KR101725585B1 - Method for producing antireflection film, antireflection film, polarizing plate, and image display device - Google Patents

Abstract

INDUSTRIAL APPLICABILITY According to the present invention, there can be provided a production method capable of easily producing an antireflection film having excellent antireflection characteristics, having excellent scratch resistance and antifouling property and suppressing the generation of minor whiteness, And a polarizing plate and an image display device using the film. (1) a step of applying a composition for forming a low refractive index layer containing at least a fluorine-containing compound, a fine particle and a binder resin on a transparent substrate to form a coating film, and (2) a step of coating the coating film with a low- (3) a step of heating the low refractive index image and the reflection image, or irradiating the low refractive index image and the retardation image with ionizing radiation to cover the entire surface of the low refractive index layer and the low refractive index layer A low refractive index layer and an antifouling layer in this order from the side of the antifouling layer to a fluorine atom / carbon atom ratio measured by X-ray photoelectron spectroscopy (XPS) of 0.6 To 1.0 and a silicon atom / carbon atom ratio of less than 0.25, and an average surface roughness (Ra ') of the antifouling layer is 10 nm or less.

Description

TECHNICAL FIELD [0001] The present invention relates to a method of manufacturing an antireflection film, an antireflection film, a polarizing plate, and an image display device,

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

Conventionally, the surface of a display such as a liquid crystal display (LCD), a plasma display panel (PDP), and a cathode ray tube display (CRT) has a high surface hardness or a high reflectivity An antireflection film is provided to impart antireflection properties. Generally, the antireflection film has a structure in which a hard coat layer and a low refractive index layer are laminated on a transparent substrate, and the low refractive index layer preferably has a lower refractive index in order to contribute to reflection prevention. As a method for achieving a low reflectivity, for example, after a layer having a higher refractive index such as a medium refractive index layer or a high refractive index layer is laminated on the hard coat layer and then the low refractive index layer is further formed Is known. Further, for example, Patent Document 1 discloses an antireflection film in which specific grains are contained in a refractive index control layer.

However, the performance required for the antireflection film is such that it is difficult to be tarnished by the scratch resistance of the surface of such a display, fingerprints, sebum, or magic, and even if these contaminants adhere thereto, that is, antifouling property. As a method of imparting antifouling properties to an antireflection film, there is a method of using an antifouling agent such as a fluorine-containing antifouling agent (for example, Patent Document 1). However, in Patent Document 1, in order to suppress the deterioration of the performance caused by the opacity of the composition containing the antifouling agent, compatibility with each component in the composition is improved, that is, fluorine having a low molecular weight Containing antifouling agent must be used, and the resulting antifouling property can not be said to be sufficient.

As a method of imparting antifouling property, a fluorine-containing compound having a perfluoroalkyl group or the like is used in an antifouling layer formed on the surface thereof, so that a specific amount of fluorine atom is present in relation to silicon element, carbon element and fluorine element (For example, Patent Document 2). The fluorine-containing compound having a perfluoroalkyl group or the like as used in Patent Document 2 is a material excellent in antifouling property, but is known to have poor compatibility with other materials forming an antifouling layer, for example, a binder resin. Containing compound is applied to form an antifouling layer, there are cases where it is difficult to form a stable antifouling layer or a problem that the antifouling layer is whitened.

In this respect, in Patent Document 2, the compatibility with other components is remarkably deteriorated. Therefore, in order to prevent occurrence of cratering, unevenness or whitening on the applied surface and adverse effects caused by whitening, the silicon element, the carbon element and the fluorine element A certain amount of fluorine atoms are present in the presence of a certain amount of a fluorine atom to form a stainproof layer by obtaining a certain compatibility and thereby to suppress the formation of a stainproof layer and the occurrence of whitening (Patent Document 2, paragraph [0039]) .

In recent years, with the high performance of the display as described above, the antireflection film is required to have high performance, and in particular, the demand for white display is increasing. In the prior art, whiteness is a degree of white transparency which can be distinguished from a glance at a glance, and it has been required to reduce such white whiteness. However, recently, there has been a demand for suppression of a slight whiteness which has not been encountered so far to such a degree that the film can be visually recognized by a person skilled in the art in a film which is thought to have a high transparency in addition to the conventional whiteness. 2, there are cases where the coating film surface is uniform, not constant, and slightly distorted, so that it is impossible to cope with it sufficiently.

