difference of each surface tension at the time of hardening, and form an uneven | corrugated shape. I think that.

In the present invention, the first resin and the second resin use a resin having a functional group reacting with each other. The resin layer hardens by reacting the functional group which 1st resin has, and the functional group which 2nd resin has. As a combination of such functional groups, for example, the imino group of a hydroxyl group and melamine resin, the combination of a methylol group, an alkoxide group, the combination of a hydroxyl group and a (block) isocyanate group, the combination of a hydroxyl group and an acid (anhydride) group, a hydroxyl group and a silanol group Combinations of different functional groups, such as combinations of epoxy groups and carboxyl groups, combinations of epoxy groups and amino groups, combinations of epoxy groups and hydroxyl groups, combinations of epoxy groups and silanol groups, combinations of oxazoline groups and carboxyl groups, combinations of active methylene groups and acryloyl groups Can be mentioned. The term "functional groups reacting with each other" as used herein means that the reaction does not proceed only by mixing only the first resin and the second resin, or the reaction rate is slow. As a catalyst which can be used here, a photoinitiator, a radical initiator, an acid-base catalyst, a metal catalyst, etc. are mentioned, for example.

As 1st resin and 2nd resin used by this invention, resin whose difference (DELTA) (gamma) of the surface tension of a 1st resin and the surface tension of a 2nd resin is 2 dyne / cm or more is used. It is preferable that it is 3 dyne / cm, and, as for this (DELTA) (gamma), it is more preferable that it is 4 dyne / cm. It is preferable that it is 30 dyne / cm, and, as for the upper limit of (DELTA) gamma, it is more preferable that it is 20 dyne / cm. When Δγ is smaller than 2 dyne / cm, a sufficient uneven shape formed based on the difference in surface tension is not obtained. Moreover, when (DELTA) (gamma) exceeds 30 dyne / cm, it will be impossible to maintain the uniform state in a solution state, and there exists a possibility that stability may fall. In addition, when apply | coating the solution (for example, the isolate | separated solution etc.) in which a uniform state is not maintained, the resin layer obtained becomes a two-layered structure, and an uneven | corrugated layer cannot be obtained. After using the resin whose difference (DELTA) (gamma) of the surface tension of a 1st resin and the surface tension of a 2nd resin is the said range, after apply | coating a coating composition to a base material, a 1st resin and a 2nd resin are based on the difference of surface tension. It is reclaimed and the resin layer which has random unevenness | corrugation on the surface is obtained.

Surface tension is a force to minimize the area of the interface of a different phase. The first resin and the second resin used in the present invention have a very high viscosity compared to liquids such as water. Therefore, it is very difficult to measure the surface tension of resin as it is by the ring method (ring-ring method, 吊環 method). Therefore, in this invention, the surface tension of a 1st resin and a 2nd resin measures the surface tension of a specific solvent, Next, prepares the solution which melt | dissolved resin in the solvent at the density | concentration of 40 mass% of resin solid content, and measured surface tension. The difference Δγ between the surface tension of the first resin and the surface tension of the second resin is measured by calculating a value obtained by subtracting the surface tension value of the solvent from the obtained measured value. In such a method, the measurement of the surface tension can be measured using, for example, Dinometha Co., Ltd., made by Big Molycrot International.

It is considered that the first resin and the second resin used in the present invention are localized due to different surface tensions, for example, in a drying step or light irradiation. And in the hardening process, since the surface tension of each resin differs, it is thought that cohesion force also changes, and the resin layer which has an unevenness | corrugation on the surface is formed by this. Since the unevenness | corrugation of the coating composition for anti-glare layer formation of this invention is formed based on the surface tension of resin used in this way, the surface shape of the uneven | corrugated resin layer of this invention does not have a special regularity, and has a random uneven | corrugated shape do. For this reason, there exists an advantage that the problem, such as the generation | occurrence | production of the moire by the interference effect of light which may arise in the unevenness which has regularity, does not arise.

In the present invention, as described above, the first resin and the second resin react with each other. Therefore, in the anti-glare layer obtained by the present invention, these first resins and the second resins are not in a completely separated state in terms of components, but in a non-uniform state in which the amount of each resin constituent is biased.

As a specific embodiment of the antiglare layer-forming coating composition of the present invention, the first resin is a group consisting of an acrylic resin, an olefin resin, a polyether resin, a polyester resin, an epoxy resin, a polycarbonate resin, a polyamide resin, and a polyurethane resin. Resin (a-1) which contains 1 or more types chosen from as a skeleton, and also has a hydroxyl group can be used, and a melamine resin (b-1) can be used as a 2nd resin. In this case, the hydroxyl group which 1st resin (a-1) has, the imino group, methylol group, and / or alkoxide group which 2nd resin (b-1) has reacted, bridge | crosslinking is formed, and it hardens.

As resin (a-1) which can be used as 1st resin, (meth) acrylic resin, for example, resin which superposed | polymerized or copolymerized the (meth) acryl monomer, and has a ethylenically unsaturated double bond different from a (meth) acryl monomer Resin copolymerized with monomers; Olefin resins such as polyethylene, polypropylene, ethylene propylene copolymers, ethylene vinyl acetate copolymers, ionomers, ethylene vinyl alcohol copolymers, ethylene vinyl chloride copolymers, and the like; Polyether resins, which are resins containing ether linkages in the molecular chain, for example polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like; Polyester resins, which are resins containing ester linkages in the molecular chain, for example unsaturated polyester resins, alkyd resins, polyethylene terephthalates and the like; Polyurethane resins, which are resins comprising urethane bonds in the molecular chain; Etc. can be mentioned. Moreover, the copolymer of these resin can also be used. And in this invention, resin which has a hydroxyl group further is used as these resin. The hydroxyl value (OH value) of the first resin (a-1) is preferably 10 to 400. When OH value of resin (a-1) is less than 10, hardening becomes inadequate, and there exists a possibility that the fall of film-forming property (resin layer formation ability) and the chemical-resistance of the resin layer obtained may arise. On the other hand, when OH value exceeds 400, there exists a possibility that the fall of the flexibility of the resin layer obtained, and the fall of mechanical strength by the crosslinking density becoming too high may occur.

In the said resin (a-1), resin which has a hydroxyl group as (meth) acrylic resin or olefin resin is used especially preferable in this invention. It is because these resin can form the resin layer which has a more favorable uneven surface by the combination which uses melamine resin (b-1) as a 2nd resin.

Melamine resin (b-1) which can be used as a 2nd resin in this form generally has resin which has various surface tension values. In this invention, the melamine resin (b-1) which uses the difference of the surface tension of said resin (a-1) to 2 or more is used. And as melamine resin (b-1), it is more preferable to use resin which has surface tension lower than the surface tension of said 1st resin (a-1). Melamine resin (b-1) can use a commercially available thing, For example, it can purchase from Japan Cytec Industries, Ltd., Dainippon Inks Corporation, Mitsui Toatsu Corporation, etc.

As another specific embodiment of the coating composition for anti-glare layer formation of this invention, a carboxyl group-containing acrylic resin (a-2) can be used as a 1st resin, and an epoxy resin (b-2) can be used as a 2nd resin. have. In this case, the carboxyl group which the 1st resin (a-2) has, and the epoxy group which the 2nd resin (b-2) has reacted, bridge | crosslinking is formed, and it hardens.

As the resin (a-2) which can be used as the first resin, an acrylic resin, for example, a polymer obtained by polymerizing or copolymerizing a (meth) acryl monomer or a monomer having an ethylenically unsaturated double bond different from the (meth) acryl monomer As acrylic resins, such as copolymerized resin, resin which has a carboxyl group on the frame | skeleton is mentioned. This carboxyl group of 1st resin (a-2) and the epoxy group which 2nd resin (b-2) has react, bridge | crosslinking is formed, and it hardens. It is preferable that it is 20-400, and, as for the acid value of 1st resin (a-2), it is more preferable that it is 50-250. When the acid value of 1st resin (a-2) is less than 20, hardening becomes inadequate and there exists a possibility that the fall of film-forming property (resin layer formation ability) and the chemical-resistance of the resin layer obtained may arise. On the other hand, when an acid value exceeds 400, there exists a possibility that the fall of the flexibility of the resin layer obtained, and the fall of mechanical strength by a crosslinking density becoming too high may occur.

As the epoxy resin (b-2) which can be used as the second resin in this embodiment, any epoxy resin generally used can be used. As an epoxy resin (b-2) which can be used, a bisphenol-type epoxy resin etc. are mentioned, for example. Moreover, an epoxy group containing polymer can also be used as an epoxy resin (b-2). As used herein, "epoxy resin" refers to a resin having an epoxy group, and the structure of the skeleton of the resin is not limited.

As an epoxy group containing polymer which can be used as an epoxy resin (b-2), For example, 30-50 mass% of radically polymerizable monomers having an epoxy group, 10-50 mass% of radically polymerizable monomers having a hydroxyl group, and other radicals The copolymer obtained by copolymerizing the monomer composition containing the residual amount of a polymerizable monomer is mentioned.

As a radically polymerizable monomer which has an epoxy group, glycidyl (meth) acrylic acid, 3,4 epoxy cyclohexanyl methyl methacrylate, etc. are mentioned, for example. As a radically polymerizable monomer which has a hydroxyl group, tetrahydroxy butyl acrylate, Fraxel FM-1 (made by Daicel Corporation), etc. are mentioned, for example, 2-hydroxyethyl (meth) acrylate. As other radically polymerizable monomer, styrene, (alpha) -methylstyrene, acrylic esters (for example, methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid n, i and t-butyl, 2 ethylhexyl acrylate, lauryl acrylate Methacrylic acid esters (e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid-n, i and t-butyl, 2-ethylhexyl methacrylate, methacrylic) Acid lauryl etc.), acrylamide, methacrylamide, etc. are mentioned. These may be used independently and may use 2 or more types together. An epoxy group containing polymer can be obtained by polymerizing these monomers in presence of radical polymerization initiators, such as t-butylperoxy-2-ethylhexanoate and dimethyl 2,2'- azobis isobutyrate.

Of these epoxy resins (b-2), those having a difference in surface tension of the epoxy resin (b-2) and the surface tension of the first resin (a-2) are two or more. And it is preferable to use what has surface tension lower than the surface tension of said 1st resin (a-2).

Moreover, it is preferable to use the epoxy resin of epoxy equivalent 100-5000, and, as for the epoxy resin (b-2) used as 2nd resin, it is more preferable to use the epoxy resin of epoxy equivalent 160-2000.

In any of the above embodiments, the weight average molecular weight of the first resin is preferably 500 to 500,000, particularly 1000 to 100000. When the weight average molecular weight of 1st resin exceeds 500000, polymer viscosity will become high and workability etc. may worsen. On the other hand, when weight average molecular weight is less than 500, there exists a possibility that localization may become inadequate. A weight average molecular weight can be calculated | required by the gel permeation chromatography method (GPC method).

Moreover, it is preferable that the weight average molecular weights of 2nd resin are 200-500000, especially 400-100000. When the weight average molecular weight of 2nd resin exceeds 500000, a polymer viscosity may become high and workability etc. may deteriorate. On the other hand, when weight average molecular weight is less than 200, there exists a possibility that localization may become inadequate. This weight average molecular weight can also be calculated | required by the gel permeation chromatography method (GPC method).

The antiglare layer forming coating composition of the present invention is prepared by mixing the first resin and the second resin in a solvent. The solvent used is not specifically limited, It selects suitably in consideration of the material of the part used as a basis of application | coating, binder resin, a coating method, etc. As a specific example of a solvent, Aromatic solvents, such as toluene and xylene; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol diethyl ether; Ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, methyl lactate, ethyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol mono Ester solvents such as methyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate and γ-butyrolactone; Amide solvents such as dimethylformaldehyde, dimethylacetamide and N-methylpyrrolidone; Carbonate solvents such as propylene carbonate, dimethyl carbonate and diethyl carbonate; aliphatic solvents such as n-butane, n-hexane and cyclohexane; alcohol solvents such as i-propanol, i-butanol, propylene glycol monomethyl ether, propylene glycol monopropyl ether and dipropylene glycol monomethyl ether. Of these solvents, ester solvents, ether solvents and alcohol solvents are preferable, and can be used alone or in combination of two or more thereof. The antiglare layer-forming coating composition of the present invention may be an aqueous coating composition. Therefore, an aqueous solvent may be used.

The 1st resin and 2nd resin are represented by solid content mass ratio (1st resin / 2nd resin) of resin, It is preferable to be used in the range of 10/90-90/10, It is used in the range of 70/30-40/60. It is more preferable. By using it in such a ratio, the resin layer which has a favorable uneven | corrugated surface, and is excellent in physical strength etc. can be obtained.

Moreover, in the coating composition for antiglare layer formation of this invention, various additives can be added as needed. Examples of such additives include rheology control agents such as waxes such as polyethylene wax and polypropylene wax, surface conditioners (leveling agents) such as acetylene diols, coupling agents, plasticizers, and dispersants.

It is preferable to contain the following silicone type surfactant or a polyoxyether compound as a specific leveling agent. As the silicone-based surfactant, polyether-modified silicone is preferable, and specifically, BYK-UV3500, BYK-UV3510, BYK-333, BYK-331, BYK-337 (manufactured by Bigchem Japan Corporation), TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (product made by GE Toshiba Silicone), KF-351, KF-351A, KF-352, KF-353, KF-354, KF-355, KF-615, KF-618, KF-945, KF-6004 Polyether modified silicone oil; Shin-Etsu Chemical Co., Ltd.) etc. are mentioned, It is not limited to these.

Moreover, in a polyoxyether compound, Preferably, it is a polyoxyethylene oleyl ether compound and is a compound generally represented by general formula ((alpha)).

<General Formula (α)>

C ₁₈ H ₃₅ -O (C ₂ H ₄ O) nH

In formula, n represents 2-40.

The average added number n of ethylene oxide with respect to an oleyl part is 2-40, Preferably it is 2-10, More preferably, it is 2-9, More preferably, it is 2-8. Moreover, the compound of general formula ((alpha)) is obtained by making ethylene oxide and oleyl alcohol react.

Specific products include emulsion 404 (polyoxyethylene (4) oleyl ether), emulsion 408 (polyoxyethylene (8) oleyl ether), emulsion 409P (polyoxyethylene (9) oleyl ether), emulsion Mulgen 420 (polyoxyethylene (13) oleyl ether), emulgen 430 (polyoxyethylene (30) oleyl ether) or more, manufactured by Kao Corporation, Japanese fat and oil agent NOFABLEEAO-9905 (polyoxyethylene (5) oleyl ether), etc. Can be mentioned.

In addition, () represents the number of n. A nonionic polyoxyether compound may use individually or in combination of 2 or more types.

These improve applicability, and it is preferable to add these components in 0.01-3 mass% with respect to the solid content component in a coating liquid.

In addition, you may contain a fluororesin. As the fluororesin, a polymer obtained by copolymerizing siloxane (including polysiloxane) and / or organosiloxane (including organopolysiloxane) by grafting or the like can be preferably used. Specifically, ZX-022H, ZX-007C, ZX-049, ZX-047-D, etc. made by Fuji Chemical Industry Co., Ltd. are mentioned. You may use these compounds in mixture.

The refractive index of 1st resin and 2nd resin in the coating composition for anti-glare layer formation of this invention may be same or different, As a preferable refractive index difference, it is 0.00-0.50, More preferably, it is 0.01-0.30.

The anti-glare layer-forming coating composition of the present invention may contain another particle component as necessary. Such a particle component can be prepared by the well-known method described in Unexamined-Japanese-Patent No. 2000-241807. As inorganic fine particles which can be used for the antiglare layer, silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, indium tin oxide (ITO), antimony dope tin oxide (ATO), zinc antimonate, zirconium oxide, magnesium oxide And calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. In particular, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.

Moreover, as organic particle | grains, polymethyl methacrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicone resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, It can be added to ultraviolet curable resin compositions, such as melamine resin powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or poly ethylene fluoride resin powder. Particularly preferably, crosslinked polystyrene particles (e.g., SX-130H, SX-200H, SX-350H) and polymethyl methacrylate particles (e.g., Soken Chemicals MX150, MX300) are mentioned. Can be.

In addition, you may use a fluorine-containing acrylic resin particle. As fluorine-containing acrylic resin particle, it is particle | grains formed from the monomer or polymer of fluorine-containing acrylic acid ester or methacrylic acid ester, for example. Specific examples of the fluorine-containing acrylic ester or methacrylic ester include 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2, 3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (purple Urooctyl) ethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2 -Hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylic Late, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 3- (perfluoro-3-methyl Butyl-2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl-2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl-2- Hydroxypropyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, trifluoroethylmetha Methacrylate, tetrafluoropropyl methacrylate, perfluorooctylethyl acrylate, 2- (perfluorobutyl) ethyl-α-fluoroacrylate, and among the fluorine-containing acrylic resin particles, Particles consisting of (perfluorobutyl) ethyl-α-fluoroacrylate, fluorine-containing polymethylmethacrylate particles, fluorine-containing To the methacrylic acid in the presence of a crosslinking agent, a vinyl monomer copolymerizable with which particles are preferred, and more preferably a fluorine-containing polymethyl methacrylate particles.

As a vinyl monomer copolymerizable with fluorine-containing (meth) acrylic acid, what is necessary is just to have a vinyl group, specifically, acrylic acid alkyl esters, such as methacrylic acid alkyl esters, such as methyl methacrylate and butyl methacrylate, methyl acrylate, ethyl acrylate, and the like. Styrene, such as styrene and (alpha) -methylstyrene, etc. are mentioned, These can be used individually or in mixture. Although it does not specifically limit as a crosslinking agent used at the time of a polymerization reaction, It is preferable to use what has two or more unsaturated groups, for example, bifunctional dimethacrylates, such as ethylene glycol dimethacrylate and polyethyleneglycol dimethacrylate Acrylate, trimethylolpropane trimethacrylate, divinylbenzene, and the like.

The polymerization reaction for producing the fluorine-containing polymethyl methacrylate particles may be either random copolymerization or block copolymerization. Specifically, the method of Unexamined-Japanese-Patent No. 2000-169658, etc. are mentioned, for example.

As a commercial item, the commercial item, such as Negami Industries Co., Ltd.:MF-0043, is mentioned. In addition, although these fluorine-containing acrylic resin particle may be used independently, you may use it in combination of 2 or more type. In addition, the state of these fluorine-containing acrylic resin particles may be added in any state, such as powder or an emulsion.

Moreover, you may use the fluorine-containing crosslinked particle of Paragraph 0028 of Unexamined-Japanese-Patent No. 2004-83707-0055. Moreover, it is preferable that the refractive index of particle | grains is 1.45-1.70, More preferably, it is 1.45-1.65. In addition, the refractive index of the particles is measured by turbidity by measuring the turbidity by uniformly dispersing the particles in a solvent in which the refractive index is changed by changing the mixing ratio of two kinds of solvents having different refractive indices, and measuring the refractive index of the solvent when the turbidity becomes extremely small by using an Abbe refractometer. It can be measured.

As for content of the said particle | grain, 1 mass part-30 mass parts are preferable with respect to 100 mass parts of said resins.

As average particle diameter of these fine particle powders, 0.01-5 micrometers is preferable, and 0.1-5.0 micrometers, Furthermore, it is especially preferable that it is 0.1-4.0 micrometers. Moreover, it is preferable to contain 2 or more types of microparticles | fine-particles from which a particle diameter differs.

However, the coating composition for anti-glare layer formation of this invention can provide an uneven | corrugated shape on the surface, without using such particle | grains, and essentially does not require the use of a particle component. In addition, even when such a particle component is used, the usage-amount is considerably less compared with the conventional thing. For example, when a particle component is contained in the quantity exceeding 10 mass% with respect to the solid content mass of the coating composition for anti-glare layer formation, there exists a possibility that the disadvantage resulting from containing a particle component, such as formation of an aggregate, may arise. .

In addition, the anti-glare layer-forming coating composition of the present invention may contain a conjugated conductive polymer and an ionic compound. The? conjugated conductive polymer can be used as long as the main chain is an organic polymer composed of a? conjugated system. For example, polythiophene, polypyrrole, polyaniline, polyphenylene, polyacetylene, polyphenylene vinylene, polyacene, polythiophene vinylene, and these copolymers are mentioned. From the point of ease of polymerization and stability, polythiophenes, polyanilines, and polyacetylenes are preferable.

As the ionic compound, an imidazole ryumgye, pyridinium-based, alicyclic amine-based, aliphatic amine-based cations and BF ₄ aliphatic phosphonium ^{nyumgye-inorganic} ion-based, such ^{_{as, CF 3 SO 2 - -,}} PF 6, (CF ^{_{3 SO 2) 2 N -,}} CF 3 CO 2 - , and the like compounds containing anions such as fluorine.