As a method of imparting antifouling properties to a film, there has been proposed a method of forming a stainproofing layer by vapor-depositing a perfluoropolyether group-containing silane coupling agent on a transparent film base material on which an antireflection layer is formed Literature 3). In the method described in Patent Document 3, as described above, the fluorine-containing compound having a perfluoroalkyl group or the like generally has poor compatibility with other materials forming the antifouling layer, and the resin composition containing the fluorine- It is difficult to form an antifouling layer, and therefore attempts have been made to form an antifouling layer comprising the above-mentioned fluorine-containing compound by using a deposition method capable of forming a layer without using other materials. However, since evaporation is used for forming the layer, other materials such as binder resin can not be used, and the layer strength of the antifouling layer and the adhesion with the transparent film base material become poor, so that the antifouling layer is peeled off from the film The antifouling property is remarkably deteriorated. Furthermore, since it is necessary to perform the deposition at a high temperature of several hundreds degrees, the transparent film substrate shrinks by heating, or the film substrate is subjected to high temperature deposition in the accelerated deterioration test There is a problem that the substrate itself which has received heat damage is disassembled.

The antifouling layer generally has a very thin thickness of about nm order. In addition to excellent antifouling properties, it is necessary to suppress the generation of minor whiteness. To satisfy these requirements at the same time, It has been thought that it can not be accomplished without doing further development while using thing.

Japanese Patent Application Laid-Open No. 2010-152311 International Publication No. 2008/38714 pamphlet Japanese Patent Application Laid-Open No. 2001-188102

An object of the present invention is to provide a production method capable of easily producing an antireflection film having excellent antireflection properties and antifouling properties under such a situation and suppressing generation of a slight whitening which has not been encountered so far, An antireflection film, and a polarizing plate and an image display apparatus using the film.

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted intensive research to achieve the above object. As a result, the inventors of the present invention have found that when a retardation layer is formed by the method of Patent Document 2, (Sea-island) structure in which a hole of a shape or an elliptical shape is unevenly distributed and a lower layer such as a substrate is exposed is sometimes seen, and the occurrence of such a structure inhibits the formation of a stable layer, And also revealed a slight white pigment. That is, the method disclosed in Patent Document 2 improves the easiness of formation of the antifouling layer by obtaining a certain amount of fluorine atoms to obtain certain compatibility, but under the situation where higher performance of the antireflection film is required, There is room for further investigation as to whether or not it is formed uniformly and constantly, whether or not the sea structure is generated, and if there is a slight whitening.

Therefore, the present inventors have found that the use of a composition for forming a low-refractive index layer containing a specific fluorine-containing compound containing a large amount of fluorine atoms having poor compatibility, rather than improving the compatibility as in the prior art, A method is adopted in which a layer is formed so as to cover the entire surface of the film with the above composition to obtain a uniform and constant low refractive index layer with a reduced average surface roughness and suppressed occurrence of the sea- And found that the above problems can be solved.

Although the fluorine-containing compound having a large content of fluorine atoms is excellent in antifouling property but is poor in compatibility, the fluorine-containing compound can be used in the present invention in the present invention, , It has become possible to obtain a very excellent antifouling property. The present invention has been completed based on such knowledge.

That is,

[1] A method for producing a photocatalyst, which comprises, in order, at least a transparent substance, a low refractive index layer and an antifouling layer, which comprises the following steps (1) to (3) Wherein the antireflection film has a fluorine atom / carbon atom ratio of 0.6 to 1.0, a silicon atom / carbon atom ratio of less than 0.25, and an average surface roughness (Ra ') of the antifouling layer of 10 nm or less,

Step (1) A step of coating a transparent substrate with a composition for forming a low refractive index layer containing at least a fluorine-containing compound, fine particles and a binder resin to form a coating film

Step (2) Step of phase-separating the coating film into a low refractive index image and a retardation image

Step (3) The antireflection layer covering the entire surfaces of the low refractive index layer and the low refractive index layer is formed by heating the low refractive index image and the retardation image, or by irradiating the low refractive index image and the retardation image with ionizing radiation fair

[2] An antireflection film produced by the method for producing an antireflection film as described in [1] above,

[3] A polarizing plate comprising an antireflection film on at least one side of a polarizing film, wherein the antireflection film is the antireflection film according to [2]

[4] An antireflection film or a polarizing film, wherein the antireflection film has a polarizing plate having an antireflection film on at least one side of the display, and the antireflection film is an antireflection film as described in [2]

.