Said conjugated conductive polymer and ionic compound are preferably at least 0.01% by mass and less than 50% by mass as the solid content concentration of the coating composition for antiglare layer formation because they are stably present in the composition.

In addition, you may add the said conjugated conductive polymer and an ionic compound to the high refractive index layer mentioned later.

As an advantage of the anti-glare layer obtained without using a particle component in this invention, the washing | cleaning property of a manufacturing apparatus improves, since the aggregation of a particle component does not generate | occur | produce, etc. are mentioned. .

An anti-glare layer can be formed using the anti-glare layer forming coating composition of the present invention, the coating step of applying the anti-glare layer forming coating composition to a transparent support, the drying step of drying the obtained coating film, and, if necessary, curing the dried coating film. It forms by the method containing the hardening process to make.

The method of apply | coating the coating composition for anti-glare layer formation to a base material is not specifically limited, It selects suitably according to the situation of the coating composition to be used, and a coating process. For example, various coating methods, such as spin coating, roll coating, screen printing, spray coating, gravure coating, and inkjet method, can be adopted.

As above-mentioned, after apply | coating the said anti-glare layer forming coating composition on a transparent support body in a solution state, solidifying and gelling an anti-glare layer so that surface shape does not change into uneven | corrugated shape, and apply | coating a low refractive index layer after that desirable.

The coating film of the anti-glare layer and the low refractive index layer thus obtained is cured so as to localize the first resin and the second resin by using a means selected from the group of drying, heating, light irradiation, microwave irradiation or electron beam irradiation.

It is preferable that drying is performed by reduced pressure drying. By drying under reduced pressure, it is thought that the solvent contained in a coating composition can be removed, and localization of a 1st resin and a 2nd resin can be carried out favorably. And in order to localize 1st resin and 2nd resin favorably, it is also preferable to dry under reduced pressure, without heating. If too much heat is applied in this drying step, the first resin and the second resin may be leveled, and localization may not be satisfactory.

The uneven | corrugated resin layer is formed by hardening the coating film localized by 1st resin and 2nd resin by a drying process again. As a hardening method, it is performed by means selected from the group of drying, heating, light irradiation, microwave irradiation, or electron beam irradiation, It is especially preferable to use light irradiation, such as heating or an ultraviolet-ray.

When heat-hardening, 50-300 degreeC of heating temperature is preferable, Preferably it is 60-250 degreeC, More preferably, it is 80-150 degreeC. Although heating time changes with heating temperature, the range of 3 to 300 minutes is suitable. Or after winding up once, it can also perform an aging process for about 1 to 20 days at the temperature of about 50-100 degreeC.

Moreover, when hardening by light irradiation, it is preferable that it is 10mJ / cm <2> -10J / cm <2>, and, as for the exposure amount of irradiation light, it is more preferable that it is 50mJ / cm <2> -1J / cm <2>. Although it does not specifically limit as a wavelength range of the light irradiated here, The light which has a wavelength of an ultraviolet range is used preferably. The ultraviolet ray can be used without limitation as long as it is a light source that generates ultraviolet rays. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. ArF excimer lasers, KrF excimer lasers, excimer lamps or synchrotron radiation can also be used. In addition, the temperature distribution of the coating film in a light irradiation process is so preferable that it is preferable, less than +/- 3 degreeC is preferable, and also it is preferable to control within +/- 1.5 degreeC. Within this range, the polymerization reaction in the in-plane and in-layer depth directions of the coating film proceeds uniformly, which is preferable.

In the case of radical photopolymerization by light irradiation, it can be performed in air or an inert gas, but in order to shorten the induction group of superposition | polymerization of a radically polymerizable monomer or to fully improve a polymerization rate, the atmosphere which made oxygen concentration as low as possible. It is preferable to set it as. Preferably the oxygen concentration is 1 volume% or less, More preferably, the oxygen concentration is 0.5 volume% or less, Especially preferably, the oxygen concentration is 0.3 volume% or less.

As a method of reducing the oxygen concentration to 1% by volume or less, it is preferable to replace the atmosphere (about 79% by volume of nitrogen, about 21% by volume of oxygen) with another gas, and more preferably by nitrogen (subject to nitrogen purge). will be. It is also possible to control uneven | corrugated shape by nitrogen purge, and it is also preferable to use together with the anti-glare layer forming coating composition which concerns on this invention.

Moreover, the method of controlling the ambient temperature at the time of light irradiation, or the method of controlling the film surface temperature to predetermined temperature can be used. Specifically, the film surface temperature at the time of light irradiation is preferably 60 ° C or higher, more preferably 80 ° C or higher, and even more preferably 90 ° C or higher. Furthermore, the method of reducing said oxygen concentration and the method of improving the membrane surface temperature can also be used together.

Moreover, an electron beam can also be used similarly. As the electron beam, energy of 50 to 1000 keV, preferably 100 to 300 keV, emitted from various electron beam accelerators such as cocroft Walton type, van degraf type, resonant transformer type, insulated core transformer type, linear type, dynamtron type and high frequency type The electron beam which has is mentioned.

Next, microwave irradiation may be performed, and microwaves can be generated by a device such as a magnetron or a klystron. The frequency of the microwave is preferably 0.9 to 20 Hz, but usually a microwave generator having a frequency of 2.45 Hz due to the limitation of the radio wave method and the microwave electron tube. However, microwaves with a frequency of 0.915 GHz may be used if they are not affected by other electronic devices (for example, communication devices).

The output is adjusted in accordance with the thickness and width of the transparent support to be dried and the conveyance speed. The area which can irradiate microwaves per unit time (minutes) is determined by the conveyance speed (m / min), and the area of the conveyance speed x transparent support becomes the area which can irradiate microwaves per unit time (minutes). In the case of the transparent support of 40-120 micrometers, it is preferable that the irradiation amount of the microwave per 1m <2> of this area is 0.1-50 Pa.min, and it is 0.2-20 Pa.min further.

Next, the antiglare layer may contain an active energy ray curable resin. Alternatively, it may be laminated as another layer.

Active energy ray hardening resin means resin hardened | cured through crosslinking reaction etc. by active ray irradiation, such as an ultraviolet-ray or an electron beam. As active energy ray hardening resin, the component containing the monomer which has an ethylenically unsaturated double bond is used preferably, and it hardens | cures by irradiating active rays, such as an ultraviolet-ray or an electron beam, and an active energy ray hardening resin layer is formed. As active energy ray hardening resin, although ultraviolet curable resin, electron beam curable resin, etc. are mentioned as a typical thing, resin hardened | cured by ultraviolet irradiation is preferable.

As ultraviolet curable resin, ultraviolet curable urethane acrylate resin, ultraviolet curable polyester acrylate resin, ultraviolet curable epoxy acrylate resin, ultraviolet curable polyol acrylate resin, ultraviolet curable epoxy resin, etc. are preferable, for example. Used. Especially, ultraviolet curable acrylate resin is preferable.

UV curable acrylic urethane resins generally contain 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter acrylates include methacrylate) in a product obtained by reacting an isocyanate monomer or a prepolymer with a polyester polyol. Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as acrylate and 2-hydroxypropyl acrylate. For example, the thing of Unexamined-Japanese-Patent No. 59-151110 can be used.

For example, a mixture of 100 parts of Unidic 17-806 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) and one part of Collonate L (manufactured by Nippon Polyurethanes Co., Ltd.) is preferably used.

As ultraviolet curing polyester acrylate type resin, what is generally formed is easily formed by making 2-hydroxyethyl acrylate and 2-hydroxy acrylate type monomer react with polyester polyol, Unexamined-Japanese-Patent No. 59 Those described in -151112 can be used.

Specific examples of the ultraviolet curing epoxy acrylate-based resin include epoxy acrylate as an oligomer, and a reactive diluent and a photopolymerization initiator are added thereto and reacted to produce them, and those described in JP-A-105738 Can be used.

Specific examples of the ultraviolet curable polyol acrylate-based resin include trimethylolpropane triacrylate, ditrimethylol propane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and alkyl modification. Dipentaerythritol pentaacrylate and the like.

Specific examples of photopolymerization initiators of these ultraviolet curable resins include benzoin and derivatives thereof, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyl oxime ester, thioxanthone, and derivatives thereof. Can be mentioned. You may use it with a photosensitizer. The said photoinitiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate type photoinitiator, sensitizers, such as n-butylamine, triethylamine, and tri-n-butylphosphine, can be used. Photoinitiator used for ultraviolet curable resin composition Moreover, a photosensitizer is 0.1-15 mass parts with respect to 100 mass parts of said compositions, Preferably it is 1-10 mass parts.

As a resin monomer, general monomers, such as a methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, styrene, are mentioned as one monomer, for example. . Moreover, as a monomer which has two or more unsaturated double bonds, ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1, 4- cyclohexane diacrylate, 1, 4- cyclohexyl dimethyl diacrylate, the said One trimethylol propane triacrylate, pentaerythritol tetraacrylic ester, etc. are mentioned.

As a commercial item of the ultraviolet curing resin which can be used by this invention, Adeka Optoma KR, BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi telephone Co., Ltd.) My); Koei hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT -102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Hiroshi Sakae Chemical Co., Ltd.); Seika beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (Daiichi Seika Industry Co., Ltd.); KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (manufactured by Daicel Yushibi Co., Ltd.); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 Ink chemical industry Co., Ltd.); Olex No. 340 clear (made by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical Co., Ltd.); SP-1509 and SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (manufactured by Grace Japan Co., Ltd.), aronix M-6100, M-8030, M-8060 (manufactured by Toa Synthetic Co., Ltd.); NK hard B-420, B-500 (made by Shin-Nakamura Chemical Co., Ltd.), etc. can be selected suitably, and can be used.

Moreover, as a specific compound example, trimethylol propane triacrylate, ditrimethylol propane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl modified dipentaerythritol penta Acrylate, isoboroyl acrylate, etc. are mentioned.

The solvent may be contained in the said anti-glare layer coating liquid, may be contained suitably as needed, and may be diluted. As an organic solvent contained in a coating liquid, For example, hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone ), Esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents can be appropriately selected or a mixture thereof can be used. 5 mass% or more of propylene glycol monoalkyl ether (1-4 as carbon atoms of an alkyl group) or propylene glycol monoalkyl ether acetic acid ester (1-4 as carbon atoms of an alkyl group), More preferably, it is 5-80 mass It is preferable to use the said organic solvent containing% or more.

The anti-glare layer containing the active energy ray curable resin can be applied by a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or an inkjet method as described above.

As a light source in the case of using ultraviolet curable resin, if it is a light source which generate | occur | produces an ultraviolet-ray, it can use without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Although the irradiation conditions after apply | coating the low refractive index layer differ with each lamp, the irradiation amount of an ultraviolet-ray is 50 mJ / cm <2> -500mJ / cm <2> normally, Preferably it is 70mJ / cm <2> -300mJ / cm <2>, Especially preferably, 100mJ / cm <2> 250 mJ / cm 2.

Moreover, when irradiating an active line, it is preferable to carry out, applying a tension to the conveyance direction of a film, More preferably, it is performed, giving a tension also to the width direction. As for the tension | tensile_strength to provide, 30-300 N / m is preferable. The method of providing a tension is not specifically limited, You may give tension to a conveyance direction on a back roll, and you may give tension to a width direction or a biaxial direction with a tenter.

[Low refractive index layer]

The low-refractive-index layer of this invention apply | coats the said anti-glare layer forming coating composition on a transparent support body in a solution state, and in the state which the said anti-glare layer surface shape was smooth, of at least 1 layer of low-refractive-index layer on the said smooth surface Application | coating is carried out and after application | coating of the said low refractive index layer, it is characterized by changing an anti-glare layer surface shape into an uneven shape by at least 1 means of drying, heating, light irradiation, microwave irradiation, or electron beam irradiation. The low refractive index layer preferably contains a component that is cured by ultraviolet irradiation, and preferably, a high refractive index layer containing conductive metal oxide fine particles is formed between the antiglare layer and the low refractive index layer.

The refractive index of the low refractive index layer which concerns on this invention is lower than the refractive index of the transparent support body which is a support body, and it is preferable that it is the range of 1.30-1.45 by 23 degreeC and wavelength 550nm measurement.

It is preferable that the film thickness of a low refractive index layer is 5 nm-0.5 micrometer, It is more preferable that it is 10 nm-0.3 micrometer, It is most preferable that it is 30 nm-0.2 micrometer.

About the composition for low refractive index layer formation used for this invention, it is preferable to contain at least 1 sort (s) of particle | grains which have an outer layer and are porous or hollow inside. It is preferable that especially the particle | grains which have the said outer layer and whose inside is porous or a cavity are hollow silica type microparticles | fine-particles.

Moreover, you may contain the organosilicon compound represented by the following general formula (OSi-1), its hydrolyzate, or its polycondensate also in the composition for low refractive index layer formation.

<General formula (OSi-1)>

Si (OR) ₄

(In formula, R is an alkyl group, Preferably it is a C1-C4 alkyl group.)

In addition, you may add a solvent, a silane coupling agent, a hardening | curing agent, surfactant, etc. as needed.

(Hollow silica-based fine particles)

Hollow silica-based fine particles are composite particles comprising (I) porous particles and a coating layer formed on the surface of the porous particles, or (II) hollow particles having a cavity and a content of which is filled with a solvent, a gas or a porous material. In addition, either the (I) composite particle or the (II) cavity particle should just be contained in the low refractive index layer, and both may be included.

In addition, the cavity particle | grains are particle | grains which have a cavity inside, and the cavity is covered by the coating layer (also called particle wall). The cavity is filled with contents, such as a solvent, gas, or a porous substance used at the time of preparation. The average particle diameter of such hollow fine particles is 5-300 nm, It is preferable to exist in the range of 10-200 nm preferably. The average particle diameter of the hollow microparticles | fine-particles used is 3 / 2-1 / 10 of the average film thickness of the low refractive index layer formed, It is preferable to exist in the range of 2 / 3-1 / 10. It is preferable to use these hollow fine particles in the state disperse | distributed to a suitable medium for formation of a low refractive index layer. As a dispersion medium, water, alcohols (for example, methanol, ethanol, isopropyl alcohol) and ketones (for example, methyl ethyl ketone, methyl isobutyl ketone), ketone alcohols (for example diacetone alcohol), or these are included Mixed solvents are preferred.

The thickness of the coating layer of the composite particles or the thickness of the particle wall of the cavity particles is preferably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of the composite particles, when the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and the silicic acid monomers, oligomers, and the like having a low polymerization degree, which are coating liquid components described later, are easily spaced inside the composite particles. It may enter into a part and increase the refractive index of particle | grains, and the effect of low refractive index may not be fully acquired. When the thickness of the coating layer exceeds 20 nm, the silicic acid monomer and oligomer do not enter the inside, but the porosity (pore volume) of the composite particles may be lowered, so that the effect of low refractive index may not be sufficiently obtained. In the case of hollow particles, when the thickness of the particle wall is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of low refractive index may not be sufficiently exhibited.

It is preferable that the particle | grain wall of the coating layer of composite particle | grains, or the particle | grain particle | grains has silica as a main component. In addition, it is optionally contain a component other than silica, and _{specifically, Al 2 O 3, B 2} O 3, TiO 2, ZrO 2, SnO 2, CeO 2, P 2 O 3, Sb 2 O 3, MoO 3 , ZnO ₂ , WO ₃ , and the like. Examples of the porous particles constituting the composite particles include those made of silica, those made of inorganic compounds other than silica and silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Among them, porous particles made of a composite oxide of an inorganic compound other than silica and silica are particularly suitable. As the inorganic compound other than _{silica, Al 2 O 3, B 2} O 3, TiO 2, ZrO 2, SnO 2, CeO 2, P 2 O 3, Sb 2 O 3, MoO 3, ZnO 2, 1 , such as WO ₃ Or 2 or more types can be mentioned. In such porous particles, the molar ratio MO _X / SiO ₂ when silica is represented by SiO ₂ and inorganic compounds other than silica in oxide equivalent (MO _X ) is 0.0001 to 1.0, preferably 0.001 to 0.3. It is desirable to be at. It is difficult to obtain that the molar ratio MO _X / SiO ₂ of the porous particles is less than 0.0001. Even if obtained, the pore volume is small and particles having a low refractive index are not obtained. In addition, when the molar ratio MO _X / SiO ₂ of the porous particles exceeds 1.0, the proportion of silica decreases, so that it is difficult to obtain a large pore volume and a low refractive index.

The pore volume of such porous particles is preferably 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles with sufficiently low refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles decreases, and the strength of the obtained film may decrease.

In addition, the pore volume of such a porous particle can be calculated | required by the mercury porosimetry. In addition, examples of the contents of the hollow particles include a solvent, a gas, a porous material, and the like used in preparing the particles. The solvent may contain the unreacted substance of the particle precursor used, the catalyst used, etc. when preparing a cavity particle. Moreover, what consists of a compound illustrated with the said porous particle as a porous substance is mentioned. These contents may consist of a single component, but may be a mixture of plural components.

As a manufacturing method of such hollow microparticles | fine-particles, the manufacturing method of the composite oxide colloidal particle disclosed, for example in Paragraph No. [0010]-[0033] of Unexamined-Japanese-Patent No. 7-133105 is employ | adopted suitably. Specifically, when the composite particles are made of inorganic compounds other than silica and silica, the hollow fine particles are produced from the following first to third steps.

First Step: Preparation of Porous Particle Precursor

In the first step, an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is prepared separately, or a mixed aqueous solution of a silica raw material and an inorganic compound raw material other than silica is prepared, and the composite oxide for the purpose of this aqueous solution. Depending on the complex ratio of to, it is gradually added while stirring in an alkaline aqueous solution of pH 10 or more to prepare a porous particle precursor.

As silica raw materials, silicates of alkali metals, ammonium or organic bases are used. As silicate of an alkali metal, sodium silicate (water glass) and potassium silicate are used. Examples of the organic base include amines such as quaternary ammonium salts such as tetraethyl ammonium salt, monoethanolamine, diethanolamine, and triethanolamine. In addition, the silicate of ammonium or the silicate of an organic base also contains the alkaline solution which added ammonia, a quaternary ammonium hydroxide, an amine compound, etc. to a silicic acid solution.

In addition, as a raw material of inorganic compounds other than silica, an alkali-soluble inorganic compound is used. Specifically, oxo acid of an element selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc., alkali metal salt or alkaline earth metal salt of the oxo acid, ammonium salt, quaternary Ammonium salt is mentioned. More specifically, sodium aluminate, sodium tetraborate, ammonium zirconyl carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, ammonium cerium nitrate, and sodium phosphate are suitable.

Although the pH value of the mixed aqueous solution changes at the same time as the addition of these aqueous solutions, an operation for controlling the pH value in a predetermined range is not particularly necessary. The aqueous solution finally becomes a pH value determined by the kind of inorganic oxide and its mixing ratio. There is no restriction | limiting in particular in the addition speed of the aqueous solution at this time. In addition, it is also possible to use the dispersion liquid of seed particle as a starting material at the time of manufacture of a composite oxide particle. As the seed particles, the art, in particular but not limited _{to, SiO 2, Al 2 O 3} , TiO 2 or ZrO _2, etc. of the inorganic oxide or fine particles of composite oxide thereof is used, it is possible to use a conventional sol thereof. Moreover, you may make the porous particle precursor dispersion liquid obtained by said manufacturing method as a seed particle dispersion liquid. When using seed particle dispersion liquid, after adjusting pH of a seed particle dispersion liquid to 10 or more, the aqueous solution of the said compound is added to the said seed particle dispersion liquid, stirring in said alkali aqueous solution. Also in this case, it is not necessary to necessarily perform pH control of a dispersion liquid. By using the seed particles in this way, it is easy to control the particle diameter of the prepared porous particles, and it is possible to obtain ones having the same particle size.

The silica raw material and the inorganic compound raw material have high solubility on the alkali side. However, when the both are mixed in a pH range having a high solubility, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or precipitate on seed particles to grow particles. This happens. Therefore, it is not necessary to necessarily perform pH control like the conventional method at the time of precipitation and growth of fine particles.

In the composite ratio of silica and inorganic compounds other than silica in the first step, the inorganic compound to silica is converted into an oxide (MO _X ), and the molar ratio of MO _X / SiO ₂ is 0.05 to 2.0, preferably 0.2 to 2.0. It is preferable to exist in the range of. Within this range, the smaller the proportion of silica, the larger the pore volume of the porous particles. However, even if the molar ratio exceeds 2.0, the volume of the pores of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When preparing a co-particle, the mole ratio of MO _X / SiO ₂ is preferably in the range of 0.25 to 2.0.