According to the present invention, it is possible to easily obtain an antireflection film having excellent antireflection characteristics, excellent antiscratching property and antifouling property, and suppressing the occurrence of minor whitening, which has not been encountered so far, A polarizing plate and an image display device can be obtained.

1 is a schematic view showing a cross section of an antireflection film of the present invention.
2 is a schematic diagram showing a cross section of the antireflection film of the present invention.
3 is a schematic diagram showing a cross section of the antireflection film of the present invention.
Fig. 4 is a diagrammatic and topological image obtained by an atomic force microscope of the surface of the antireflection film obtained in Example 1. Fig.
Fig. 5 is a top view of a surface of an antireflection film obtained in Example 2 by an atomic force microscope. Fig.
Fig. 6 is a top view and a top view of the surface of the antireflection film obtained in Example 3 by an atomic force microscope. Fig.
FIG. 7 is a diagrammatic and topological image of an antireflection film obtained in Example 4 by an atomic force microscope. FIG.
FIG. 8 is a top view of a surface of an antireflection film obtained in Example 5 by an atomic force microscope. FIG.
Fig. 9 is a top view of a surface of an antireflection film obtained in Comparative Example 1 by an atomic force microscope. Fig.
Fig. 10 is a top view of a surface of an antireflection film obtained in Comparative Example 2 by an atomic force microscope. Fig.
11 is a diagrammatic and topological image of the surface of the antireflection film obtained in Comparative Example 3 by an atomic force microscope.

[Method for producing antireflection film]

(1) a step of applying a composition for forming a low refractive index layer containing at least a fluorine-containing compound, a fine particle and a binder resin on a transparent substrate to form a coating film, (2) A step of separating the coating film from a low refractive index phase and a scattering phase; and (3) a step of heating the low refractive index phase and the retardation phase, or by irradiating the low refractive index phase and the retardation phase with ionizing radiation, (XPS) from the side of the antifouling layer, and a step of forming an antioxidant layer covering the entire surface of the low refractive index layer in this order, wherein at least a transparent substrate, a low refractive index layer, Wherein the antireflection film has a fluorine atom / carbon atom ratio of 0.6 to 1.0, a silicon atom / carbon atom ratio of less than 0.25, and an average surface roughness (Ra ') of the antifouling layer of 10 nm or less, A method for manufacturing.

The low refractive index phase and the scattering phase formed in the step (2) are phases formed in a coating film coated with the composition for forming a low refractive index layer, the binder resin in the low refractive index layer forming composition is in an uncured state, The solvent preferably contained in the composition is in a state of being vaporized enough to complete the phase separation. On the other hand, by passing through these steps (3), the binder resin in the layer becomes cured, and the solvent evaporates to form a low refractive index layer and an antifouling layer in which most of the solvent is not present. Therefore, in the present invention, the state existing in the coating film is referred to as a low-refractive index layer or an anti-reflection phase, and the low refractive index layer and the antifouling layer are respectively referred to as a low refractive index layer and an antifouling layer. In the present invention, the uncured state means that the composition for forming a low refractive index layer has a physical fluidity, that is, a state capable of measuring viscosity. The cured state means that the composition for forming a low refractive index layer is a physical That is, a state in which viscosity can not be measured.

Hereinafter, each process will be described.

(Step (1))

The step (1) is a coating film formation step for forming a coating film by applying a composition for forming a low refractive index layer containing at least a fluorine-containing compound, fine particles and a binder resin on a transparent substrate.

The coating film forming step in the present invention is preferably carried out by preparing a transparent substrate separately from the transparent substrate, preparing a composition for forming a low refractive index layer, and applying the composition for forming a low refractive index layer to the transparent substrate.