Second Step: Removal of Inorganic Compounds Other Than Silica from Porous Particles

In the second step, at least a part of inorganic compounds (elements other than silicon and oxygen) other than silica are selectively removed from the porous particle precursor obtained in the first step. As a specific removal method, the inorganic compound in a porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or it is contacted with a cation exchange resin and ion-exchange-removed.

In addition, the porous particle precursor obtained by a 1st process is the particle | grains of the network structure which the silicon and the inorganic compound structural element couple | bonded through oxygen. Thus, by removing an inorganic compound (elements other than silicon and oxygen) from a porous particle precursor, the porous particle which is further porous and has a large pore volume is obtained. Moreover, when the quantity which removes inorganic oxides (elements other than silicon and oxygen) from a porous particle precursor is increased, cavity particle | grains can be prepared.

Furthermore, before removing an inorganic compound other than silica from a porous particle precursor, the silicic acid solution or valence containing the fluorine-substituted alkyl group containing silane compound obtained by de-alkali alkali metal salt of silica to the porous particle precursor dispersion liquid obtained by a 1st process. It is preferable to form a silica protective film by adding a decomposable organosilicon compound. The thickness of a silica protective film should just be 0.5-15 nm thick. Moreover, even if a silica protective film is formed, since the protective film in this process is porous and thin, it is possible to remove inorganic compounds other than the above-mentioned silica from a porous particle precursor.

By forming such a silica protective film, inorganic compounds other than the above-mentioned silica can be removed from a porous particle precursor, maintaining particle shape. In addition, when forming the silica coating layer mentioned later, the pore of a porous particle does not become occluded by a coating layer, For this reason, the silica coating layer mentioned later can be formed without reducing pore volume. In addition, when the amount of the inorganic compound to be removed is small, the particles do not crack, so it is not necessary to form a protective film.

Moreover, when preparing cavity particle | grains, it is preferable to form this silica protective film. When preparing a cavity particle, when an inorganic compound is removed, the precursor of the cavity particle which consists of a silica protective film, the solvent in the silica protection film, and the porous solid content of an undissolved | dissolved solution will be obtained, and if the coating layer mentioned later is formed in the precursor of this cavity particle, The coating layer becomes a particle wall to form cavity particles.

It is preferable that the quantity of the silica source added for the said silica protective film formation is small in the range which can maintain a particle shape. If the amount of the silica source is too large, the silica protective film becomes too thick, so that it may be difficult to remove inorganic compounds other than silica from the porous particle precursor. Examples of the organic silicon compound hydrolyzable to be used in for the silica to form a protective film, the general formula _{R n Si (OR ') 4} -n [R, R': such as an alkyl group, an aryl group, a vinyl group, an acryl group hydrocarbon group, n Alkoxysilane represented by = 0, 1, 2 or 3] can be used. In particular, tetraalkoxysilanes, such as a fluorine-substituted tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane, are used preferably.

As the addition method, a solution in which a small amount of alkali or acid as a catalyst is added to a mixed solution of these alkoxysilanes, pure water and alcohol is added to the dispersion of the porous particles, and the silicic acid polymer produced by hydrolyzing the alkoxysilane is formed as an inorganic oxide. Deposit on the surface of the particles. At this time, you may add an alkoxysilane, an alcohol, and a catalyst in a dispersion liquid simultaneously. As an alkali catalyst, ammonia, the hydroxide of an alkali metal, and amines can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

When the dispersion medium of the porous particle precursor is high in water alone or in a ratio of water to an organic solvent, it is also possible to form a silica protective film using a silicic acid solution. When using a silicic acid solution, a predetermined amount of a silicic acid solution is added to a dispersion liquid, an alkali is added simultaneously, and a silicic acid liquid is deposited on the surface of a porous particle. Moreover, you may produce a silica protective film using a silicic acid solution and the said alkoxysilane together.

3rd process: formation of a silica coating layer

In the third step, the particles are added by adding a hydrolyzable organosilicon compound or silicic acid solution containing a fluorine-substituted alkyl group-containing silane compound to the porous particle dispersion prepared in the second step (co-particle precursor dispersion in the case of hollow particles). The surface of is coated with a polymer such as a hydrolyzable organosilicon compound or a silicic acid solution to form a silica coating layer.

Examples of the organic silicon compound hydrolyzable to be used in for silica coating layer formed by the general formula _{R n Si (OR ') 4} -n [R, R' as described above: an alkyl group, an aryl group, a hydrocarbon such as a vinyl group, an acrylic group Alkoxysilane represented by a hydrogen group, n = 0, 1, 2 or 3] can be used. In particular, tetraalkoxysilanes, such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane, are used preferably.

As an addition method, the solution which added a small amount of alkali or an acid as a catalyst to the mixed solution of these alkoxysilanes, pure water, and alcohol is added to the said porous particle (co-particle precursor in the case of co-particles) dispersion, and alkoxysilane is hydrolyzed. The silicic acid polymer thus produced is deposited on the surface of the porous particles (cavity precursor in the case of hollow particles). At this time, you may add an alkoxysilane, an alcohol, and a catalyst in a dispersion liquid simultaneously. As an alkali catalyst, ammonia, the hydroxide of an alkali metal, and amines can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

In the case where the dispersion medium of the porous particles (co-particle precursor in the case of co-particles) is water alone or a mixed solvent with an organic solvent and a mixed solvent having a high ratio of water to organic solvent, the coating layer may be formed using a silicic acid solution. . The silicic acid solution is an aqueous solution of a low polymer of silicic acid obtained by ion exchange treatment of aqueous solutions of alkali metal silicates such as water glass.

The silicic acid solution is added to the porous particle (co-particle precursor in the case of co-particles) dispersion and at the same time alkali is added to deposit the silicic acid low polymer on the surface of the porous particles (co-particle precursor in the case of co-particles). In addition, you may use a silicic acid liquid together with the said alkoxysilane for forming a coating layer. The addition amount of the organosilicon compound or silicic acid solution used for forming a coating layer should just be a grade which can fully coat the surface of a colloidal particle, and the quantity of a silica coating layer finally obtained becomes 1-20 nm, and it is a porous particle ( In the case of hollow particles, the hollow particle precursor) is added to the dispersion. When the silica protective film is formed, the organosilicon compound or the silicic acid solution is added in an amount such that the total thickness of the silica protective film and the silica coating layer is in the range of 1 to 20 nm.

Next, the dispersion liquid of the particle | grains in which the coating layer was formed is heat-processed. In the case of a porous particle by heat processing, the silica coating layer which coat | covered the porous particle surface is densified, and the dispersion liquid of the composite particle by which the porous particle was coat | covered with the silica coating layer is obtained. In the case of the cavity particle precursor, the coating layer formed is densified to form a cavity particle wall, whereby a dispersion of cavity particles having a cavity filled with a solvent, a gas or a porous solid is obtained.

There is no restriction | limiting in particular if the heat processing temperature at this time is the grade which can occlude the micropore of a silica coating layer, The range of 80-300 degreeC is preferable. If the heat treatment temperature is less than 80 ° C., the fine pores of the silica coating layer may be completely blocked and densified, and in some cases, a long time may be required for the treatment time. Moreover, when heat processing temperature exceeds 300 degreeC and processing for a long time, it may become a dense particle and the effect of a low refractive index may not be acquired.

The refractive index of the inorganic fine particles thus obtained is low, lower than 1.42. It is inferred that these inorganic fine particles have a low refractive index because the porosity inside the porous particles is maintained or the inside is a cavity. Moreover, what is marketed from Catalytic Co., Ltd. can be used suitably for hollow silica type fine particles.

Moreover, it is preferable that the polymer which has a hydrocarbon backbone on the surface is covalently bonded as hollow silica type microparticles | fine-particles from the stability at the time of coating composition.

Next, the hollow silica-based particle to which the polymer which has a hydrocarbon backbone is covalently bonded is demonstrated.

A polymer having a hydrocarbon backbone is a covalent bond between a silica having a direct covalent bond or a surface of a hollow silica-based particle and a polymer having a hydrocarbon backbone, a covalent bond between silica and a binder, and a covalent bond between the binder and the polymer. It also means. As the binder, a silane coupling agent is preferably used.

Hollow silica-based fine particles covalently bonded to a polymer having a hydrocarbon backbone include: (1) a functional group capable of forming a covalent bond with the hollow silica-based particle surface in a state in which the hollow silica-based particle surface is untreated or treated with a silane coupling agent or the like. A method of reacting a polymer having a polymer with a polymer having a molecular weight thereof and grafting the polymer to the surface of the hollow silica-based particle, or (2) treating the monomer from the surface of the hollow silica-based particle in a state in which the surface of the hollow silica-based particle is untreated or treated with a silane coupling agent or the like. It can manufacture by the method of growing a polymer chain by superposing | polymerizing and surface grafting. As a specific manufacturing method, the method of Unexamined-Japanese-Patent No. 2006-257308 can be used. As the hollow silica-based fine particles, hollow silica-based particles having a conductive metal oxide coating layer may be used, and an antimony oxide coating layer is preferable as the conductive metal oxide coating layer.

It is preferable that content in the low refractive index layer of the hollow silica-type microparticles | fine-particles which has an outer layer and is porous or hollow inside is 10-50 mass%. In obtaining the effect of a low refractive index, 15 mass% or more is preferable, and when it exceeds 50 mass%, a binder component will become small and a film strength will become inadequate. Especially preferably, it is 20-50 mass%.

In the present invention, the low refractive index layer may contain a fluorine-substituted alkyl group-containing silane compound represented by the following general formula (OSi-2).

The fluorine-substituted alkyl group-containing silane compound represented by general formula (OSi-2) will be described.

Wherein, R ¹ ~ R ⁶ has a carbon number of 1-16, and preferably 1-4 alkyl groups, having 1 to 6 carbon atoms, preferably 1-4 halogenated alkyl group, having 6 to 12, preferably from 6 to 10 of the An aryl group, a C7-14, preferably 7-12 alkyl aryl group, an arylalkyl group, a C2-8, preferably 2-6 alkenyl group, or a C1-6, preferably 1-3 An alkoxy group, a hydrogen atom, or a halogen atom is represented.

Rf represents-(C _a H _b F _c )-, a is an integer of 1-12, b + c is 2a, b is an integer of 0-24, c represents an integer of 0-24. As such Rf, the group which has a fluoro alkylene group and an alkylene group is preferable. Specifically, such a fluorine-containing silicon compound (MeO) ₃ SiC ₂ H ₄ C ₂ F ₄ C ₂ H ₄ Si (MeO) ₃ , (MeO) ₃ SiC ₂ H ₄ C ₄ F ₈ C ₂ H ₄ Si ( MeO) ₃ , (MeO) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (MeO) ₃ , (H ₅ C ₂ O) ₃ SiC ₂ H ₄ C ₄ F ₈ C ₂ H ₄ Si (OC ₂ H ₅₎ it can be mentioned _{3, (H 5 C 2 O} ) 3 SiC 2 H 4 C 6 F 12 C 2 H 4 Si (OC 2 H 5) methoxydiethylene silane compound which is represented by _3, and so on.

When the binder contains a fluorine-substituted alkyl group-containing silane compound, the formed transparent film itself has hydrophobicity, so that even if the transparent film is not sufficiently densified and is porous or has cracks or voids, the water or acid and Entry into the transparent film by chemicals such as alkali is suppressed. Furthermore, microparticles | fine-particles, such as a metal, contained in the surface of a board | substrate or an underlayer, and chemical | medical agents, such as water and an acid and an alkali, do not react. For this reason, such a transparent film has the outstanding chemical resistance.

In addition, when the fluorine-substituted alkyl group-containing silane compound is included as the binder, not only such hydrophobicity but also good sliding property (low contact resistance), a transparent film excellent in scratch strength can be obtained. In addition, when the binder contains a fluorine-substituted alkyl group-containing silane compound having such a structural unit, when the conductive layer is formed in the lower layer, since the shrinkage ratio of the binder is equal to or close to that of the conductive layer, the adhesive has excellent adhesiveness with the conductive layer. A film can be formed. In addition, when heat-processing a transparent film, the conductive layer peels from the difference of shrinkage rate, and the part without electrical contact in a transparent conductive layer does not arise. For this reason, sufficient electroconductivity can be maintained as a whole.

The transparent coating film containing the fluorine-substituted alkyl group-containing silane compound and the above-described outer layer and hollow silica-based fine particles having a porous or hollow interior therein has a high scratch strength and a film strength evaluated by eraser strength or toenail strength, The pencil hardness is also high, and a transparent film excellent in strength can be formed.

The low refractive index layer which concerns on this invention may contain a silane coupling agent. As the silane coupling agent, methyl trimethoxysilane, methyltriethoxysilane, methyl trimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyl trimethoxysilane, ethyltriethoxysilane, vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxy Silane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-gly Cydyloxypropyltriethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, β- (3,4 -Epoxycyclohexyl) ethyltriethoxysilane, γ-acryloyloxypropyltrimethok Cysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysisilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyl tree Ethoxysilane, N- (beta)-(aminoethyl)-(gamma) -aminopropyl trimethoxysilane, and (beta) -cyanoethyl triethoxysilane are mentioned.

Moreover, as an example of the silane coupling agent which has a bisubstituted alkyl group with respect to silicon, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyl diethoxysilane, phenylmethyl diethoxysilane, (gamma)-glycidyloxypropyl methyl diethoxy Silane, γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimeth Oxysilane, γ-acryloyl oxypropylmethyl diethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyl diethoxysilane, γ-mercaptopropylmethyldimethoxysilane , γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane and methylvinyldiethoxysilane.

Among them, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-meta having a double bond in the molecule Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyl as having a di-substituted alkyl group with respect to silicon Preferred are oxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, methylvinyldimethoxysilane and methylvinyldiethoxysilane, and γ-acryloyloxypropyltrimethoxysilane and γ-meta Cryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyl methyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-metha Lilo yl oxy propyl methyl diethoxy silane is particularly preferred.

You may use together 2 or more types of coupling agents. In addition to the silane coupling agent shown above, you may use another silane coupling agent. Other silane coupling agents include alkyl esters of ortho silicate (for example, methyl ortho silicate, ethyl ortho silicate, n-propyl ortho silicate, ortho silicate i-propyl, n-butyl ortho silicate, sec-butyl ortho silicate, ortho silicate) t-butyl) and its hydrolyzate.

As a polymer used as another binder of a low refractive index layer, For example, polyvinyl alcohol, polyoxyethylene, polymethylmethacrylate, polymethyl acrylate, fluoroacrylate, diacetyl cellulose, triacetyl cellulose, nitro Cellulose, polyester, and alkyd resin.

It is preferable that a low refractive index layer contains the binder of 5-80 mass% in the whole. The binder has a function of adhering the hollow silica fine particles and maintaining the structure of the low refractive index layer containing the voids. The amount of the binder used is appropriately adjusted to maintain the strength of the low refractive index layer without filling the voids.

(menstruum)

It is preferable that the low refractive index layer which concerns on this invention contains an organic solvent. Examples of specific organic solvents include alcohols (e.g. methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (e.g. methyl acetate, acetic acid) Ethyl, 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 Hydrogen (e.g. benzene, toluene, xylene), amide (e.g. dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (e.g. diethyl ether, dioxane, tetrahydrofuran), ether alcohol ( For example, 1-methoxy-2-propanol) can be mentioned. Especially, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and butanol are especially preferable.

It is preferable that solid content concentration in a low-refractive-index layer coating composition is 1-4 mass%, and by making the solid content concentration 4 mass% or less, it becomes difficult to produce a coating nonuniformity, and drying load is reduced by making it 1 mass% or more.

(High refractive index layer)

In the present invention, it is preferable to form a high refractive index layer containing conductive metal oxide fine particles between the antiglare layer and the low refractive index layer as the antireflection layer.

The kind of metal oxide fine particles is not particularly limited, and is selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. Metal oxides having at least one kind of element can be used, and these metal oxide fine particles may be doped with a small amount of atoms such as Al, In, Sn, Sb, Nb, a halogen element and Ta. Moreover, these mixtures may be sufficient. In the present invention, at least one metal oxide fine particle selected from zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium tin oxide (ITO), antimony-doped tin oxide (ATO) and zinc antimony acid as a main component It is especially preferable to use it. It is particularly preferable to contain zinc antimonate particles.

The average particle diameter of the primary particle of these metal oxide microparticles | fine-particles is the range of 10 nm-200 nm, and it is especially preferable that it is 10-150 nm. The average particle diameter of metal oxide fine particles can be measured from the electron micrograph by a scanning electron microscope (SEM). You may measure with a particle size distribution meter etc. which use a dynamic light scattering method, a static light scattering method, etc. When the particle diameter is too small, it becomes easy to aggregate and the dispersibility deteriorates. If the particle diameter is too large, the haze is significantly increased, which is not preferable. The shape of the metal oxide fine particles is preferably particulate, spherical, cubic, fusiform, needle or irregular.

The refractive index of a high refractive index layer is specifically higher than the refractive index of a transparent support body, and it is preferable that it is the range of 1.5-2.2 in 23 degreeC and a wavelength 550nm measurement. Since the kind and addition amount of metal oxide microparticles | fine-particles dominate the means of adjusting the refractive index of a high refractive index layer, it is preferable that the refractive index of metal oxide microparticles is 1.80-2.60, and it is more preferable that it is 1.85-2.50.

The metal oxide fine particles may be surface treated with an organic compound. By surface modification of the surface of metal oxide fine particles with an organic compound, dispersion stability in an organic solvent can be improved, control of dispersion particle diameter becomes easy, and aggregation and sedimentation with time can also be suppressed. For this reason, the surface tree amount in a preferable organic compound is 0.1 mass%-5 mass% with respect to a metal oxide particle, More preferably, they are 0.5 mass%-3 mass%. Examples of the organic compound used for the surface treatment include polyols, alkanol amines, stearic acid, silane coupling agents and titanate coupling agents. Among these, the silane coupling agent mentioned later is preferable. You may combine 2 or more types of surface treatment.

It is preferable that the thickness of the high refractive index layer containing the said metal oxide fine particle is 5 nm-1 micrometer, It is more preferable that it is 10 nm-0.2 micrometer, It is most preferable that it is 30 nm-0.1 micrometer.

The ratio of metal oxide fine particles to be used and binders such as ionizing radiation curable resins to be described later varies depending on the type, particle size, etc. of the metal oxide fine particles, but in the volume ratio, the latter 2 is about 1 to 2 for the former and 2 for the former. desirable.

5 mass%-85 mass% are preferable in a high refractive index layer, as for the usage-amount of the metal oxide fine particle used by this invention, it is more preferable that it is 10 mass%-80 mass%, and 20-75 mass% is the most preferable. If the amount is small, the desired refractive index and the effect of the present invention are not obtained. If the amount is too large, the film strength deteriorates or the like.

The metal oxide fine particles are provided in a coating liquid for forming a high refractive index layer in a state of a dispersion dispersed in a medium. It is preferable to use the liquid whose boiling point is 60-170 degreeC as a dispersion medium of metal oxide particle. Specific examples of the dispersion solvent include water, alcohol (e.g. methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ketone alcohol (e.g. Acetone alcohol), 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 alcohol (for example, 1-methoxy-2-propanol), propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. Especially, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and butanol are especially preferable.

Moreover, metal oxide fine particles can be disperse | distributed in a medium using a disperser. Examples of dispersers include sand grinder mills (eg, bead mills with pins), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. Particular preference is given to sand grinder mills and high speed impeller mills. In addition, you may perform a preliminary dispersion process. Examples of the disperser used for the preliminary dispersion treatment include ball mills, Mitsmoto roll mills, kneaders and extruders. It is also preferable to contain a dispersing agent.

In the present invention, the metal oxide fine particles having a core / shell structure may also be contained. The shell may be formed in one layer around the core or in multiple layers in order to further improve light resistance. It is preferable that the core is completely covered by the shell.

The core may be titanium oxide (rutile type, anatase type, amorphous type, etc.), zirconium oxide, zinc oxide, cerium oxide, indium oxide doped with tin, tin oxide doped with antimony, or the like. It may be a main component.

The shell is preferably formed of an oxide or sulfide of a metal mainly composed of inorganic compounds other than titanium oxide. For example, inorganic compounds based on silicon dioxide (silica), aluminum oxide (alumina) zirconium oxide, zinc oxide, tin oxide, antimony oxide, indium oxide, iron oxide, zinc emulsion and the like are used. Among them, alumina, silica, and zirconia (zirconium oxide) are preferable. Moreover, these mixtures may be sufficient.

The coating amount of the shell with respect to the core is 2-50 mass% in average coating amount. Preferably it is 3-40 mass%, More preferably, it is 4-25 mass%. When the coating amount of the shell is large, the refractive index of the fine particles decreases, and when the coating amount is too small, light resistance deteriorates. You may use together 2 or more types of inorganic fine particles.

The titanium oxide used as a core can use what was produced by the liquid phase method or the vapor phase method. As a method of forming the shell around the core, for example, U.S. Patent 3,410,708, Japanese Patent Publication No. 58-47061, U.S. Patent 2,885,366, U.S. Patent 3,437,502, U.S. Patent 1,134,249, U.S.A. The method described in patent 3,383,231, British patent 2,629,953, 1,365,999, etc. can be used.

The high refractive index layer or the low refractive index layer which concerns on this invention can contain the compound represented by the following general formula (CL1), or its chelate compound, and can improve physical properties, such as hardness.

<General Formula (CL1)>

A _n MB _xn

In the formula, M represents a metal atom, A represents a hydrocarbon group having a hydrolyzable functional group or a hydrolyzable functional group, and B represents an atomic group covalently or ionized bonded to the metal atom M. x is the valence of the metal atom M, n is an integer of 2 or more and less than x.

As functional group A which can be hydrolyzed, halogen, ester groups, an amide group, etc., such as an alkoxyl group and a chlor atom, are mentioned, for example. The metal compound which belongs to said Formula 2 contains the alkoxide which has 2 or more alkoxyl groups couple | bonded with the metal atom directly, or its chelate compound. As a preferable metal compound, titanium alkoxide, zirconium alkoxide, or those chelate compounds are mentioned. Titanium alkoxide has a high reaction rate, has a high refractive index, and is easy to handle. However, titanium alkoxide deteriorates light resistance when added in large quantities because of photocatalytic action. Since zirconium alkoxide has a high refractive index but is easy to be cloudy, care should be taken in dew point management and the like during coating. Moreover, since titanium alkoxide has the effect of accelerating the reaction between the ultraviolet curable resin and the metal alkoxide, the physical properties of the coating film can be improved only by adding a small amount.

As titanium alkoxide, for example, tetramethoxy titanium, tetraethoxy titanium, tetra-iso-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium And tetra-tert-butoxy titanium.

As zirconium alkoxide, for example, tetramethoxy zirconium, tetraethoxy zirconium, tetra-iso-propoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium And tetra-tert-butoxy zirconium.

Preferred chelating agents for coordinating to metal compounds of glass to form chelate compounds include alkanol amines such as diethanolamine and triethanolamine, glycols such as ethylene glycol, diethylene glycol and propylene glycol, acetylacetone and ethyl acetate Examples thereof include molecular weight of 10,000 or less. By using these chelating agents, it is possible to form a chelating compound that is stable against mixing of water and the like and excellent in reinforcing effect of the coating film.

It is preferable to adjust the addition amount of a metal compound so that content of the metal oxide derived from the said metal compound contained in a high refractive index layer may be 0.3-5 mass%. If it is less than 0.3 mass%, scratch resistance will run short, and if it exceeds 5 mass%, there exists a tendency for light resistance to deteriorate.

In the high refractive index layer used in the present invention, the ionizing radiation curable resin can be contained as a binder of the metal oxide fine particles in order to improve film forming properties and physical properties of the coating film. As the ionizing radiation curable resin, a monomer or oligomer having two or more functional groups capable of directly or indirectly generating a polymerization reaction by the action of a photopolymerization initiator by irradiation of ionizing radiation such as ultraviolet rays or electron beams can be used. As a functional group, the group which has unsaturated double bonds, such as a (meth) acryloyloxy group, an epoxy group, a silanol group, etc. are mentioned. Especially, the radically polymerizable monomer and oligomer which has two or more unsaturated double bond can be used preferably. You may combine a photoinitiator as needed. As such an ionizing radiation curable resin, polyol acrylate, epoxy acrylate, urethane acrylate, polyester acrylate or a mixture thereof is used. Examples of the polyfunctional acrylate compound include pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. It is preferable that it is a compound chosen from the group which consists of. Here, a polyfunctional acrylate compound is a compound which has a 2 or more acryloyloxy group and / or a methacroyl oxy group in a molecule | numerator.

As a monomer of a polyfunctional acrylate compound, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, trimethyl All ethane triacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin Triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tris (acryloyloxyethyl) isocyanate, ethylene Glycol Dimethacrylate, Diethylene Glycol Dimethacrylate, 1,6-hexanediol dimethacrylate, neopentylglycol dimethacrylate, trimethylolpropanetrimethacrylate, trimethylolethanetrimethacrylate, tetramethylolmethanetrimethacrylate, tetra Methylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate, dipentaerythritol tree A methacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, and dipentaerythritol hexamethacrylate are mentioned preferably. These compounds are used individually or in mixture of 2 or more types, respectively. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient.

It is preferable that the addition amount of an ionizing radiation curable resin is 15 mass% or more and less than 50 mass% in solid content in a high refractive index composition.

In order to accelerate the curing of the ionizing radiation curable resin used in the present invention, it is preferable to contain 3: 7 to 1: 9 of an acryl-based compound having two or more polymerizable unsaturated bonds in a photopolymerization initiator and a molecule.

Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxy benzophenone, mihilerketone, α-amyl oxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.

As an organic solvent used when coating the high refractive index layer used for this invention, alcohol (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentane) Ool, hexanol, cyclohexanol, benzyl alcohol, etc., polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol , Hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc., polyhydric alcohol ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol mono) Methyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, Ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether and the like, amines (for example, ethanolamine, Diethanolamine, triethanolamine, N-methyl diethanolamine, N-ethyl diethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine , Pentamethyldiethylenetriamine, tetramethylpropylenediamine, and the like), amides (for example, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclic (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, and the like, sulfoxides (for example , Dimethyl sulfoxide, etc.), alcohol Acids (for example, sulfolane, etc.), urea, acetonitrile, acetone and the like can be mentioned, in particular, alcohols, polyhydric alcohols, polyhydric alcohol ethers are preferable.

[Back coat layer]

It is preferable that the anti-glare antireflection film of this invention forms a backcoat layer in the surface on the opposite side to the side in which the anti-glare layer was formed. The back coat layer is formed in order to correct curl generated by forming an antiglare layer or other layers. In other words, the degree of curl can be balanced by giving the property of rounding the inner side of the back coat layer. In addition, the backcoat layer is preferably applied as a blocking prevention layer, and in that case, it is preferable that fine particles are added to the backcoat layer coating composition in order to give a blocking prevention function.

As fine particles added to the backcoat layer, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, indium oxide and zinc oxide. , ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate.

These microparticles | fine-particles are marketed under the brand names of aerosol R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above Japan Aerosol Co., Ltd.), for example, Can be used. The fine particles of zirconium oxide are commercially available under the trade names of, for example, Aerosil R976 and R811 (above, Aerogel Co., Ltd.) and can be used. Examples of the polymer include silicone resins, fluororesins and acrylic resins. A silicone resin is preferable, and it is especially preferable to have a three-dimensional network structure, for example, Tospearl 103, 105, 108, 120, 145, 3120 and 240 (above Toshiba Silicone Co., Ltd.). It is marketed under a brand name of) and can use it.

Among them, aerosil 200V and aerosil R972V are particularly preferably used because the blocking prevention effect is large while keeping the haze low. It is preferable that the anti-glare antireflection film of this invention is 0.9 or less, especially 0.1-0.9, the dynamic friction coefficient of a back surface side with an anti-glare layer.

The fine particles contained in the backcoat layer are 0.1-50 mass% with respect to a binder, Preferably it is 0.1-10 mass%. It is preferable that the increase of haze at the time of forming a backcoat layer is 1% or less, It is preferable that it is 0.5% or less, It is especially preferable that it is 0.0 to 0.1%.

Examples of the solvent used for coating the backcoat layer include dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, and ethylene. Chloride, tetrachloroethane, trichloroethane, chloroform, water, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol, cyclohexanone, cyclohexanol, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether or hydrocarbons (toluene, xylene), etc. are mentioned, It is used combining suitably.

It is preferable to apply these coating compositions with a wet film thickness of 1 to 100 µm on the surface of the transparent support using a gravure coater, dip coater, reverse coater, wire bar coater, die coater or spray coating, inkjet coating, and the like. It is preferable that it is -30 micrometers. As resin used as a binder of a backcoat layer, For example, a vinyl chloride-vinyl acetate copolymer, a vinyl chloride resin, a vinyl acetate resin, a copolymer of vinyl acetate and a vinyl alcohol, the partially hydrolyzed vinyl chloride-vinyl acetate copolymer, Vinyl-based polymers such as vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, and ethylene-vinyl acetate copolymer Cellulose derivatives such as coalescing, nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.8 to 2.3, propionyl group substitution degree 0.1 to 1.0), diacetyl cellulose, cellulose acetate butyrate resin, maleic acid and / or Copolymers of acrylic acid, acrylic ester copolymers, acrylonitrile-styrene balls Polymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, urethane resin, poly Ester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene-butadiene resin, butadiene-acrylonitrile resin and other rubber resins, silicone type Although resin, fluorine resin, etc. are mentioned, It is not limited to these. For example, as an acrylic resin, acryl pet MD, VH, MF, V (made by Mitsubishi Rayon Co., Ltd.), Hipearl M-4003, M-4005, M-4006, M-4202, M-5000, M- 5001, M-4501 (manufactured by Negami Industrial Co., Ltd.), diamond BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR-79 , BR-80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR -105, BR-106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118, etc. (made by Mitsubishi Rayon Co., Ltd.); Various homopolymers, copolymers, etc. which were manufactured using the methacrylic monomer as a raw material are commercially available, and a preferable mono may be selected suitably from these. For example, as resin used as a binder, it is preferable to use the blended thing of cellulose ester resins, such as a cellulose diacetate and a cellulose acetate propionate, and an acrylic resin, and using microparticles | fine-particles which consist of an acrylic resin, By making the refractive index difference less than 0 to 0.02, a high backcoat layer can be obtained.

The order of applying the backcoat layer may be before or after applying the antiglare layer of the present invention. However, when the backcoat layer also serves as a blocking prevention layer, it is preferable to apply the backcoat layer first. Alternatively, the back coat layer may be applied in two or more times. Moreover, it is also preferable that a backcoat layer also serves as an easily bonding layer for improving adhesiveness with a polarizer.

(Reflectivity of anti-glare antireflection film)

The reflectance of the anti-glare antireflection film according to the present invention can be measured by a spectrophotometer. In that case, after roughening the back surface of the measurement side of a sample, after performing light absorption process using a black spray, the reflected light of visible region (400-700 nm) is measured. Although the reflectance is so preferable that it is low, it is preferable that the average value in the wavelength of a visible light region is 1.5% or less, and it is preferable that the minimum reflectance is 0.8% or less. It is also desirable to have a reflection spectrum of flat shape in the wavelength region of visible light.

In addition, the reflection color of the surface of the display device subjected to the anti-reflective treatment is often reflected by red or blue light because the reflectance of the short wavelength region or the long wavelength region is increased in the visible light region due to the design of the anti-reflection film. ) Is different depending on the use, and when used for the outermost surface of a thin television or the like, neutral color tone is desired. In this case, the generally desired reflection color range is 0.17 ≦ x ≦ 0.27 and 0.07 ≦ y ≦ 0.17 on the XYZ color system (CIE1931 color system).

The film thickness of the high refractive index layer and the low refractive index layer is calculated by calculation according to a conventional method in consideration of reflectance and color taste of the reflected light rather than the refractive index of each layer.

Moreover, since the anti-glare antireflection film in this invention has hard coat property, since it is hard to be damaged at the grade of a polarizing plate chemical process etc., it is preferable. Hard coat property here means the film whose pencil hardness is H-8H. Especially preferably, they are 2H-6H, More preferably, they are 3H-6H, More preferably, they are 4H-6H. Pencil hardness is a pencil prescribed by JIS K 5400, using a test pencil prescribed by JIS S 6006 after humidifying the produced anti-glare antireflection film at a temperature of 23 ° C. and a relative humidity of 55% for 2 hours or more. It is the value measured according to the hardness evaluation method.

It is preferable to surface-treat this invention before apply | coating each layer. Examples of the surface treatment method include a washing method, an alkali treatment method, a frame plasma treatment method, a high frequency discharge plasma method, an electron beam method, an ion beam method, a sputtering method, an acid treatment, a corona treatment method, and an atmospheric pressure glow discharge plasma method.

Corona treatment is a process performed by applying and discharging a high voltage of 1 kV or more between electrodes under atmospheric pressure, and the gas can be performed using an apparatus commercially available from Electric Co., Ltd., Toyo Electric Co., Ltd. or the like. The intensity of corona discharge treatment depends on the distance between electrodes, the output per unit area, and the frequency of the generator. A commercially available electrode (A electrode) of one of the corona treatment apparatuses can be used, but the material can be selected from aluminum, stainless steel and the like. The other is an electrode (B electrode) for embedding a plastic film, which is a roll electrode provided at a constant distance from the A electrode so that corona treatment is stably and uniformly performed. It is also possible to use commercially available ones, and rolls of ceramics, silicon, EPT rubber, hyparon rubber, or the like are preferably used for rolls made of aluminum, stainless steel, and metals thereof. The frequency used for the corona treatment used for this invention is a frequency of 20 Hz or more and 100 Hz or less, and the frequency of 30 Hz-60 Hz is preferable. When the frequency is lowered, the uniformity of the corona treatment is deteriorated, and nonuniformity of the corona treatment occurs. In addition, when the frequency is increased, there is no particular problem when performing a high output corona treatment, but when performing a low output corona treatment, it becomes difficult to perform a stable process, and as a result, a process nonuniformity arises. Although the output of a corona treatment is 1-5 W * min. / M <2>, the output of 2-4 W * min. / M <2> is preferable. Although the distance of an electrode and a film is 5 mm or more and 50 mm or less, Preferably they are 10 mm or more and 35 mm or less. When the gap is open, a higher voltage is required to maintain a constant output, and nonuniformity tends to occur. In addition, when the gap is too narrow, the voltage to be applied is too low, and nonuniformity tends to occur. In addition, when conveying a film and carrying out a continuous process, a film contacts a electrode and a scratch arises.

The alkali treatment method is not particularly limited as long as it is a method of immersing the film coated with the antiglare layer in an aqueous alkali solution.

As aqueous alkali solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, ammonia aqueous solution, etc. can be used, Especially, sodium hydroxide aqueous solution is preferable.

0.1-25 mass% is preferable, and, as for the alkali concentration of aqueous alkali solution, for example, sodium hydroxide concentration, 0.5-15 mass% is more preferable.

Alkali treatment temperature is 10-80 degreeC normally, Preferably it is 20-60 degreeC.

Alkali treatment time is 5 second-5 minutes, Preferably it is 30 second-3 minutes. It is preferable to wash with water sufficiently, after neutralizing with the acidic substance the film after alkali treatment.

Moreover, as plasma processing, such as an atmospheric pressure plasma process and an atmospheric pressure plasma process, it is disclosed by Unexamined-Japanese-Patent No. 2004-352777, Unexamined-Japanese-Patent No. 2004-352777, 2007-314707, etc., for example. Reference may be made to plasma processing techniques.

Moreover, as a processing apparatus, AP-T series etc. which are the atmospheric pressure plasma processing apparatus by Sekisui Chemical Co., Ltd. can be used.

Each layer of the antireflection layer is formed on the antiglare layer by a dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, micro gravure coating method, extrusion coating method or ink jet method. It can form by application | coating using it.

In addition, the anti-glare antireflection film of the present invention is produced by laminating the anti-reflection layer and solidifying the anti-glare layer into an uneven shape, and then, manufacturing the anti-glare antireflection film by heat-processing at 50 to 160 ° C. in the state of being wound in a roll shape. desirable. What is necessary is just to determine suitably the period of heat processing according to the temperature set, for example, if it is 50 degreeC, Preferably it is the period of 3 days or more and less than 30 days, and if it is 160 degreeC, the range of 10 minutes or more and 1 day or less is preferable. . Usually, it is preferable to set relatively low temperature, and it is preferable to carry out about 7 days in 50-60 degreeC vicinity so that the heat processing effect of a roll outer part, a roll center part, and a roll core part may not be biased.

In order to perform heat processing stably, it is necessary to carry out in the place where temperature and humidity are adjustable, and it is preferable to carry out in heat processing rooms, such as a clean room without dust.

The roll core at the time of winding the anti-glare antireflection film coated with the functional thin film in the shape of a roll is not particularly limited as long as it is a cylindrical core, but is preferably a hollow plastic core and a heat-resistant plastic that can withstand the heat treatment temperature. This is preferable and resin, such as a phenol resin, xylene resin, melamine resin, a polyester resin, an epoxy resin, is mentioned, for example. Moreover, the thermosetting resin reinforced by fillers, such as glass fiber, is preferable.

It is preferable that the number of windings to these roll cores is 100 times or more, It is more preferable that it is 500 times or more, It is preferable that a winding thickness is 5 cm or more.

In this way, when the said thin film is coated on a long roll of plastic film base material, and the said heat processing is performed in the state wound up the roll wound by the plastic core, it is preferable to rotate the roll, and rotation is 1 minute. The speed of 1 rotation or less is preferable, and continuous or intermittent rotation may be sufficient. Moreover, it is preferable to perform rewinding of the roll 1 or more times during a heating period.

In order to rotate the anti-glare anti-reflective film roll of the long roll wound up to the core during heat processing, it is preferable to provide the exclusive swivel to a heat processing chamber.

In the case of intermittent rotation, the stopping time is preferably within 10 hours, the stopping position is preferably uniform in the circumferential direction, and the stopping time is more preferably within 10 minutes. Most preferably, it is continuous rotation.

As for the rotation speed in continuous rotation, the time required for one rotation becomes like this. Preferably it is 10 hours or less, and since it becomes an apparatus burden as soon as possible, substantially the range of 15 minutes-2 hours is preferable.

Moreover, in the case of the exclusive trolley | bogie which has a rotation function, anti-glare antireflection film roll can be rotated also during a movement and storage, and in this case, rotation is effective as a black band countermeasure which arises when a storage period is long. Function.

[Transparent support]

Next, the transparent support which can be used by this invention is demonstrated.

As a transparent support body used for this invention, what is easy to manufacture, adhesiveness with an actinic-rays curable resin layer is favorable, optically isotropic, and optically transparent is mentioned as a preferable requirement.

The transparency as used in the present invention refers to a transmittance of visible light of 60% or more, preferably 80% or more, and particularly preferably 90% or more.

Although it does not have a restriction | limiting in particular if it has the said property, For example, a cellulose ester film, a polyester film, a polycarbonate film, a polyarylate film, a polysulfone (including polyether sulfone) type film, a polyethylene tere Polyester film such as phthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose triacetate, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol Films, ethylene vinyl alcohol films, syndiotactic polystyrene films, polycarbonate films, cycloolefin polymer films (Aton (manufactured by JSR), Zeonex, Zeonoa (above, manufactured by Nihon Xeon)), polymethylpentene films, polyethers Ketone film, polyether Ketone imide film, a polyamide film, a fluororesin film, a nylon film, a polymethyl methacrylate film, an acrylic film, a glass plate, etc. are mentioned. Among them, a cellulose triacetate film, a polycarbonate film, a polysulfone (including polyether sulfone) film is preferable, and in the present invention, in particular, a cellulose ester film (for example, Konica Minolta Tech, product name KC8UX2MW, KC4UX2MW, KC8UY, KC4UY, KC5UN, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4UEW, KC4FR-1, KC4FR-2 (manufactured by Konica Minolta Opto Co., Ltd.) It is used preferably from a viewpoint of adhesiveness. These films may be a film manufactured by a melt casting agent film, or a film manufactured by a solution casting agent film may be sufficient as them.

(Cellulose ester resin)

In this invention, it is preferable to contain a cellulose ester resin (henceforth simply a cellulose ester) as a transparent support body. As a cellulose ester, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable, and cellulose acetate butyrate, cellulose acetate phthalate, cellulose acetate propionate, and cellulose acetate butyrate are especially used preferably.

In particular, when the degree of substitution of X, propionyl or butyryl groups is Y as the degree of substitution of the acetyl group, it is preferable that X and Y are cellulose ester films having mixed fatty acid esters of cellulose in the following ranges.

2.3≤X + Y≤3.0

0.1≤Y≤2.0

Specifically, 2.4≤X + Y≤2.9

It is preferable that 0.3 <= Y <= 1.5.

When using a cellulose ester as a transparent support body used for this invention, although there is no limitation in particular as a cellulose of the raw material of a cellulose ester, Cotton linter, wood pulp (derived from hardwoods, derived from hardwoods), kenaf, etc. are mentioned. In addition, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively. When the acylating agent is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride), these cellulose esters use an organic solvent such as acetic acid or methylene chloride, and a cellulose raw material using a protic catalyst such as sulfuric acid. It can be obtained by reacting with.