(Preparation of composition for forming low refractive index layer)

The composition for forming a low refractive index layer is prepared by homogeneously mixing a fluorine-containing compound, a fine particle, a binder resin, a fluorine-containing polymer to be used, various kinds of additives, etc., which will be described later, and dissolving them in a solvent as required.

It is preferable that the composition for forming the low refractive index layer is in a liquid state dissolved in a solvent in consideration of productivity. The viscosity of the composition for forming a low refractive index layer which is in the liquid phase is not particularly limited as long as it is capable of forming a coating film on the surface of the transparent substrate by a coating and coating method which will be described later.

(Formation of Coating Film)

The coating film can be formed by applying the composition for forming a low refractive index layer as described above to a surface of a transparent substrate in such a manner that the thickness after curing becomes a predetermined thickness to be described later, For example, a gravure coat or a die coat, by a known method such as a spraying method, a comma method or a die method.

Next, each component for forming the transparent base material and the composition for forming the low refractive index layer will be described.

(Transparent substrate)

The transparent substrate to be used in the present invention is not particularly limited as long as it is transparent generally used as a substrate of the antireflection film, but a plastic film, a plastic sheet and the like can be appropriately selected depending on the application.

As such a plastic film or plastic sheet, those containing various synthetic resins may be mentioned. Examples of the synthetic resin include linear resins such as polyethylene resin, ethylene alpha-olefin copolymer, polypropylene resin, polymethylpentene resin, polybutene resin, ethylene-propylene copolymer, propylene-butene copolymer, olefinic thermoplastic elastomer, Or cyclic polyolefin resin; Polyester resins such as polyethylene terephthalate resin (PET), polybutylene terephthalate resin, polyethylene naphthalate-isophthalate copolymer resin and polyester thermoplastic elastomer; Acrylic resins such as poly (meth) acrylate resin, poly (meth) acrylate resin and poly (meth) acrylate butyl resin; Polyamide resins represented by nylon 6 or nylon 66; Cellulose resins such as triacetylcellulose resin (TAC), diacetylcellulose, acetate butyrate cellulose, and cellophane; A cycloolefin resin obtained from a cycloolefin such as norbornene, dicyclopentadiene or tetracyclododecene; Polystyrene resin; Polycarbonate resins; Polyarylate resins; Or a polyimide resin.

As the transparent substrate, it is possible to use a single or a mixture of two or more selected from the above-mentioned plastic film or plastic sheet as a mixture, but from the viewpoint of mechanical strength, polyethylene terephthalate resin or acrylic resin is preferable and in view of optical anisotropy Triacetyl cellulose resin or cyclopolyolefin is preferable.

The thickness of the transparent substrate is not particularly limited, but is usually about 5 to 1000 占 퐉, preferably 15 to 80 占 퐉, and more preferably 20 to 60 占 퐉, in view of durability and handling properties.

(Composition for forming a low refractive index layer)

The composition for forming a low refractive index layer used in the present invention is a resin composition containing a fluorine-containing compound, fine particles and a binder resin. Hereinafter, each component will be described.

(Fluorine-containing compound)

The composition for forming a low refractive index layer contains a fluorine-containing compound for the purpose of forming an antifouling layer on the antireflection film of the present invention. As the fluorine-containing compound to be used in the present invention, a compound having a reactive group and a perfluoropolyether group is preferable, and a compound containing a silane unit having a reactive group and a silane unit having a perfluoropolyether group is preferable . In the present invention, since the fluorine-containing compound has a reactive group, the fluorine-containing compound easily bonds with other components in the composition, so that a more rigid layer can be formed, resulting in a thin and excellent scratch-resistant layer. In addition, in the present invention, excellent antiscratchability of the outermost surface of the antireflection film means that the outermost layer also has excellent adhesion to the underlayer. That is, when the fluorine-containing compound in the composition for forming a low refractive index layer exists in such a manner that a large amount of the fluorine-containing compound in the low refractive index phase and the retardation phase is caused by the retardation phase and the curing in the step (3) By the reaction of the reactive groups in the fluorine-containing compound, very good adhesion between the low refractive index layer and the antifouling layer is obtained. Further, the reaction between the reactive group of the fluorine-containing compound and the reactive group of the binder resin or the curing of the binder resin itself further improves the adhesion of the antifouling layer and increases the hardness, resulting in a highly excellent scratch resistance .