When the acylating agent is an acid chloride (CH ₃ COCl, C ₂ H ₅ COCl, C ₃ H ₇ COCl), the reaction is carried out using a basic compound such as an amine as a catalyst. Specifically, it can synthesize | combine with reference to the method of Unexamined-Japanese-Patent No. 10-45804, etc. Moreover, the cellulose ester used for this invention mixes and reacts the said acylating agent amount according to each substitution degree, and, as for cellulose ester, these acylating agents react with the hydroxyl group of a cellulose molecule. The cellulose molecule consists of a plurality of linked glucose units, and there are three hydroxyl groups in the glucose unit. The number in which the acyl group was derived from these three hydroxyl groups is called substitution degree (mol%). For example, cellulose triacetate has an acetyl group bonded to all three hydroxyl groups of the glucose unit (actually 2.6 to 3.0).

As substitution degree of the cellulose ester used for this invention, the 2nd, 3rd, and 6th positions may be substituted by the acyl group normally, or the cellulose ester substituted by the 6th position more or less is also used preferably. Preferable degree of substitution in the 6th position is 0.7-0.97, More preferably, it is 0.8-0.97.

As described above, as the cellulose ester used in the present invention, a mixed fatty acid ester of cellulose in which a propionate group or a butyrate group is bound, in addition to an acetyl group such as cellulose acetate propionate, cellulose acetate butyrate or cellulose acetate propionate butyrate It is preferably used. The butyryl group forming the butyrate may be linear or branched.

The cellulose acetate propionate containing a propionate group as a substituent is excellent in water resistance and is useful as a film for liquid crystal image display devices.

The measuring method of substitution degree of an acyl group can be measured according to the prescription | regulation of ASTM-D 817-96.

As for the number average molecular weight of a cellulose ester, the mechanical strength at the time of 70000-250000 shape | molding is strong, and also becomes moderate dope viscosity, It is preferable, More preferably, it is 80000-150000.

In addition, a cellulose ester may contain the acrylic resin described below, and especially the outstanding scratch resistance is obtained by blending an acrylic resin.

Next, an acrylic resin is demonstrated.

Acrylic resin also includes methacryl resin. Although it does not restrict | limit especially as resin, What consists of 50-99 mass% of methyl methacrylate units and 1-50 mass% of other monomeric units copolymerizable with this is preferable.

Examples of other copolymerizable monomers include alkyl methacrylate having 2 to 18 carbon atoms in alkyl, alkyl acrylate having 1 to 18 carbon atoms in alkyl, alpha, beta -unsaturated acids such as acrylic acid and methacrylic acid, maleic acid and fumaric acid. Aromatic vinyl compounds, such as unsaturated group containing divalent carboxylic acid, styrene, (alpha) -methylstyrene, and nuclear substituted styrene, (alpha), (beta)-unsaturated nitrile, such as acrylonitrile and methacrylonitrile, and maleic anhydride And maleimide, N-substituted maleimide, glutaric anhydride, and the like, and these can be used alone or in combination of two or more thereof.

Among these, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, etc. are preferable from the viewpoint of the thermal decomposition resistance and fluidity of a copolymer, , Methyl acrylate and n-butyl acrylate are particularly preferably used.

It is preferable that an acrylic resin has a weight average molecular weight (Mw) of 80000-1 million from the mechanical strength as a film and the fluidity | liquidity at the time of producing a film. The weight average molecular weight (Mw) can be measured using the above-mentioned high performance liquid chromatography.

There is no restriction | limiting in particular as a manufacturing method of an acrylic resin (A), You may use any of well-known methods, such as suspension polymerization, emulsion polymerization, block polymerization, or solution polymerization. Here, as a polymerization initiator, the thing of normal poxide type and azo type can be used, and it can also be set as a redox system. About superposition | polymerization temperature, in suspension or emulsion polymerization, it can carry out at 80-100 degreeC by 30-100 degreeC, agglomeration, or solution polymerization. In addition, in order to control the reduced viscosity of the product copolymer, polymerization may be performed using alkyl mercaptan or the like as a chain transfer agent. By setting it as this molecular weight, both heat resistance and brittleness can be aimed at. As an acrylic resin, a commercially available thing can also be used. For example, Delpet 60N, 80N (made by Asahi Chemical Co., Ltd.), diamond BR52, BR80, BR83, BR85, BR88 (made by Mitsubishi Rayon), KT75 (made by Denki Chemical Industries, Ltd.), etc. Can be mentioned.

Next, the cellulose ester may further contain acrylic particles in addition to the acrylic resin, and further excellent film strength (scratch resistance and pencil hardness) is obtained by containing the acrylic particles.

Next, the acrylic particles will be described. The acrylic particles are, for example, made of a PTFE resin having a pore diameter of less than the average particle diameter of the acrylic particles at a time when a predetermined amount of the produced acrylic resin-containing film is collected, dissolved in a solvent, stirred, and sufficiently dissolved and dispersed. It is preferable that the weight of the insoluble matter collected by filtering using a membrane filter is 90 mass% or more of the acrylic particle added to the acrylic resin containing film.

Although an acryl particle is not specifically limited, It is preferable that it is an acryl particle which has a layer structure of two or more layers, and it is especially preferable that it is the following multilayer structure acrylic granular composite_body | complex.

The multi-layered acrylic granular composite refers to a granular acrylic polymer having a structure in which the innermost hard layer polymer, the crosslinked soft layer polymer exhibiting rubber elasticity, and the outermost hard layer polymer overlap each other in a layer form from the center portion to the outer peripheral portion. .

As a preferable aspect of the multilayer structure acrylic granular composite body used for an acrylic resin composition, the following are mentioned. (a) Inner hardest obtained by superposing | polymerizing the monomer mixture which consists of 80-98.9 mass% of methyl methacrylates, 1-20 mass% of alkyl acrylates with 1-8 carbon atoms of an alkyl group, and 0.01-0.3 mass% of polyfunctional grafting agents. In the presence of the layer polymer and (b) the innermost hard layer polymer, 75 to 98.5 mass% of alkyl acrylate having 4 to 8 carbon atoms of alkyl group, 0.01 to 5 mass% of polyfunctional crosslinking agent and 0.5 to 5 mass% of polyfunctional grafting agent Crosslinked soft layer polymer obtained by superposing | polymerizing the monomer mixture which consists of a (c) alkyl of 80-99 mass% of methyl methacrylates and C1-C8 of an alkyl group in presence of the polymer which consists of said innermost hard layer and crosslinked soft layer. It has a three layer structure which consists of an outermost hard layer polymer obtained by superposing | polymerizing the monomer mixture which consists of 1-20 mass% of acrylates, and the obtained three layer structure polymer is the innermost hard layer polymer (a) 5 It consists of -40 mass%, a soft layer polymer (b) 30-60 mass%, and the outermost hard layer polymer (c) 20-50 mass%, and when fractionated with acetone, there exists an insoluble part and the methyl ethyl ketone swelling degree of the insoluble part And acrylic granular composite having 1.5 to 4.0.

Further, as disclosed in Japanese Patent Publication No. 60-17406 or Japanese Patent Publication No. Hei 3-39095, not only the composition and particle diameter of each layer of the multilayered acrylic granular composite are prescribed, but also the multilayered acrylic granular By setting the tensile modulus of elasticity and the methyl ethyl ketone swelling degree of the acetone insoluble portion within a specific range, it is possible to realize a sufficient balance of impact resistance and stress whitening resistance.

Here, the innermost hard-layer polymer (a) which comprises a multilayered acryl-type granular composite_body | complex has 80-98.9 mass% of methyl methacrylates, 1-20 mass% of alkyl acrylates with 1-8 carbon atoms of an alkyl group, and a polyfunctional grafting agent It is preferable to obtain by superposing | polymerizing the monomer mixture which consists of 0.01-0.3 mass%.

As the alkyl acrylate having 1 to 8 carbon atoms of the alkyl group, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like can be given. Methyl acrylate or n-butyl acrylate can be used preferably.

When the ratio of the alkyl acrylate unit in the innermost hard layer polymer (a) is 1-20 mass%, when the unit is less than 1 mass%, the thermal decomposition property of a polymer will become large, and if the unit exceeds 20 mass%, Since the glass transition temperature of an innermost hard layer polymer (c) falls and the impact resistance imparting effect of a three-layered acryl-type granular composite lowers, it is unpreferable.

As a polyfunctional graft agent, the polyfunctional monomer which has another polymerizable functional group, for example, the allyl ester of acrylic acid, methacrylic acid, maleic acid, and fumaric acid, etc. are mentioned, Allyl methacrylate is used preferably. A polyfunctional graft agent is used in order to chemically bond an innermost hard layer polymer and a soft layer polymer, and the ratio used at the time of innermost hard layer superposition | polymerization is 0.01-0.3 mass%.

The crosslinked soft layer polymer (b) constituting the acrylic granular composite is 75 to 98.5% by mass of an alkyl acrylate having 1 to 8 carbon atoms of an alkyl group in the presence of the innermost hard layer polymer (a), and 0.01 to polyfunctional crosslinking agent. It is preferable to obtain by superposing | polymerizing the monomer mixture which consists of 5 mass% and 0.5-5 mass% of polyfunctional grafting agents.

Here, as the alkyl acrylate having 4 to 8 carbon atoms in the alkyl group, n-butyl acrylate and 2-ethylhexyl acrylate are preferably used.

Moreover, it is also possible to copolymerize 25 mass% or less of other copolymerizable monofunctional monomer with these polymerizable monomers.

Other monofunctional monomers copolymerizable include styrene and substituted styrene derivatives. As for the ratio of the alkyl acrylate and styrene of 4-8 carbon atoms of an alkyl group, the glass transition temperature of the produced polymer (b) falls, that is, it softens as there are many electrons.

On the other hand, it is more advantageous from the viewpoint of transparency of a resin composition to make refractive index in normal temperature of a soft layer polymer (b) close to an innermost hard layer polymer (a), an outermost hard layer polymer (c), and a rigid thermoplastic acrylic resin. In consideration of these, the ratio of both is selected.

For example, in applications where the coating layer thickness is small, the styrene may not necessarily be copolymerized.

As a polyfunctional graft agent, what was illustrated by the term of the innermost layer hard polymer (a) can be used. The polyfunctional graft agent used here is used in order to chemically bond a soft layer polymer (b) and an outermost hard layer polymer (c), and the ratio used at the time of innermost hard layer polymerization is 0.5 from a viewpoint of impact resistance provision effect. -5 mass% is preferable.

As a polyfunctional crosslinking agent, generally known crosslinking agents, such as a divinyl compound, a diaryl compound, a diacryl compound, and a dimethacryl compound, can be used, but polyethyleneglycol diacrylate (molecular weight 200-600) is used preferably. .

The polyfunctional crosslinking agent used here is used in order to produce a crosslinked structure at the time of superposition | polymerization of a soft layer (b), and to express the effect of imparting impact resistance. However, when the previous multifunctional graft agent is used in the polymerization of the soft layer, to some extent, it produces a crosslinked structure of the soft layer (b), so that the multifunctional crosslinking agent is not an essential component, but the polyfunctional crosslinking agent is used during the soft layer polymerization. As for the ratio used to, 0.01-5 mass% is preferable from a viewpoint of an impact resistance provision effect.

The outermost hard layer polymer (c) constituting the multilayered acrylic granular composite has 80 to 99 mass% of methyl methacrylate and carbon number of an alkyl group in the presence of the innermost hard layer polymer (a) and the soft layer polymer (b). It is preferable to obtain by superposing | polymerizing the monomer mixture which consists of 1-20 mass% of alkyl acrylates which are 1-8.

Here, although the above-mentioned thing is used as an acryl alkylate, methyl acrylate and ethyl acrylate are used preferably. As for the ratio of the alkyl acrylate unit in outermost hard layer (c), 1-20 mass% is preferable.

At the time of polymerization of the outermost hard layer (c), for the purpose of improving the compatibility with the acrylic resin (A), in order to adjust the molecular weight, alkyl mercaptan or the like can also be used as a chain transfer agent.

In particular, it is preferable to set the gradient in which the molecular weight gradually decreases from the inner side to the outermost hard layer in improving the balance between elongation and impact resistance. As a specific method, it is possible to reduce the molecular weight from the inside to the outside by a method of dividing the monomer mixture for forming the outermost hard layer into two or more and sequentially increasing the amount of the chain transfer agent added each time. . The molecular weight formed at this time can also be investigated by polymerizing the monomer mixture used for each time on the same conditions independently, and measuring the molecular weight of the obtained polymer. Although it does not specifically limit about the particle diameter of the acryl-type granular composite which is a multilayer structure polymer, It is preferable that it is 10 nm or more and 1000 nm or less, Furthermore, it is more preferable that it is 20 nm or more and 500 nm or less, Especially 50 nm or more, 400 Most preferably, it is nm or less.

Although the mass ratio of a core and a shell is not specifically limited in the acrylic granular composite which is a multilayered structure polymer, When the whole multilayered structure polymer is 100 mass parts, it is preferable that a core layer is 50 mass parts or more and 90 mass parts or less, and also It is more preferable that they are 60 mass parts or more and 80 mass parts or less.

As an example of the commercial item of such a multilayer-structure acryl-type granular composite, For example, "Metablene" by Mitsubishi Rayon, "Kanesu" by Kanega Fuchi Chemical Industry, "Paraloid" by Kureha Chemical Industry, "Acryloid" by Rohm and Haas, Inc. "" Staphiloid "by Kantsu Kasei Kogyo Co., Ltd.," parapet SA "by Claresa, etc. are mentioned, These can use single or 2 types or more.

Specific examples of the acrylic particles (c-1) which are graft copolymers suitably used as the acrylic particles include unsaturated carboxylic acid ester monomers, unsaturated carboxylic acid monomers, aromatic vinyl monomers, and necessities in the presence of a rubbery polymer. Therefore, the graft copolymer which copolymerized the monomer mixture which consists of another vinylic monomer copolymerizable with these is mentioned.

There is no restriction | limiting in particular in the rubbery polymer used for the acryl particle | grain (c-1) which is a graft copolymer, A diene rubber, an acrylic rubber, ethylene rubber, etc. can be used. Specific examples include polybutadiene, styrene-butadiene copolymers, block copolymers of styrene-butadiene, acrylonitrile-butadiene copolymers, butyl-butadiene acrylates, polyisoprene, butadiene-methyl methacrylate copolymers, and butyl acrylates. Methyl methacrylate copolymer, butadiene-ethyl acrylate copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-isoprene copolymer, ethylene-methyl acrylate copolymer and the like. These rubbery polymers can be used by 1 type, or 2 or more types of mixtures.

Moreover, when each refractive index of an acrylic resin and an acryl particle is approximating, since transparency of a base film can be obtained, it is preferable. Specifically, the refractive index difference between the acrylic particles (C) and the acrylic resin (A) is preferably 0.05 or less, more preferably 0.02 or less, particularly preferably 0.01 or less.

In order to satisfy such refractive index conditions, the refractive index difference can be made small by the method of adjusting the monomer unit composition ratio of an acrylic resin, and / or the composition ratio of the rubbery polymer or monomer used for acrylic particle, etc., An acrylic resin containing film excellent in transparency can be obtained.

In addition, with the refractive index difference here, an acrylic resin containing film is melt | dissolved in the solvent in which an acrylic resin is soluble under suitable conditions sufficiently, it is made into a cloudy solution, and this is isolate | separated into a solvent soluble part and an insoluble part by operation, such as centrifugation, After refine | purifying this soluble part (acrylic resin and an insoluble part (acrylic particle), respectively), the difference of the measured refractive index (23 degreeC, measurement wavelength: 550 nm) is shown.

There is no restriction | limiting in particular in the method of mix | blending an acrylic particle with an acrylic resin, After blending an acrylic resin and other arbitrary components previously, Usually, it carries out by single- or twin-screw extruder, adding acrylic particle at 200-350 degreeC. The method of melt-kneading uniformly is used preferably.

As the acrylic particles, commercially available ones can be used. For example, metablene W-341 (C2) (made by Mitsubishi Rayon Co., Ltd.), Chemisuno MR-2G (C3), MS-300X (C4) (made by Soken Chemical Co., Ltd.), etc. are mentioned.

It is preferable that an acryl particle contains 0.5-45 mass% of acryl particle with respect to the gross mass of a cellulose ester resin and an acrylic resin.

Moreover, the film which consists of a cellulose ester resin and an acrylic resin (henceforth a cellulose ester resin and an acrylic resin film) is 105-145 degreeC of tension softening points, and the film which does not produce ductile fracture is preferable. A ductile fracture is generated by a greater stress than the strength of a certain material, and is defined as rupture involving significant elongation or shrinkage of the material until the final fracture. As a specific measuring method of the tension softening point temperature, an acrylic resin-containing film is cut out as 120 mm (length) x 10 mm (width), for example using a tensilon tester (RTC-1225A manufactured by ORIENTEC Corporation), The temperature is continued at a temperature increase rate of 30 ° C./min while pulling under tension, and the temperature at the time point of 9 N can be measured three times, and the average value can be obtained.

Moreover, it is preferable that glass transition temperature (Tg) of the film which consists of a cellulose ester resin and an acrylic resin is 110 degreeC or more. More preferably, it is 120 degreeC or more. Especially preferably, it is 150 degreeC or more.

The glass transition temperature is an intermediate point glass transition temperature (Tmg) measured at a heating rate (20 ° C / min) and determined according to JIS K7121 (1987) using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer). .

As for the film which consists of a cellulose ester resin and an acrylic resin, it is preferable that the elongation at break of at least one direction is 10% or more in the measurement based on JIS-K7127-1999, More preferably, it is 20% or more. Although the upper limit of breaking elongation is not specifically limited, In reality, it is about 250%. In order to enlarge a breaking elongation, it is effective to suppress the fault in the film resulting from a foreign material and foaming. It is preferable that the thickness of the film which consists of cellulose ester resin and an acrylic resin is 20 micrometers or more.

More preferably, it is 30 micrometers or more. Although the upper limit of thickness is not specifically limited, When film-forming by the solution film forming method, an upper limit is about 250 micrometers from the viewpoint of coating property, foaming, and solvent drying. In addition, the thickness of a film can be suitably selected according to a use.

It is preferable that the film which consists of a cellulose ester resin and an acrylic resin contains an acrylic resin and a cellulose ester resin in the mass ratio of 95: 5-30: 70 from the point of compatibility of workability and heat resistance, and also the acyl group of a cellulose ester resin The total substitution degree (T) is 2.00 to 3.00, the acetyl group substitution degree (ac) is 0 to 1.89, carbon number of acyl groups other than the acetyl group is 3 to 7, and the weight average molecular weight (Mw) is 75000 to 280000 desirable. In addition, the gross mass of an acrylic resin and a cellulose ester resin is 55-100 mass% of an acrylic resin containing film, Preferably it is 60-99 mass%.

The film which consists of a cellulose ester resin and an acrylic resin may contain another acrylic resin and may be comprised. The mechanical strength of a film | membrane becomes strong by containing an acrylic resin and acrylic particle in a cellulose ester resin.

The film containing these cellulose ester resins is pressurized on the casting support of the endless metal belt or rotating metal drum which transfers the cellulose ester dissolution liquid (dope) generally called the solution casting film forming method to infinity, for example. It is preferable to manufacture by the method of casting (casting) dope from a die and forming a film.

(Organic solvent)

As an organic solvent used for preparation of these dope, a cellulose ester can be melt | dissolved and it is preferable that it is a suitable boiling point, for example, methylene chloride, methyl acetate, ethyl acetate, amyl acetate, methyl acetate, acetone , Tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro- 1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3, 3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, 1,3-dimethyl-2-imidazolidinone, and the like, but methylene Organic halogen compounds, such as chloride, a dioxolane derivative, methyl acetate, ethyl acetate, acetone, methyl acetate, etc. are mentioned as a preferable organic solvent (namely, good solvent). .

Moreover, as demonstrated in the following film forming process, when drying a solvent from the web (dope film) formed on the casting support in a solvent evaporation process, it is a boiling point of the organic solvent used from a viewpoint of preventing foaming in a web. The boiling point of the good solvent described above is, for example, methylene chloride (boiling point 40.4 degrees), methyl acetate (boiling point 56.32 degrees), acetone (boiling point 56.3 degrees), ethyl acetate (boiling point 76.82). And the like).

Among the good solvents described above, methylene chloride or methyl acetate excellent in solubility is preferably used.

It is preferable to contain 0.1-40 mass% C1-C4 alcohol other than the said organic solvent. Especially preferably, it is preferable that the said alcohol is contained in 5-30 mass%. They soften the dope as described above to the casting support, and then, when the solvent starts to evaporate and the proportion of alcohol increases, the web (dope film) gels, which makes the web strong and facilitates peeling from the casting support. When used as a solvent or when the ratio is small, it also plays a role of promoting dissolution of the cellulose ester of the non-chlorine organic solvent.

Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, and the like.

Among these solvents, ethanol is preferable because of the good dope stability, relatively low boiling point, good dryness and no toxicity. Preferably, it is preferable to use the solvent containing 5-30 mass% of ethanol with respect to 70-95 mass% of methylene chloride. Methyl acetate may be used instead of methylene chloride. At this time, you may prepare dope by a cooling solution method.

Or methylene chloride and methyl acetate can also be used together and can be used together, for example by mass ratio of 10.1-3. It is preferable to further contain the above-mentioned alcohol here.

(Plasticizer)

When using a cellulose ester film for the anti-glare antireflection film of this invention, it is preferable to contain the following plasticizers. Examples of the plasticizer include a phosphate ester plasticizer, a phthalic ester plasticizer, a trimellitic acid ester plasticizer, a pyromellitic acid plasticizer, a glycolate plasticizer, a citric acid ester plasticizer, a polyester plasticizer and a polyhydric alcohol ester plasticizer. Etc. can be used preferably.

In the phosphate ester plasticizer, in the phthalate ester plasticizer, such as triphenyl phosphate, tricredil phosphate, credil diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate and tributyl phosphate, diethyl phthalate, In trimellitic acid plasticizers, such as dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butylbenzyl phthalate, diphenyl phthalate and dicyclohexyl phthalate, tributyl trimellitate In pyromellitic acid ester plasticizers, such as a triphenyl trimellitate and a triethyl trimellitate, in a glycolate plasticizer, such as tetrabutyl pyromellitate, tetraphenyl pyromellitate, and tetraethyl pyromellitate, triacetin, Tributyline, In citric acid ester plasticizers, such as ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, and butyl phthalyl butyl glycolate, triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, and acetyl tri- n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used. Examples of other carboxylic acid esters include trimethylolpropane tribenzoate, butyl oleate, methyl acetyl ricinolic acid, dibutyl sebacate, and various trimellitic acid esters.

The polyhydric alcohol ester plasticizer is a plasticizer composed of an ester of a divalent or higher aliphatic polyhydric alcohol and a mono carboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. Preferably they are 2-20 valent aliphatic polyhydric alcohol ester.

As the polyester plasticizer, copolymers of dibasic acids and glycols such as aliphatic dibasic acids, alicyclic dibasic acids and aromatic dibasic acids can be used. Although it does not specifically limit as aliphatic dibasic acid, Adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1, 4- cyclohexyl dicarboxylic acid, etc. can be used. As glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, etc. can be used. Can be. These dibasic acids and glycols may be used independently, respectively, and may mix and use 2 or more types.

As for the usage-amount of these plasticizers, 1-20 mass% is preferable with respect to a cellulose ester from a point of film performance, workability, etc., Especially preferably, it is 3-13 mass%.

(UV absorber)

The ultraviolet absorber is used suitably for the anti-glare antireflection film of this invention.

As a ultraviolet absorber, the thing excellent in the absorptivity of the ultraviolet-ray of wavelength 370nm or less, and the absorption of visible light of wavelength 400nm or more from a viewpoint of favorable liquid crystal display property is used preferably.

As a specific example of the ultraviolet absorber used preferably for this invention, For example, an oxy benzophenone type compound, a benzotriazole type compound, a triazine type compound, a salicylic acid ester type compound, a benzophenone type compound, a cyano acrylate type compound, nickel Although complex salt compounds etc. are mentioned, It is not limited to these.

As a benzotriazole type ultraviolet absorber, although the following ultraviolet absorber is mentioned as a specific example, this invention is not limited to these, for example.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole

UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butyl phenyl) benzotriazole

UV-3: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole

UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butyl phenyl) -5-chloro benzotriazole

UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidemethyl) -5'-methylphenyl) benzotriazole

UV-6: 2,2-methylene bis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)

UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro benzotriazole

UV-8: 2- (2H-benzotriazol-2-yl) -6- (straight and branched dodecyl) -4-methyl phenol (TINUVIN171, made by Ciba)

UV-9: octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3 A mixture of -tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba)

In addition, although the following specific example is shown as a benzophenone type ultraviolet absorber, this invention is not limited to these.

UV-10: 2,4-dihydroxy benzophenone

UV-11: 2,2'-dihydroxy-4-methoxy benzophenone

UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone

UV-13: bis (2-methoxy-4-hydroxy-5-benzoylphenylmethane)

As the ultraviolet absorber which is preferably used in the present invention, a benzotriazole-based ultraviolet absorber or a benzophenone-based ultraviolet absorber, which has high transparency and is excellent in preventing the deterioration of the polarizing plate and the liquid crystal, is preferable, and the benzotriazole-based ultraviolet ray having less unnecessary coloring is used. Absorbents are particularly preferably used.

Moreover, the ultraviolet absorber whose distribution coefficient described in Unexamined-Japanese-Patent No. 2001-187825 is 9.2 or more improves the surface quality of a long film, and is excellent also in applicability | paintability. In particular, it is preferable to use an ultraviolet absorbent having a distribution coefficient of 10.1 or more.

Moreover, the polymeric ultraviolet absorber (or ultraviolet absorbent polymer) described in General formula 1 or General formula 2 of Unexamined-Japanese-Patent No. 6-148430, and General formula 2, 6, 7 of Japanese Patent Application 2000-156039 is also used preferably. do. As a polymer ultraviolet absorber, PUVA-30M (made by Otsuka Chemical Co., Ltd.) etc. is marketed.

(Particulates)

In addition, microparticles | fine-particles can be used for the cellulose ester film used for this invention in order to provide slipperiness | lubricacy.

Examples of the inorganic compound include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, calcium hydrate silicate, aluminum silicate, magnesium silicate and calcium phosphate. Can be mentioned. It is preferable that microparticles | fine-particles contain silicon in the point that turbidity becomes low, and especially silicon dioxide is preferable.

5-50 nm is preferable and, as for the average diameter of the primary particle of microparticles | fine-particles, 7-20 nm is more preferable. It is preferable to contain these mainly as a secondary aggregate of particle size 0.05-0.3 micrometers. It is preferable that it is 0.05-1 mass%, and, as for content of these microparticles | fine-particles in a cellulose ester film, 0.1-0.5 mass% is especially preferable. In the case of the cellulose-ester film of the multilayered constitution by a covalent smoke method, it is preferable to contain this addition amount microparticles on the surface.

The fine particle of silicon dioxide is marketed under the brand name of aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above Japan Aerosil Co., Ltd. make), for example. There is it and can use it.

The fine particles of zirconium oxide are commercially available under the trade names of, for example, Aerosil R976 and R811 (above, Japan Aerosol Co., Ltd.) and can be used.

Examples of the polymer include silicone resins, fluororesins and acrylic resins. A silicone resin is preferable, and it is especially preferable to have a three-dimensional network structure, for example, tospearl 103, 105, 108, 120, 145, 3120, and 240 (above Toshiba Silicone (main) It is marketed under a brand name of) and can use it.

Among these, aerosil 200V and aerosil R972V are particularly preferably used because the effect of lowering the coefficient of friction is great while keeping the turbidity of the cellulose ester film low.

(Method for producing cellulose ester film)

The cellulose ester film of the present invention can be preferably used either by the solution casting method or the melt casting method.

Hereinafter, the manufacturing method of a cellulose ester film is demonstrated, taking a solution casting method as an example.

The manufacture of a cellulose ester film is a process of preparing a dope by dissolving a cellulose ester and an additive in a solvent, the process of casting dope on a belt-shaped or drum-shaped metal support, the process of drying a flexible dope as a web, and the metal support from It is performed by the process of peeling, the process of extending | stretching or holding a width, the process of drying, and the process of winding up the finished film.

The process of preparing dope is demonstrated. The higher concentration of the cellulose ester in the dope can reduce the dry load after being flexible to the metal support. However, if the concentration of the cellulose ester is too high, the load during filtration increases and the filtration accuracy deteriorates. As a density | concentration which makes these compatible, 10-35 mass% is preferable, More preferably, it is 15-25 mass%.

Although the solvent used by dope may be used independently or may use 2 or more types together, it is preferable to mix and use the good solvent and poor solvent of a cellulose ester from a point of production efficiency, and the one with many good solvents is solubility of a cellulose ester. It is preferable at the point of. The preferable range of the mixing ratio of a good solvent and a poor solvent is 70-98 mass% of good solvents, and is 2-30 mass% of poor solvents. A good solvent and a poor solvent are defined as a poor solvent which melt | dissolves the cellulose ester to be used independently and swells alone or does not melt | dissolve alone. Therefore, a good solvent and a poor solvent change with acyl group substitution degree of a cellulose ester, For example, when using acetone as a solvent, the acetic acid ester of a cellulose ester (acetyl group substitution degree 2.4), cellulose acetate propionate In the case of a good solvent, in the acetate ester of cellulose (acetyl group substitution degree 2.8), it becomes a poor solvent.

Although the good solvent used for this invention is not specifically limited, Organic halogen compounds, such as methylene chloride, dioxolane, acetone, methyl acetate, acet methyl acetate, etc. are mentioned. Especially preferably, methylene chloride or methyl acetate is mentioned.

In addition, the poor solvent used for this invention is although it does not specifically limit, For example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone, etc. are used preferably. Moreover, it is preferable to contain 0.01-2 mass% of water in dope.

As a dissolution method of the cellulose ester at the time of preparing the dope described above, a general method can be used. Combining heating and pressurization enables heating above the boiling point at normal pressure. It is preferable to melt and dissolve while heating at a temperature in a range not lower than the boiling point of the solvent at a normal pressure and the solvent does not boil under pressure, because it prevents the formation of gel or lump debris called mamako. Moreover, after mixing a cellulose ester with a poor solvent and making it wet or swell, the method of adding and dissolving a good solvent again is also used preferably.

Pressurization may be performed by a method of press-fitting an inert gas such as nitrogen gas, or by increasing the vapor pressure of the solvent by heating. It is preferable to perform heating from the outside, for example, a jacket type thing is preferable because temperature control is easy.

The higher the heating temperature at which the solvent is added is preferable from the viewpoint of the solubility of the cellulose ester, but when the heating temperature is too high, the required pressure becomes large and the productivity becomes poor. Preferable heating temperature is 45-120 degreeC, 60-110 degreeC is more preferable, and 70 degreeC-105 degreeC is still more preferable. In addition, the pressure is adjusted so that the solvent does not boil at the set temperature.

Or a cooling solution method is also used preferably and can dissolve a cellulose ester in solvent, such as methyl acetate, by this.

Next, this cellulose ester solution is filtered using suitable filter media, such as a filter paper. As a filter medium, although the absolute filtration precision is preferable in order to remove an insoluble matter etc., when the absolute filtration precision is too small, there exists a problem that clogging of a filter medium is easy to produce. For this reason, the filter medium of 0.008 mm or less of absolute filtration accuracy is preferable, A 0.001-0.008 mm filter medium is more preferable, A 0.003-0.006 mm filter medium is still more preferable.

There is no restriction | limiting in particular in the material of a filter medium, Although a normal filter medium can be used, The filter medium made from plastics, such as a polypropylene and Teflon (trademark), and the metal filter material, such as stainless steel, are preferable because there is no fallout of a fiber. It is preferable to remove and reduce the impurities contained in the cellulose ester of the raw material, in particular, the bright point foreign matter by filtration.

A bright spot foreign material means that two polarizing plates are placed in a cross nicol state, a cellulose ester film is placed therebetween, light is aligned from one polarizing plate side, and the light from the opposite side is observed when viewed from the other polarizing plate side. It refers to the leaked point (foreign substance), and it is preferable that the number of bright spots whose diameter is 0.01 mm or more is 200 pieces / cm <2> or less. More preferably, it is 100 piece / cm <2> or less, More preferably, it is 50 piece / m <2> or less, More preferably, it is 0-10 piece / cm <2> or less. Moreover, the one with less bright point of 0.01 mm or less is also preferable.

Although filtering of dope can be performed by a normal method, the method of filtering, heating at the temperature of the range which is more than the boiling point in the normal pressure of a solvent and does not boil under pressurization is the difference of the filtration pressure before and behind filtration (differential pressure is Rise) is small and preferable. Preferable temperature is 45-120 degreeC, 45-70 degreeC is more preferable, and it is still more preferable that it is 45-55 degreeC.

The smaller the filtration pressure is, the better. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and even more preferably 1.0 MPa or less.

Here, the softening of the dope will be described.

It is preferable that the surface of the metal support body in the casting process is mirror-treated, and as a metal support body, the drum which plated the surface with the stainless steel belt or the casting is used preferably. The width of the cast can be 1 to 4 m. The surface temperature of the metal support of a casting process is set to -50 degreeC-below the temperature at which a solvent boils and does not foam. The higher the temperature, the faster the drying speed of the web. However, if the temperature is too high, the web may foam or the flatness may deteriorate. As preferable metal support temperature, it determines suitably at 0-100 degreeC, and 5-30 degreeC is more preferable. Or it is also a preferable method to gelatinize a web by cooling and peeling from a drum in the state containing many residual solvents. The method of controlling the temperature of the metal support is not particularly limited, but there is a method of blowing hot or cold air or a method of bringing hot water into contact with the back side of the metal support. Since the use of warm water makes heat transfer more efficient, the time until the temperature of the metal support becomes constant is preferable. In the case of using the warm air, in consideration of the temperature drop of the web due to latent heat of evaporation of the solvent, the wind of temperature higher than the target temperature may be used while preventing the foaming while using the warm air above the boiling point of the solvent. It is preferable to change the temperature of a metal support body and the temperature of a drying wind until it peels from casting | flow_spread especially, and to dry efficiently.

In order for a cellulose-ester film to show favorable planarity, the amount of residual solvent at the time of peeling a web from a metal support body is preferable, More preferably, it is 20-40 mass% or 60-130 mass%, Especially preferably, it is 20-30 mass% or 70-120 mass%.

In the present invention, the residual solvent amount is defined by the following formula.

Residual solvent amount (mass%) = {(M-N) / N} × 100

In addition, M is the mass of the sample extract | collected at the arbitrary time after manufacture of a web or a film, and N is the mass after heating M at 115 degreeC for 1 hour.

Moreover, in the drying process of a cellulose ester film, it is preferable to peel a web from a metal support body, to dry again, and to make residual solvent amount 1 mass% or less, More preferably, it is 0.1 mass% or less, Especially preferably, It is 0-0.01 mass% or less.

In the film drying process, generally, the method of drying while conveying a web is employ | adopted by the roll drying method (the method of passing the web through several webs rolled up and down alternately), and a tenter system.

In order to manufacture the cellulose-ester film for anti-glare antireflection film of this invention, the tenter which extends to a conveyance direction at the time of many residual solvent amounts of the web immediately after peeling from a metal support body, and grips both ends of a web with a clip etc. It is especially preferable to extend | stretch in the width direction in a manner. In the longitudinal direction and the transverse direction, the preferred draw ratio is 1.05 to 1.5 times, more preferably 1.05 to 1.3 times, and more preferably 1.05 to 1.15 times. It is preferable that the area is 1.1 to 2 times by the longitudinal direction and the lateral direction stretching. This can be calculated | required by the draw ratio of a draw ratio of the longitudinal direction x a transverse direction.

In order to extend | stretch to a longitudinal direction immediately after peeling, it is preferable to extend | stretch by peeling tension and subsequent conveyance tension. For example, it is preferable to peel peeling tension at 210 N / m or more, Especially preferably, it is 220-300 N / m.

There is no restriction | limiting in particular in the means for drying a web, Generally, although it can carry out by hot air, an infrared ray, a heating roll, a microwave, etc., it is preferable to carry out by hot air from the point of simplicity.

It is preferable to make a drying temperature in the drying process of a web step by step high at 30-150 degreeC, and since carrying out in 50-140 degreeC improves dimensional stability, it is more preferable.

Although the film thickness of a cellulose ester film is not specifically limited, 10-200 micrometers is used preferably. Especially since it is excellent also in productivity, it is preferable that the film thickness of a cellulose-ester film is 10-70 micrometers. More preferably, it is 20-60 micrometers. Most preferably, it is 30-60 micrometers. Moreover, the cellulose ester film which set it as a multilayered structure by the co-combustion method can also be used preferably. Even when a cellulose ester is a multilayered structure, it has a layer containing a ultraviolet absorber and a plasticizer, and it may be a core layer, a skin layer, or both.

As the anti-glare antireflection film of the present invention, a cellulose ester film having a width of 1.4 to 4 m is preferably used. In particular, the film of 1.5-3 m is preferable from a point of productivity, and the film of 2-3 m is more preferable.

[Polarizing plate]

The polarizing plate using the anti-glare antireflection film of this invention is demonstrated.

A polarizing plate can be manufactured by a general method. Alkali reduction treatment of the back surface side of the anti-glare antireflection film of this invention, and the at least one surface of the polarizing film produced by immersing and extending | stretching the processed anti-glare antireflection film in the iodine solution, a fully saponified polyvinyl alcohol aqueous solution It is preferable to join using. You may use the anti-glare antireflection film for the other surface, or you may use another polarizing plate protective film. About the anti-glare antireflection film of this invention, the polarizing plate protective film used for the other side is an optical compensation film which has a phase difference whose in-plane retardation Ro is 590 nm, 20-70 nm, and Rt is 100-400 nm. It is preferable that it is (retardation film). These can be produced, for example, by the methods described in Japanese Patent Application Laid-Open No. 2002-71957 and Japanese Patent Application No. 2002-155395. Or it is preferable to use the polarizing plate protective film which also serves as the optical compensation film which has the optically anisotropic layer formed by orienting liquid crystal compounds, such as a discotic liquid crystal again. For example, an optically anisotropic layer can be formed by the method of Unexamined-Japanese-Patent No. 2003-98348. Or an unoriented film whose Ro is 0-5 nm and Rt is -20-20 + 20 nm at 590 nm is also used preferably.

By using it in combination with the anti-glare antireflection film of this invention, the polarizing plate which is excellent in planarity and has a stable viewing angle enlargement effect can be obtained.

As a polarizing plate protective film used for a back surface side, it is a commercially available cellulose ester film, KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC4FR-2 (Konica Minolta Opto Co., Ltd. product) etc. are used preferably.

The polarizing film which is a main component of a polarizing plate is an element which passes only the light of the polarization plane of a fixed direction, and the typical polarizing film currently known is a polyvinyl alcohol-type polarizing film, and this is the thing which dyed iodine to the polyvinyl alcohol-type film, Although there exist some which dyed a dichroic dye, it is not limited only to this. The polarizing film forms a polyvinyl alcohol aqueous solution, uniaxially stretches this dye, or dyes or uniaxially stretches after dyeing, and preferably a durable treatment with a boron compound is used. As for the film thickness of a polarizing film, the polarizing film of 5-30 micrometers, Preferably 8-15 micrometers is used preferably. On the surface of the polarizing film, one surface of the anti-glare antireflection film of the present invention is bonded to form a polarizing plate. Preferably, it joins by the water-based adhesive which has a fully saponified polyvinyl alcohol etc. as a main component.

[Display device]

By incorporating the antiglare antireflection film surface of the polarizing plate using the antiglare antireflection film of the present invention on the viewing surface side of the display device, a display device excellent in various visibility can be produced. Anti-glare antireflection film of the present invention is a reflective, transmissive, semi-transmissive LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, etc. It is preferably used. In addition, the anti-glare antireflection film of the present invention has a remarkably small color unevenness of the reflected light of the antireflection layer, low reflectance, excellent flatness, plasma display, field emission display, organic EL display, inorganic EL display, It is also preferably used for various display devices such as electronic paper. In particular, in a large-screen image display device having a 30-inch or larger screen, there is little color unevenness or wave unevenness, and there is an effect that the eyes are not tired even in long time viewing.

Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to this. In addition, "part" in an Example shows a "mass part" unless there is particular notice.

(Example 1)

<< production of anti-glare antireflection film 1 >>

<Production of Transparent Support>

The transparent support 1 of the transparent cellulose triacetate film (film thickness of 80 micrometers) was produced as follows.

(Dope composition)

100 parts by mass of cellulose triacetate (average acetylation degree 61.0%)

8 parts by mass of triphenylphosphate

2 parts by mass of ethyl phthalyl ethyl glycolate

Chinubin 109 (Chiba specialty chemicals company) 1 mass part

Chinubin 171 (product of Chiba specialty chemicals company) 1 mass part

Methylene chloride 430 parts by mass

90 parts by mass of methanol

The composition was placed in a sealed container, kept at 80 ° C under pressure, and dissolved completely while stirring to obtain a dope composition.