Further, since the silyl unit-containing compound has affinity with the fine particles contained on the low refractive index, when a spark phase is formed on the low refractive index surface, the compound imparting wettability to the entire surface of the surface And the wettability can be maintained even in a state where the solvent is almost evaporated from the phase of the solvent, so that it is important in obtaining a uniform and constant antifouling layer on the entire surface of the surface. Further, since such a compound is flexible, the slidability is improved, so that a layer having excellent scratch resistance can be obtained. Since the film has affinity and stable wettability can be obtained continuously, it is possible to cause craters or evaporation of the solvent when the solvent evaporates, and it is possible to suppress the occurrence of slight whitening due to these. Further, by using a fluorine-containing compound having a silane unit and a perfluoroether group in the same molecule, the phase separation of the silane unit and the perfluoropolyether is suppressed, and a more uniform and uniform surface tends to be obtained. Here, the silane unit is a unit represented by the following formula (1).

In Formula 1, X represents a single bond or an oxygen atom, R ¹ and R ² represent a monovalent organic group, and at least one of R ¹ and R ² represents a monovalent group containing a reactive group or a perfluoropolyether group It is an organic device. The fluorine-containing compound used in the present invention may be, for example, ^one having a silane unit in which R ¹ is a monovalent organic group containing a reactive group and a silane unit in which R ¹ is a monovalent organic group containing a perfluoropolyether group, R ¹ may be a monovalent organic group containing a reactive group and R ² may be a silane unit having a monovalent organic group including a perfluoropolyether group. Further, if in a plurality of silane units, R ^1, R ² and X are independent, that is, fluorine-containing compounds of the present invention has a silane units having a polyether with a silane unit and perfluoroalkyl having at least reactive, with a variety of And may have a silane unit.

In the present invention, these silane units are preferably units having a siloxane skeleton. That is, it is preferable that X in the above formula (1) is an oxygen atom. Since the fluorine-containing compound has a siloxane skeleton, as described above, the affinity with the fine particles contained in the low refractive index layer is improved, so that an antifouling layer having uniform, constant and excellent antifouling property can be obtained, .

The weight average molecular weight (weight average molecular weight in terms of polystyrene measured by the GPC method) of the fluorine-containing compound is preferably 5,000 or more, more preferably 5,000 to 100,000, and still more preferably 5,000 to 50,000. When the weight average molecular weight of the fluorine-containing compound is 5,000 or more, excellent antifouling property is obtained. When the weight average molecular weight is 100,000 or less, good solubility in an organic solvent is obtained, and a uniform and uniform surface tends to be obtained.

The reactive group is preferably a reactive group having an ethylenically unsaturated double bond group such as a (meth) acryloyl group or a vinyl group, or an epoxy group, a carboxyl group, an amino group or a hydroxyl group, and among these, a (meth) acryloyl group, a vinyl Is preferably a reactive group having an ethylenically unsaturated double bond group. When the reactive group is the above-mentioned group, it becomes easy to bond with other components in the composition for forming a low refractive index layer, so that it is possible to form a layer having more firm adhesion between the low refractive index layer and the antifouling layer as described above, Layer is obtained.

As the perfluoropolyether group, for example, those represented by the following general formula (2) are preferable.

In the formula (2), a to e are integers of 0 to 50, and may be the same or different. a to d are preferably integers such that the weight average molecular weight of the perfluoropolyether group represented by the general formula (2) is in the range of 200 to 6000, and e is preferably in the range of 0 to 2. Xa, xb, xc and xd are integers of 1 to 4 and may be the same or different. When xa, xb, xc and xd are 3 and 4, -C _xa F _2xa , -C _xb F _2xb , -C _xc F _2xc and -C _xd F _2xd may be linear or branched.

The content of the fluorine atom in the fluorine-containing compound is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, and still more preferably 20 to 60 parts by mass. When the content of fluorine atoms in the fluorine-containing compound is 5 parts by mass or more, excellent antifouling properties are obtained. When the content of fluorine atoms is 80 parts by mass or less, good solubility in a solvent is obtained and a uniform and uniform surface tends to be obtained.