Next, this dope composition was filtered, it cooled, it hold | maintained at 33 degreeC, it was made to be uniformly flexible on a stainless band, and it peeled from a stainless band at the time of evaporating a solvent until peeling is possible, and it was a tenter in the width direction After extending | stretching by 1.1 times, it dried while conveying with many rolls, the knurling of 10 micrometers in height was provided in both ends, it wound up, and the transparent support body 1 (cellulose triacetate film) of 80 micrometers in thickness, 2 m in width, and 3000 m in length was obtained.

<Formation of Back Coat Layer>

Furthermore, the following backcoat layer coating liquid was die-coated so that it might be set to 14 micrometers of wet film thickness, it dried at 85 degreeC, it wound up, and formed the backcoat layer.

(Coating liquid for back coat layer)

Acetone 30 parts by mass

45 parts by mass of ethyl acetate

10 parts by mass of isopropyl alcohol

0.6 parts by mass of diacetyl cellulose

Ultrafine Silica 2% Acetone Dispersion (Aerosil 200V manufactured by Japan Aerosol Co., Ltd.)

                                           0.2 parts by mass

(Preparation of anti-glare antireflection film 1)

<Formation of Anti-glare Layer 1>

Die-coating the following anti-glare layer 1 coating liquid on the surface opposite to the surface on which the back coat layer of the prepared transparent supporter 1 was applied, dried at 60 ° C. for 1 minute, and then irradiated with 80 mJ / cm 2 UV light using a high pressure mercury lamp to cure. The anti-glare layer 1 was formed so that the film thickness after this might be 6 micrometers.

(Antiglare Layer 1 Coating Liquid)

Synthesis Example 1

(Preparation of carboxyl group-containing acrylic resin solution 1)

433 g of propylene glycol monopropyl ether (PFG) was contained in a 1 L reaction vessel equipped with a thermometer, a stirrer, a cooling tube and a nitrogen introduction tube, and the temperature was raised to 120 ° C under stirring. A solution containing a monomer and a polymerization initiator comprising 155.9 g of styrene (ST), 52.4 g of n-butyl acrylate (NBA), 91.7 g of acrylic acid, and 9.0 g of t-butylperoxy-2-ethylhexanoate was added thereto. Was dripped over 3 hours using the dropping lot. After completion | finish of dripping, after maintaining at 120 degreeC under stirring, the solution which consists of 1.5 g of t-butylperoxy-2-ethylhexanoate and 6.9 g of PFG was dripped over 30 minutes. After completion | finish of dripping, it stirred at 120 degreeC for 2 hours, and continued reaction again, and obtained the resin solution 1 of 40.0% of non volatile matters, and the weight average molecular weight 10000. Obtained resin is acid value 238, This can be used as 1st resin in this invention.

Synthesis Example 2

(Preparation of epoxy group-containing acrylic resin solution 2)

457.6 g of diethylene glycol dimethyl ether (DMDG) was contained in the 1 L reaction container provided with a thermometer, a stirrer, a cooling tube, and a nitrogen introduction tube, and it heated up at 120 degreeC under stirring. A monomer comprising 32.0 g of methyl methacrylate (MMA), 72.0 g of styrene (ST), 216.0 g of glycidyl methacrylate (GMA), and 6.4 g of t-butylperoxy-2-ethylhexanoate; The solution containing a polymerization initiator was dripped over 3 hours using the dropping lot.

After completion | finish of dripping, after maintaining at 120 degreeC under stirring, the solution which consists of 1.0 g of t-butylperoxy-2-ethylhexanoate and 7.4 g of propylene glycol monopropyl ether (PFG) was dripped over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 120 ° C for 2 hours to continue the reaction, thereby obtaining a resin solution 2 having a nonvolatile content of 40.0% and a weight average molecular weight of 16600. Obtained resin is epoxy equivalent 211, and this can be used as 2nd resin in this invention.

(Surface tension measurement)

Each resin was dissolved in diethylene glycol dimethyl ether (DMDG) solvent so as to be 40 mass% of resin solid content, and the solution for surface tension measurement was prepared. The surface tension of this solution was measured at 20 degreeC using the dinometa made from Big Moline Crot International.

On the other hand, when the surface tension of the solvent was measured under the same conditions, the surface tension of the diethylene glycol dimethyl ether (DMDG) solvent was 32.0 dyne / cm, and the surface tension of the propylene glycol monopropyl ether (PFG) solvent was 29.0 dyne / cm. It was. By subtracting the surface tension value of the propylene glycol monomethyl ether acetate (PGMAC) solvent from the measured values for each resin, and then subtracting the difference (3.0 dyne / cm) between the surface tension of the PGMAC solvent and the surface tension of the PFG solvent. And (PFG) which is the surface tension approximation value of the resin component based on the PFG solvent were computed.

The surface tension was measured by the measuring method using the same solvent as the solvent used at the time of the synthesis | combination of resin made into the measuring object the said measuring method. The difference Δγ between the surface tension of the first resin and the surface tension of the second resin was obtained by determining the difference between the numerical values of γ (PFG) of the first resin and γ (PFG) of the second resin thus obtained.

Measured value of surface tension of the first resin: 33.5 dyne / cm

Γ (PFG) of the first resin: -1.5 dyne / cm

Measurement value of the surface tension of the second resin: 31.5 dyne / cm

Γ (PFG) of the second resin: -3.5 dyne / cm

The difference Δγ between the surface tensions of the first resin described in Synthesis Example 1 and the second resin described in Synthesis Example 2 was 2 dyne / cm from the measurement result.

(Antiglare Layer 1 Coating Solution Preparation)

22.50 parts by mass of epoxy group-containing acrylic resin solution 2 (second resin) of Synthesis Example 2 and 15.00 parts by mass of carboxyl group-containing acrylic resin solution 1 (first resin) of Synthesis Example 1 are propylene glycol monomethyl ether acetate (PGMAC) as a dilution solvent. In addition to 62.34 parts by mass, 0.20 parts by mass of SF104E (Sapinol 104E, manufactured by Air Products Japan, Inc., additives) was also added and mixed to prepare an antiglare layer 1 coating liquid.

(Arithmetic mean roughness (Ra))

The arithmetic mean roughness Ra of the surface of the antiglare layer 1 was measured according to JIS B 0601: 2001 and measured for an area of 1.2 mm x 0.9 mm using an optical interference surface roughness meter RST / PLUS (manufactured by WYKO). Nm.

<Formation of Anti-reflective Layer>

(Formation of low refractive index layer 1)

After coating the low refractive index layer coating liquid on the antiglare layer 1 and drying at 80 ° C. for 5 minutes, a low refractive index layer 1 was formed so as to have a film thickness of 92 nm by irradiating 200 mJ / cm 2 ultraviolet light with a high pressure mercury lamp. And the anti-glare antireflection film 1 was produced.

By the said drying and ultraviolet irradiation, the anti-glare layer 1 phase-separated 1st resin and 2nd resin showed the uneven | corrugated shape, and the arithmetic mean roughness Ra of the surface of the low refractive index layer 1 was 350 nm.

In addition, the refractive index of the low refractive index layer 1 was 1.38. The refractive index of the refractive index layer was obtained from the measurement result of the spectral reflectance of the spectrophotometer. The spectrophotometer uses U-4000 type (manufactured by Hitachi, Ltd.) to roughen the back side of the sample side, and then absorbs light with a black spray to prevent reflection of light from the back side. The reflectance of the visible light region (400-700 nm) was measured on condition of.

(Low Refractive Index Layer 1 Coating Liquid)

Propylene glycol monomethyl ether 430 parts by mass

Isopropyl alcohol 430 parts by mass

120 parts by mass of tetraethoxy silane hydrolyzate A (following, in terms of solid content 21%)

γ-methacryloxypropyl trimethoxysilane (brand name: KBM503, Shin-Etsu Chemical Co., Ltd.) 3.0 parts by mass

40 parts by mass of hollow silica fine particles (1) isopropyl alcohol dispersion (average particle diameter 45 nm, particle diameter variation coefficient 30%)

3.0 parts by mass of aluminum ethyl acetate acetate diisopropylate (manufactured by Kawaken Fine Chemicals)

3.0 parts by mass of FZ-2207 (10% propylene glycol monomethyl ether solution, Nippon Unicar Company make)

Acetic acid 4.0 parts by mass

(Preparation of tetraethoxysilane hydrolyzate A)

Tetraethoxysilane hydrolyzate by mixing 230 g of tetraethoxysilane (brand name: KBE04, manufactured by Shin-Etsu Chemical Co., Ltd.) and 440 g of ethanol, adding 120 g of a 2% acetic acid aqueous solution to this, followed by stirring at room temperature (25 ° C) for 28 hours. A was prepared.

(Preparation of hollow silica fine particles 1 isopropyl alcohol dispersion liquid)

A mixture of 100 g of silica sol having an average particle diameter of 5 nm and 20 mass% of SiO ₂ concentration and 1900 g of pure water was heated to 80 ° C. The pH of the reaction mother liquor is 10.5 and, as SiO ₂ in the same mother liquor is 0.98% by mass of aqueous solution of sodium silicate 9000g and Al ₂ O ₃ as sodium aluminate was added to 9000g of an aqueous solution 1.02% by weight at the same time. In the meantime, the temperature of the reaction liquid was kept at 80 degreeC. Immediately after addition, the pH of the reaction solution rose to 12.5, and little changed thereafter. After the addition was completed, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ · Al ₂ O ₃ nuclear particle dispersion having a solid content concentration of 20% by mass (step (a)).

1,700 g of pure water is added to 500 g of the core particle dispersion, and heated to 98 ° C, and 3000 g of a silicic acid solution (3.5 mass% of SiO ₂ concentration) obtained by de-alkaliating an aqueous sodium silicate solution with a cation exchange resin is added while maintaining this temperature. 1 The dispersion liquid of the nuclear particle in which the silica coating layer was formed was obtained (process (b)).

Next, 1125 g of pure water is added to 500 g of the nuclear particle dispersions which were washed with an ultrafiltration membrane to form a first silica coating layer having a solid content concentration of 13% by mass, and 35.5% of concentrated hydrochloric acid was added dropwise to pH 1.0, followed by dealumination treatment. Was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and the SiO ₂ · Al ₂ O ₃ porous particles in which a part of the constituents of the nucleus particles forming the first silica coating layer were removed. A dispersion was prepared (step (c)). The mixture of 1500 g of the porous particle dispersion and 500 g of pure water, 1, 750 g of ethanol, and 626 g of 28% ammonia water was heated to 35 ° C, and 104 g of ethyl silicate (28 mass% of SiO ₂ ) was added thereto to form a first silica coating layer. The surface of the porous particles was coated with a hydrolyzed polycondensate of ethyl silicate to form a second silica coating layer. Next, the dispersion liquid of the hollow silica microparticles 1 of 20 mass% of solid content concentration which substituted the solvent with the isopropyl alcohol using the ultrafiltration membrane was prepared.

The thickness of the first silica coating layer of the hollow silica fine particles 3㎚, average particle diameter was 45㎚, MOx / SiO ₂ (molar ratio) was 0.0017, and the refractive index was 1.28. Here, the variation coefficient of average particle diameter and particle diameter was measured by the dynamic light scattering method.

<< production of anti-glare antireflection film 2 >>

The antiglare reflection was performed in the same manner as in the preparation of the antiglare antireflection film 1 except that the following antiglare layer 2 coating liquid described in JP 2004-69753 A was prepared and used instead of the antiglare layer 1 coating liquid. The prevention film 2 was produced.

The arithmetic mean roughness Ra of the surface of the antiglare layer 2 was 60 nm.

Arithmetic mean roughness Ra of the anti-glare antireflection film 2 surface was 300 nm.

(Antiglare Layer 2 Coating Solution Preparation)

18 mass parts of acrylic resin A (made by Nihon Paint Corporation, glycidyl methacrylate / styrene = 30/70, solid content 40%, SP value 9.6, weight average molecular weight 16000)

9 mass parts of acrylic resin B (made by Nihon Paint Corporation, acrylic acid / styrene = 30/70, solid content 40%, SP value 13.3, weight average molecular weight 12500)

The following crosslinked resin particles (manufactured by Nippon Paint Co., Ltd., average particle size: 0.5 μm, solid content: 10%)

                                                72 parts by mass

1 part by mass of propylene glycol monomethyl ether acetate

<Crosslinked resin particles>

In a reaction vessel equipped with a stirring heating device, a thermometer, a nitrogen introduction tube, a cooling tube, and a decanter, 213 parts of bishydroxyethyl taurine, 208 parts of neopentyl glycol, 296 parts of phthalic anhydride, 376 parts of azeline acid, and 30 parts of xylene were contained It heated up. The water produced by the reaction was removed by azeotroping with xylene. The reaction solution temperature was set to 210 ° C. over about 3 hours from the start of reflux, and stirring and dehydration were continued to react until the acid value of the carboxylic acid became 135 mgKOH / g. After cooling liquid temperature to 140 degreeC, 500 parts of "Cadula E10" (brand name: Versatic acid glycidyl ester by a shell company) are dripped for 30 minutes, After that, stirring is continued for 2 hours and it complete | finishes reaction. It was. An amphoteric ion-containing polyester resin having an acid value of 55 mgKOH / g, a hydroxyl value of 91 mg / KOH, and a number average molecular weight of 1250 was obtained.

The monomer suspension was adjusted by vigorously stirring in 10 parts of this amphoteric ion-containing polyester resin, 140 parts of deionized water, 1 part of dimethylethanolamine, 50 parts of styrene, and 50 parts of ethylene glycol dimethacrylate in a stainless steel beaker. In addition, an initiator aqueous solution was prepared by mixing 0.5 part of azobis cyano valeric acid, 40 parts of deionized water, and 0.32 part of dimethylethanolamine.

The reaction container provided with the stirring heating apparatus, the thermometer, the nitrogen introduction tube, and the cooling tube contained 5 parts of said positive ion group containing polyester resin, 280 parts of deionized water, and 0.5 part of dimethylethanolamine, and it heated up at 80 degreeC. 251 parts of monomer suspensions and 40.82 parts of initiator aqueous solutions were dripped here simultaneously over 60 minutes, and reaction continued for 60 minutes, and then reaction was complete | finished.

Propylene glycol monomethyl ether acetate is added to the crosslinked resin particle emulsion obtained as described above, water is removed by azeotropic distillation under reduced pressure, the medium is replaced with propylene glycol monomethyl ether acetate, and the crosslinked solid content is 30%. The propylene glycol monomethyl ether acetate solution of the resin particle was obtained.

<< production of anti-glare antireflection film 3 >>

The antiglare reflection was performed in the same manner as in the preparation of the antiglare antireflection film 1 except that the following antiglare layer 3 coating liquid described in Japanese Patent Application Laid-Open No. 2000-267086 was prepared and used instead of the antiglare layer 1 coating liquid. The prevention film 3 was produced.

The arithmetic mean roughness Ra of the surface of the antiglare layer 3 was 65 nm.

Arithmetic mean roughness Ra of the surface of anti-glare antireflection film 3 was 320 nm.

(Antiglare Layer 3 Coating Solution Preparation)

After mixing acrylic resin (refractive index 1.56) and the epoxy resin (refractive index 1.3) which introduced the fluorine group in 1: 2, the two-component mixed resin which stirred for about 2 hours was prepared as anti-glare layer 3 coating liquid.

<< production of anti-glare antireflection film 4 >>

An anti-glare antireflection film 4 was produced in the same manner as the anti-glare antireflection film 1 except that the following high refractive index layer 1 was formed between the anti-glare layer 1 and the low refractive index layer 1.

Arithmetic mean roughness Ra of the antiglare layer 1 surface was 76 nm.

Arithmetic mean roughness Ra of the anti-glare antireflection film 4 surface was 410 nm.

(Formation of high refractive index layer)

After coating the following high refractive index layer 1 coating liquid on the surface of the said glare-proof layer 1, and drying at 80 degreeC, 100 mJ / cm <2> ultraviolet-rays were irradiated with a high pressure mercury lamp, and the high refractive index layer so that the film thickness after hardening may be 110 nm. 1 was installed.

The refractive index of the high refractive index layer 1 was 1.60.

(High refractive index layer 1 coating liquid)

40 parts by mass of PGME (propylene glycol monomethyl ether)

25 parts by mass of isopropyl alcohol

25 parts by mass of methyl ethyl ketone

Pentaerythritol triacrylate 0.9 parts by mass

1.0 parts by mass of pentaerythritol tetraacrylate

0.6 parts by mass of urethane acrylate (brand name: U-4HA, Shinnakamura Chemical Co., Ltd.)

20 parts by mass of particle dispersion A (below)

0.4 mass part of 1-hydroxy cyclohexyl phenyl ketone (irgacure 184, Chiba specialty chemicals company make)

0.2 parts by mass of 2-methyl-1- [4- (methylthio) phenyl] -2-monopolynopropane-1-one (irgacure 907, manufactured by Chiba Specialty Chemicals)

FZ-2207 (10% propylene glycol monomethyl ether solution, manufactured by Nippon Unicar Company)

                                               0.4 parts by mass

(Preparation of Particle Dispersion A)

To 6.0 kg of methanol dispersed antimony double oxide colloid (solid content 60%, Nissan Chemical Co., Ltd. product, antimony acid sol, brand name: Celnax CX-Z610M-F2), 12.0 kg of isopropyl alcohol is slowly added, stirring, and particle | grains Dispersion A was prepared.

<< production of anti-glare antireflection film 5 >>

Except for using the acrylic resin solution 1 containing the hydroxyl group of Synthesis Example 3 in place of the carboxyl group-containing acrylic resin solution 1 of the antiglare layer 1 coating liquid to form an antiglare layer 5, , Anti-glare antireflection film 5 was produced.

The difference Δγ between the surface tension of the first resin and the surface tension of the second resin was 2.4.

The arithmetic mean roughness Ra of the surface of the antiglare layer 5 was 85 nm.

Arithmetic mean roughness Ra of the surface of the anti-glare antireflection film 5 was 450 nm.

Synthesis Example 3

(Preparation of acrylic resin solution 1 containing hydroxyl group)

320.0 g of propylene glycol monopropyl ether (PFG) was contained in the 1 L reaction container provided with a thermometer, a stirrer, a cooling tube, and a nitrogen introduction tube, and it heated up at 110 degreeC under stirring. 302.0 g of methyl methacrylate (MMA), 128.0 g of 4-hydroxybutyl acrylate (4HBA), 47.0 g of hydroxyethyl methacrylate (HEMA), 23.0 g of methacrylic acid (MAA) and t-butylper The monomer and initiator solution which consist of 6.0 g of oxy-2-ethylhexanoate were dripped over 3 hours using the dropping lot. After completion | finish of dripping, it hold | maintained at 110 degreeC under stirring for 30 minutes, and then the solution which consists of 1.0 g of t-butylperoxy-2-ethylhexanoate and 12.0 g of PFG was dripped over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 110 ° C for 2 hours, and the reaction was continued to obtain a resin solution 1 having a nonvolatile content of 55% and a weight average molecular weight of 60000. Obtained resin is hydroxyl value 140 and acid value 30, and this can be used as 1st resin in this invention.

<< Fabrication of Anti-glare Anti-reflection Film 6: Comparative Example >>

In the production of the anti-glare antireflection film 1, after the anti-glare layer 1 is applied, the first resin and the second resin are phase separated and dried at 85 ° C. for 5 minutes, and then irradiated with ultraviolet rays of 220 mJ / cm 2 for anti-glare. The anti-glare antireflection film 6 was produced in the same manner except that the layer 6 was produced.

The arithmetic mean roughness Ra of the surface of the antiglare layer 6 was 270 nm.

Arithmetic mean roughness Ra of the surface of anti-glare antireflection film 6 was 245 nm.

`` Production of an anti-glare antireflection film 7: Comparative example. ''

The following anti-glare layer 7 coating liquid was filtered through a polypropylene filter having a pore diameter of 20 μm on the surface of the transparent support 1 (B surface side; a surface in contact with a support mirror surface such as a stainless steel band used in the flexible film forming method; support side). Anti-glare layer 7 The coating liquid was prepared, and this was applied using a microgravure coater, dried at 90 ° C., and then the ultraviolet-ray lamp was used to cure the coating layer at a dose of 100 mJ / cm 2, and the anti-glare layer 7 having a thickness of 5 μm. Formed.

An anti-glare antireflection film 7 was produced in the same manner as in the preparation of the anti-glare antireflection film 1 except that the anti-glare layer 7 was used.