The content of the solid content of the fluorine-containing compound relative to 100 parts by mass of the total amount (solid content) of the fine particles to be described later in the composition for forming a low refractive index layer and the binder resin (when the fluorine-containing monomer and the fluorine- And preferably 5 to 30 parts by mass. The fluorine-containing compound, fine particles and binder resin are commercially available, but are generally sold in the form contained in a solvent. In this case, the amount of these solids is the amount excluding the solvent from the total amount of the commercial product. Further, for example, the photopolymerization initiator is one of arbitrary solid components contained in the composition but is not used for calculating the content of the fluorine-containing compound.

When the content of the fluorine-containing compound is 5 parts by mass or more, the whole surface of the fluorine-containing compound can be covered with a uniform and uniform antioxidant layer, so that the sea water structure is not expressed and little whitening occurs. When the amount is 30 parts by mass or less, uniformity and uniformity of the antioxidant layer can be obtained without occurrence of roughness of the coating film surface such as unevenness of the coating film surface, unevenness and uneven whitening, . That is, by setting the content of the fluorine-containing compound within the above-mentioned range, a uniform, uniform and smooth antifouling layer having an average surface roughness (Ra ') of 10 nm or less can be obtained.

For the same reason as above, the content of the fluorine-containing compound is more preferably 5 to 20 parts by mass, further preferably 5 to 15 parts by mass, and most preferably 10 parts by mass. By setting the maximum content to be 10 parts by mass, it becomes possible to make the average surface roughness (Ra '), which will be described later, also 5 nm or less, and the surface becomes smoother and the scratch resistance can be improved.

(Fine particles)

The composition for forming a low refractive index layer contains fine particles. The fine particles are used for the purpose of lowering the refractive index of the layer, that is, for improving the antireflection property.

As the fine particles, any of inorganic or organic materials can be used without limitation, and from the viewpoint of further improving the antireflection property and ensuring a satisfactory surface hardness, fine particles of silica and fine particles of magnesium fluoride are preferably used Fine particles having spherical shape at the point of shape and having voids themselves are preferably used. In the case of having a void, it is also possible to use alumina fine particles having a refractive index higher than that of the cured film of the binder resin.

Among them, silica fine particles are preferable in view of durability to humid heat and the like in terms of materials. In the present invention, in order to form the anti-scattering layer so as to cover the entire surface of the low refractive index layer, the combination of the materials for forming these layers becomes one of the important conditions. Since the fine particles exist in a state in which they are mostly finely filled on the entire surface of the low refractive index layer, the properties of the surface of the low refractive index layer tend to be affected by the fine particles. The higher the affinity between the fine particles contained in the low refractive index layer and the material forming the antifouling layer, the easier it is for the antifouling layer to cover the entire surface of the low refractive index layer. This is because when the scattered phase is phase separated from the low refractive index phase, the scattered phase has wettability to the entire surface of the low refractive index surface and can maintain the wettability until the step (3) is completed. From this viewpoint, the combination of the fine particles of fine silica particles made of silica and the fluorine-containing compound having silane units, and furthermore, siloxane units, that is, fluorine-containing compounds containing silica atoms is particularly preferable.

The fine particles having voids themselves have a feature that their refractive indices are low because they have fine voids in the outside or inside thereof and are filled with a gas such as air having a refractive index of 1.0, for example. Examples of the fine particles having such voids include inorganic or organic porous fine particles and hollow fine particles. Preferred examples thereof include porous polymer fine particles and hollow polymer fine particles using porous silica, hollow silica fine particles, acrylic resin, etc. have. As the inorganic fine particles, silica fine particles having voids produced by using the technique disclosed in Japanese Patent Application Laid-Open No. 2001-233611 can be used. As the organic fine particles, the technique disclosed in Japanese Patent Application Laid-Open No. 2002-80503 can be used And hollow polymer fine particles prepared by the above method.

The silica or porous silica having the voids as described above is preferable from the viewpoint of lowering the refractive index of the low refractive index layer because the refractive index is lower than that of common silica fine particles having a refractive index of about 1.20 to 1.44 and a refractive index of about 1.45.