The arithmetic mean roughness Ra of the surface of the antiglare layer 7 was 133 nm.

Arithmetic mean roughness Ra of the anti-glare antireflection film 6 surface was 118 nm.

(Antiglare Layer 7 Coating Solution Preparation)

Acrylic monomers; 200 parts by mass of Kayarad DPHA (Dipentaerythritol hexaacrylate, Nippon Gunpowder)

Photopolymerization initiator (irgacure 184 (product of Chiba specialty chemicals))

                                               25 parts by mass

110 parts by mass of propylene glycol monomethyl ether

110 parts by mass of ethyl acetate

Synthetic Silica Fine Particles Average Particle Diameter 1.8㎛ 40 parts by mass

Surfactant (silicone surfactant; 10 mass% propylene glycol monomethyl ether solution of FZ2207 (made by Nippon Unicar Co.)) 0.6 part by mass

<< Production of Anti-glare Antireflection Film 8: Comparative Example >>

In the production of the anti-glare antireflection film 1, except that the anti-glare layer 1 was replaced by the following hard coat layer 1, a low-refractive index layer was formed in the same manner, and the anti-reflection film was produced. (Indentation of fine concavo-convex structure of convex part height 1 m, convex part size (long side) 10 m and convex part distance 50 m) Pressing a heat roll provided with a mold on the surface of the low refractive index layer of the film with the prevention film interposed therebetween, arranging a back roll on the opposite surface side, and forming an unevenness on the low refractive index layer by passing between the rolls, and embossing One anti-glare antireflection film 8 was produced.

Arithmetic mean roughness Ra of the surface of hard-coat layer 1 was 20 nm.

Arithmetic mean roughness Ra of the surface of the anti-glare antireflection film 8 was 360 nm, but the variation was large depending on the measurement place.

(Preparation of hard coat layer 1 coating liquid)

Acrylic monomer; 60 parts by weight of KAYARAD DPHA (Dipentaerythritol hexaacrylate, Nippon Gunpowder)

40 parts by mass of trimethylolpropane triacrylate

Photopolymerization initiator (irgacure 184 (product of Chiba specialty chemicals))

                                                  4 parts by mass

50 parts by mass of ethyl acetate

50 parts by mass of propylene glycol monomethyl ether

Silicone type surfactant (BYK-307 (made by BIC Chemie Japan))

                                                   0.5 parts by mass

The following evaluation was performed about the produced anti-glare antireflection films 1-8.

<< evaluation of anti-glare antireflection film >>

(Bright spot defect)

The diameter and the number of bright spots when the light was passed through one side of the anti-glare antireflection film samples disposed on two polarizing plates in the cross nicol state and observed under a microscope were counted.

The bright point number of 5-50 micrometers,

◎: It is not recognized by the naked eye in less than 100

(Circle): It is recognized very little visually in 100 or more-less than 300, but there is no problem in use.

×: It is not usable for liquid crystal display use more than 300

(Scratch resistance)

The sample was subjected to a load of 250 g / cm 2 on a # 0000 steel wool (SW) under an environment of 23 ° C. and 55% RH, and the number of scratches per 1 cm width when measured for 10 round trips was measured. In addition, the number of scratches is measured in the place with the largest number of scratches among the parts to which load is applied. Although it is not a problem practically if it is 10 pieces / cm or less, 5 pieces / cm or less are preferable and 3 pieces / cm or less are more preferable.

◎: Less than three / cm

○: less than 3 / cm-5 / cm

△: less than 5 / cm-10 / cm

×: 10 or more / cm

(reflection)

In an office with a window, each film was spread out on a desk, and the reflection of the fluorescent lamp illumination of the ceiling and the external light on the film was evaluated as follows.

◎: The outline of fluorescent lamps and outside light are blurred and reflection is not minded at all

(Circle): The outline of fluorescent lamp and reflection of exterior light are recognized slightly

(Triangle | delta): The outline of a fluorescent lamp is understood and a reflection is slightly worried

X: We are worried about contour of fluorescent lamp and reflection of outside light

(Shiny)

About the produced film, glare was judged visually.

◎: I do not know the glitter at all

○: I can see the glitter very little

(Triangle | delta): A little glitter is understood.

X: I am worried about glitter pretty

(reflectivity)

About the produced anti-glare antireflection film, the spectral reflectance at the incident angle of 5 degrees was measured in the wavelength range of 380-780 nm using the spectrophotometer (U-4000, the Hitachi make). Since the antireflection performance is better as the reflectance is smaller in a wide wavelength range, the lowest reflectance at 450 to 650 nm is obtained from the measurement results. After the roughening process of the back surface of the observation side, the light absorption process was performed using the black spray, the reflection of the light in the film back surface was prevented, and the reflectance was measured.

◎: Less than 0.8% of reflectance

○: Reflectance 0.8% or more but less than 1.2%

(Triangle | delta): 1.2% or more of reflectance or less than 1.6%

X: More than 1.6% of reflectance

(Clarity)

<Production of Polarizing Plate and Liquid Crystal Display Panel>

The polyvinyl alcohol film of thickness and 120 micrometers was uniaxially stretched (temperature 110 degreeC, draw ratio 5 times). This was immersed for 60 seconds in the aqueous solution which consists of 0.075g of iodine, 5g of potassium iodide, and 100g of water, and then it was immersed in the 68 degreeC aqueous solution which consists of 6g of potassium iodide, 7.5g of boric acid, and 100g of water. This was washed with water and dried to obtain a polarizing film.

Next, according to the following steps 1 to 5, a cellulose ester film Konica Minolta Tech KC4FR-1 (manufactured by Konica Minolta Opto Co., Ltd.) having a commercially available retardation on the polarizing film, the anti-glare antireflection films 1 to 8, and the back side was manufactured. It bonded together and produced the polarizing plate.

Step 1: An anti-glare antireflection film and a cellulose ester film obtained by immersing in a 1 mol / L sodium hydroxide solution at 50 ° C. for 60 seconds, then washing with water and drying, were sensitized.

Process 2: The said polarizing film was immersed for 1-2 second in the polyvinyl alcohol adhesive bath of 2 mass% of solid content.

Step 3: Lightly wipe off the excess adhesive adhering to the polarizing film in step 2, place it on the anti-glare antireflective film and cellulose ester film treated in step 1, and again laminate and place the anti-reflection layer to the outside. .

Process 4: The anti-glare antireflection film laminated | stacked at the process 3, the polarizing film, and the cellulose-ester film sample were bonded at the pressure of 20-30 N / cm <2>, and conveyance speed at about 2 m / min.

Process 5: The sample which bonded the polarizing film, the cellulose-ester film, and anti-glare antireflection film 1-8 produced at the process 4 in 80 degreeC dryer was dried for 2 minutes, and the polarizing plate was produced.

Next, carefully peeling off the polarizing plate of the outermost surface of a commercially available liquid crystal display panel (color liquid crystal display MultiSync LCD1525J: product name LA-1529HM made from NEC), bonding the polarizing plate using the produced anti-glare antireflection film to it, and A display panel was produced.

Using the produced liquid crystal display panel, backlight lighting was performed in the bright room and visual evaluation was performed on the following references | standards about visibility.

◎: Black is seen clearly, and contrast is high

(Circle): Black is seen clearly, but sharpness is slightly low

(Triangle | delta): Black is not sure, vividness is low, and contrast is low

X: The above evaluation results are shown in Table 1 below.

Anti-glare Anti-reflection Film No. Spot defect Scratch resistance reflection Glitter reflectivity Sharpness Remarks One ◎ ◎ ○ ◎ ○ ◎ The present invention 2 ◎ ◎ ○ ◎ ○ ◎ The present invention 3 ◎ ◎ ○ ◎ ○ ◎ The present invention 4 ◎ ◎ ◎ ◎ ◎ ◎ The present invention 5 ○ ◎ ◎ ◎ ◎ ◎ The present invention 6 × △ × △ × × Comparative example 7 × △ △ × × △ Comparative example 8 × × × △ △ × Comparative example

It is understood that the anti-glare antireflection films 1 to 5 of the present invention are excellent in respect to bright spot defects, scratch resistance, reflection, reflectance, glossiness, and clarity with respect to Comparative Examples anti-glare antireflection films 6 to 8.

Moreover, as a result of changing and experimenting with the other resin used for the Example of Unexamined-Japanese-Patent No. 2004-69753, the result similar to the anti-glare antireflection film 2 was obtained.

Moreover, as a result of changing and experimenting with the other resin used for the Example of Unexamined-Japanese-Patent No. 2006-3647, the result similar to anti-glare antireflective films 1 and 5 was obtained.

Subsequently, similar experiments were carried out using a cycloolefin polymer film (Zeonoa manufactured by Nihon Xeon Co., Ltd.) instead of the transparent support 1, and as a result, the anti-glare antireflection film of the constitution of the present invention had bright spot defects, scratch resistance, Excellent effects on reflection, reflectance, glitter and sharpness were reproduced.

(Example 2)

In the production of the antiglare antireflection film 1 of Example 1, antiglare antireflection films 9 to 17 were prepared in the same manner as the antiglare antireflection film 1 except that the amount of ultraviolet irradiation to the antiglare layer 1 was changed as shown in Table 2. It was.

Evaluation similar to Example 1 was performed about the obtained anti-glare antireflection films 9-17, and the result was shown in Table 2.

Anti-glare Anti-reflection Film No. UV irradiation amount (mJ / ㎠) Uneven state of arithmetic mean roughness Ra of the antiglare layer surface Spot defect Scratch resistance reflection Glitter reflectivity Sharpness Remarks 9 0 Inability to measure (liquid state) × ○ △ △ × △ The present invention 10 5 15 nm △ ○ ○ ◎ ○ ◎ The present invention 11 20 28 nm ○ ◎ ◎ ◎ ◎ ◎ The present invention 12 30 42 nm ○ ◎ ◎ ◎ ◎ ◎ The present invention 13 50 56 nm ○ ◎ ◎ ◎ ◎ ◎ The present invention 14 100 95 nm △ ○ ○ ○ △ ○ The present invention 15 150 158 nm × △ × △ × × Comparative example 16 200 253 nm × △ × △ × × Comparative example 17 300 268 nm × △ × △ × × Comparative example

Arithmetic mean roughness Ra of the surface of an antiglare layer is 100 nm or less, and the anti-glare antireflection films 9-14 of this invention which can be said to be a smooth state have a bright spot defect with respect to the comparative examples anti-glare antireflection films 15-17. It can be seen that it is excellent in scratch resistance, reflection, reflectance, glitter, and clarity.

(Example 3)

In preparation of the anti-glare antireflection film 1 of Example 1, the anti-glare antireflection films 18 and 19 were similarly produced except having changed the transparent support into the following transparent support 2 and 3.

<Production of Transparent Support 2>

<Production of cellulose ester resin, acrylic resin film 1>

(Dope composition 2)

70 parts by mass of acrylic resin diamond BR80 (manufactured by Mitsubishi Rayon Co., Ltd.)

(MW95000)

30 parts by mass of CAP482-20 (acyl group total substitution degree 2.75, acetyl group substitution degree 0.19, propionyl group substitution degree 2.56, Mw = 200000 Istoman Chemical Co., Ltd. product)

Chinubin 109 (Chiba Specialty Chemicals Co., Ltd.) 1 part by mass

Chinubin 171 (Chiba Specialty Chemicals Co., Ltd.) 1 part by mass

300 parts by mass of methylene chloride

40 parts by mass of ethanol

Butanol 5 parts by mass

The composition was dissolved while heating, to prepare a dope liquid. In addition, CAP is a cellulose acetate propionate resin.

(Film forming of cellulose ester resin acrylic resin film 1)

The produced dope liquid was uniformly cast on the stainless steel band support body at the temperature of 22 degreeC, and 2 m width using the belt casting apparatus. In the stainless steel band support, the solvent was evaporated until the amount of residual solvent became 100%, and peeled on the stainless steel band support with a peeling tension of 162 N / m.

The peeled web of acrylic resin was evaporated at 35 degreeC, the solvent was slitted in 1.6 m width, and it dried at the drying temperature of 135 degreeC, extending | stretching 1.1 times in the width direction with a tenter after that. At this time, the amount of residual solvent when extending | stretching started with a tenter was 10%.

After extending | stretching with a tenter and relaxing for 5 minutes at 130 degreeC, drying is terminated, conveying the drying zone of 120 degreeC and 130 degreeC with many rolls, it slitted to 1.5 m width, 10 mm in width 10 mm in the both ends of a film, The knurling process was performed and the cellulose-ester resin acrylic resin film 1 of winding up, the film thickness of 80 micrometers, length 4000m, and refractive index 1.50 was obtained.

The draw ratio in the MD direction calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.1 times.

<Production of Transparent Support 3>

In the preparation of the transparent support 2, a transparent support 3 (a cellulose ester resin-acrylic resin film 1 containing acrylic particles) was produced in the same manner except for changing to the following dope liquid composition 2.

(Preparation of acrylic particles)

Into a reactor equipped with a 60 liter reflux condenser, 38.2 liters of ion-exchanged water and 111.6 g of sodium dioctyl sulfo succinate were added thereto, and the temperature was raised to 75 ° C. under a nitrogen atmosphere while stirring at 250 rpm, and the influence of oxygen This was virtually absent. 0.36 g of APS was added, and after stirring for 5 minutes, a monomer mixture composed of 1657 g of MMA, 21.6 g of BA, and 1.68 g of ALMA was added in a batch, and after the detection of the exothermic peak, the mixture was held for another 20 minutes to complete polymerization of the innermost hard layer. Then, 3.48 g of APS was added, and after stirring for 5 minutes, a monomer mixture consisting of BA 8105 g, 31.9 g of PEGDA (200), and 264.0 g of ALMA was continuously added over 120 minutes, and after the addition was completed, the mixture was maintained for 120 minutes. The polymerization of the soft layer was completed.

Next, 1.32 g of APS was added, and after stirring for 5 minutes, a monomer mixture consisting of 2106 g of MMA and 201.6 g of BA was continuously added over 20 minutes, and after the addition was completed, the mixture was held for another 20 minutes to complete polymerization of the outermost hard layer 1. It was.

Next, 1.32 g of APS was added, and after 5 minutes, a monomer mixture consisting of 3148 g of MMA, 201.6 g of BA, and 10.1 g of n-OM was continuously added over 20 minutes, and maintained for another 20 minutes after the addition was completed. Next, it heated up at 95 degreeC and hold | maintained for 60 minutes, and completed superposition | polymerization of outermost hard layer 2.

The polymer latex thus obtained was collected in a small amount, and the flat particle diameter was determined by the absorbance method. As a result, it was 0.10 µm. The remaining latex was poured into a 3 mass% sodium sulfate hot water solution, salted and coagulated, and then dehydrated and washed repeatedly, followed by drying to obtain acrylic particles having a three-layer structure.

Said symbol is respectively the following material.

MMA; Methyl methacrylate

MA; Methyl acrylate

BA; n-butyl acrylate

ALMA; Allyl methacrylate

PEGDA; Polyethylene Glycol Diacrylate (Molecular Weight 200)

n-OM; n-octyl mercaptan

APS; Ammonium Persulfate

(Preparation of cellulose ester resin acrylic resin film 1 containing acrylic particle)

(Dope solution composition 3)

70 parts by mass of diamond BR80 (manufactured by Mitsubishi Rayon Co., Ltd.)

CAP482-20 30 parts by mass

20 parts by mass of the acrylic particles prepared above

Tinuvin 109 (Chiba Specialty Chemicals) 1 part by mass

Tinuvin 171 (made by Chiba Specialty Chemicals) 1 part by mass

300 parts by mass of methylene chloride

40 parts by mass of ethanol

Butanol 5 parts by mass

The composition was dissolved while heating, to prepare a dope liquid.

"evaluation"

The anti-glare antireflection films 1, 18, and 19 produced above were irradiated with a weatherproof tester (I-Super UV Tester, manufactured by Iwasaki Electric Co., Ltd.) for 200 hours with the anti-glare antireflection layer as the surface side to prepare a weather resistance test sample. And it evaluated by the method described in Example 1. In addition, about the weather resistance test sample, after humidifying for 2 hours on condition of the temperature of 23 degreeC, and 55% of a relative humidity, pencil hardness was evaluated by the following method.

The obtained results are shown in Table 3.

In addition, the base film shown in Table 3 was shown by the following abbreviated-name.

Base film 1: cellulose ester film 1

Base film 2: Cellulose ester resin, acrylic resin film 1

Base film 3: cellulose ester resin and acrylic resin film 1 containing acrylic particles

(Pencil hardness)

In accordance with the pencil hardness evaluation method prescribed by JIS-K5400, using the test pencil prescribed by JIS-S6006, using a 500 g weight, the surface of the conductive layer was repeatedly scratched five times with a pencil of each hardness, and up to one scratch Phosphorus hardness was measured. The higher the number, the higher the hardness.

Anti-glare Anti-reflection Film No. Base film Spot loss Scratch resistance Pencil hardness reflection Glitter reflectivity Sharpness One One ◎ ○ 3H ◎ ◎ ◎ ◎ 18 2 ◎ ◎ 3H ◎ ◎ ◎ ◎ 19 3 ◎ ◎ 4H ◎ ◎ ◎ ◎

As can be seen from the results in Table 3, in the evaluation after the weather resistance test, the transparent support is composed of a transparent support 2 composed of a cellulose ester resin and an acrylic resin rather than a cellulose ester film, and furthermore, a cellulose ester resin and an acrylic resin. The transparent support film 3 containing acrylic particles is particularly excellent with respect to film strength such as scratch resistance and pencil hardness. In addition, the transparent supports 2 and 3 containing the acrylic resin and the acrylic particles did not deteriorate in performance such as bright spot defects, reflections, reflectances, glitters, and sharpness, and were satisfactory.

Claims (12)

In the manufacturing method of an anti-glare antireflection film which has an anti-glare layer and one or more low refractive index layers on a transparent support body, The anti-glare layer is applied to the transparent support in a solution state of the anti-glare layer-forming coating composition, the surface of the anti-glare layer in the applied state is smooth, by one or more means of drying, heating, light irradiation, microwave irradiation or electron beam irradiation The smooth surface shape has a function of changing into an uneven shape showing anti-glare property, In the state where the surface of the antiglare layer is smooth, one or more layers of the low refractive index layer are applied on the smooth surface, and after the application of the low refractive index layer, The said antiglare layer surface shape is changed to an uneven | corrugated shape by the said means, The manufacturing method of the anti-glare antireflection film characterized by the above-mentioned. The method of claim 1, After apply | coating the said anti-glare layer forming coating composition on a transparent support body in a solution state, the said means of the extent that a surface shape does not change into uneven | corrugated shape is performed, and the low-refractive-index layer is apply | coated after that, anti-glare reflection prevention characterized by the above-mentioned. Method for producing a film. The method according to claim 1 or 2, The anti-glare layer-forming coating composition is formed of a coating composition comprising a first resin and a second resin, wherein the first resin and the second resin are resins having functional groups that react with each other, and the surface tension of the first resin The difference? Of the surface tension of the second resin is two or more resins having 2 dyne / cm or more, the means is light irradiation, and the light irradiation is ultraviolet irradiation. The method according to any one of claims 1 to 3, Said low refractive index layer contains the component hardened | cured by ultraviolet irradiation, The manufacturing method of the anti-glare antireflection film characterized by the above-mentioned. The method according to any one of claims 1 to 4, Arithmetic mean roughness Ra of the surface of an anti-glare layer before apply | coating the said low refractive index layer is 100 nm or less, The manufacturing method of the anti-glare antireflection film characterized by the above-mentioned. The method according to any one of claims 1 to 5, A high refractive index layer containing conductive metal oxide fine particles is formed between the antiglare layer and the low refractive index layer, wherein the anti-glare antireflection film is produced. The method according to any one of claims 1 to 6, The said transparent support body contains a cellulose ester resin, The manufacturing method of the anti-glare antireflection film characterized by the above-mentioned. The method according to any one of claims 1 to 6, The said transparent support body contains a cellulose ester resin and an acrylic resin, The manufacturing method of the anti-glare antireflection film characterized by the above-mentioned. The method according to any one of claims 1 to 6, The said transparent support body contains a cellulose ester resin, an acrylic resin, and an acrylic particle, The manufacturing method of the anti-glare antireflection film characterized by the above-mentioned. It was manufactured by the manufacturing method of the anti-glare antireflection film in any one of Claims 1-9, The anti-glare antireflection film characterized by the above-mentioned. The anti-glare antireflection film of Claim 10 was formed in at least one surface, The polarizing plate characterized by the above-mentioned. The anti-glare antireflection film of Claim 10 or the polarizing plate of Claim 11 was used, The display apparatus characterized by the above-mentioned.