The fine particles are also preferably fine particles capable of forming a nanoporous structure on at least a part of the inside and / or the surface depending on the shape, structure, aggregation state, and dispersion state inside the film.

Examples of such fine particles include fine particles of the above-mentioned silica and fine particles made of a porous fine particle which is prepared for the purpose of increasing the specific surface area and which is used for a filling column and a porous portion of the surface to absorb various chemical substances, Or a dispersion or an aggregate of hollow microparticles for the purpose of being used for a heat insulating material or a low dielectric constant material. Specific examples thereof include "Nipsil (trade name)", "Nipgel (trade name)": manufactured by Nippon Silica Chemical Co., Ltd., "Colloidal Silica UP series (trade name)" manufactured by Nissan Chemical Industries, have.

The average particle diameter of the primary particles of the fine particles is preferably 5 to 200 nm, more preferably 5 to 100 nm, and further preferably 10 to 80 nm. When the average particle diameter of the fine particles is 5 nm or more, an excellent refractive index reduction effect is obtained. When the average particle diameter of the fine particles is 200 nm or less, a good dispersion state of the fine particles is obtained without deteriorating the transparency of the low refractive index layer 3. In the present invention, if the average particle diameter is within the above range, fine particles may be formed in a chain-like shape. Here, the average particle diameter of the primary particles of the fine particles was measured by observing an arbitrary 3-field portion of the cross section of the antireflection film using a transmission electron microscope (TEM), and measuring the number of arbitrary 20 particles Min) were measured in the photograph to obtain an average particle diameter.

The fine particles used in the present invention are preferably surface-treated. As the surface treatment, a surface treatment using a silane coupling agent is preferable. Among them, a surface treatment using a silane coupling agent having a (meth) acryloyl group is preferable. By carrying out the surface treatment on the fine particles, the affinity with the binder resin described later is improved, the dispersion of the fine particles becomes uniform, and the coagulation of the fine particles becomes difficult to occur, so that the reduction in transparency of the low- , The coating properties of the composition for forming a low refractive index layer and the coating film strength of the composition are suppressed. When the silane coupling agent has a (meth) acryloyl group, since the silane coupling agent has ionizing radiation curability, the silane coupling agent easily reacts with the binder resin to be described later. Therefore, in the coating film of the composition for forming a low refractive index layer, Is fixed to the binder resin. That is, the fine particles have a function as a crosslinking agent in the binder resin. As a result, a tensional effect of the entire coating film is obtained, and it becomes possible to impart excellent surface hardness to the low refractive index layer with the flexibility inherent in the binder resin left. Therefore, since the low refractive index layer is deformed by taking advantage of its own flexibility, it has an absorbing force and a restoring force against an external impact, so that occurrence of scratches is suppressed, and high surface hardness with excellent scratch resistance is obtained.

Examples of the silane coupling agent preferably used in the present invention include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxy Silane, 3- (meth) acryloxypropylmethyldiethoxysilane, 2- (meth) acryloxypropyltrimethoxysilane, 2- (meth) acryloxypropyltriethoxysilane and the like.

The content of the fine particles in the low refractive index layer is preferably 10 to 95 mass%, more preferably 20 to 90 mass%, and still more preferably 30 to 90 mass%. Here, the content of the fine particles in the low refractive index layer may be appropriately determined depending on the total solid content of the low refractive index layer composition, that is, the fluorine-containing polymer optionally used in addition to the fluorine-containing compound, the fine particles and the binder resin, And the content of the fine particles in the total amount of the additives (the total amount of all the compounds other than the solvent contained in the composition). When the content of the fine particles is 10 mass% or more, the effect of using the fine particles is sufficiently obtained. When the content of fine particles is 95% or less, the average surface roughness (Ra ') of the antifouling layer can be reduced. So that excellent surface hardness can be obtained.

Further, in the present invention, solid fine particles having no voids can be used at the same time for the purpose of improving scratch resistance. The average particle diameter of the primary particles of the solid fine particles is preferably 1 to 200 nm, more preferably 1 to 100 nm, and further preferably 5 to 20 nm. If it is 1 nm or less, the contribution to the improvement of the surface hardness is small. If it is 200 nm or more, the transparency of the low refractive index layer is impaired and it is difficult to obtain a good dispersion state of the fine particles.

The content of the solid particles may be suitably adjusted in accordance with the required scratch resistance, refractive index, etc. of the low refractive index layer. For example, it is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, based on the total mass of solids in the low refractive index layer composition.

It is preferable that the surface treatment is performed in the same manner as the fine particles having the voids in view of scratch resistance and transparency.

As the solid particles, solid particles used in conventionally known antireflection films, hard coat films and the like can be used. Examples of commercially available products include MIBK-ST (average primary particle diameter: 12 nm) and MIBK-ST-ZL (average primary particle diameter: 88 nm) manufactured by Nissan Chemical Industries, And OSCAL series (average primary particle size: 7 to 100 nm) manufactured by Nippon Kayaku Co., Ltd., and the like.

(Binder resin)

The composition for forming a low refractive index layer contains a binder resin from the viewpoints of film formability and film strength. The binder resin can be fixed by heating or irradiating with ionizing radiation such as ultraviolet rays or electron beams to the above-mentioned fluorine-containing compound, fine particles, and other components to be added as required, into the layer of the low refractive index layer Are preferably used. In the present invention, a resin having low compatibility with the above-mentioned fluorine-containing compound is preferably used so that the fluorine-containing compound is phase-separated efficiently and an antifouling layer that completely covers the low refractive index layer is obtained.

More specifically, as the binder resin, for example, a thermosetting resin such as a melamine resin, a urea resin, an epoxy resin, a ketone resin, a diallyl phthalate resin, an unsaturated polyester resin and a phenol resin, or an ionizing radiation curable resin, . Among them, an ionizing radiation curable resin is preferable.

An ionizing radiation curable resin refers to a resin having energy both capable of polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, a resin which is cured by irradiation with ultraviolet rays or electron beams. Specifically, it can be appropriately selected from the polymerizable monomers and polymerizable oligomers (or prepolymers) conventionally used as ionizing radiation-curable resins.

As the polymerizable monomer, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and among these, a polyfunctional (meth) acrylate monomer is preferable.

The multifunctional (meth) acrylate monomer may be any (meth) acrylate monomer having two or more ethylenic unsaturated bonds in the molecule and is not particularly limited. Specific examples thereof include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, dicyclopentanyl di (meth) acrylate, isocyanurate di Bifunctional (meth) acrylates such as methyl (meth) acrylate; Trifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (acryloxyethyl) isocyanurate; (Meth) acrylate such as pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) Acrylate; Ethylene oxide modified product, caprolactone modified product, and propionic acid modified product of the above-mentioned polyfunctional (meth) acrylate monomer.

Of these, trifunctional or more (meth) acrylates are preferable from the viewpoint of obtaining excellent scratch resistance. These polyfunctional (meth) acrylate monomers may be used singly or in combination of two or more. More specifically, in the present invention, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate and the like can be preferably used to obtain desired effects such as antifouling property, scratch resistance Trifunctional (meth) acrylates such as acrylate and tris (acryloxyethyl) isocyanurate; (Meth) acrylate such as pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) Acrylate is preferable, and pentaerythritol tri (meth) acrylate is particularly preferable.

In the present invention, monofunctional (meth) acrylate monomers may be added together with the above-mentioned polyfunctional (meth) acrylate monomers in a range that does not impair the purpose of the present invention, for example, can do. Further, in order to adjust the coating appropriately by increasing the viscosity and to prevent curling due to curing shrinkage, the following polymerizable oligomer or polymer can be used.

Examples of the polymerizable oligomer include oligomers having radically polymerizable unsaturated groups in the molecule such as epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate and polyether ) Acrylate-based oligomers.

Further, in the present invention, for example, a copolymer is obtained by polymerizing methyl methacrylate and glycidyl methacrylate in advance, followed by condensation of a glycidyl group of the copolymer with a carboxyl group of methacrylic acid or acrylic acid The resulting reactive polymer may be used. Such a reactive polymer is available as a commercial product, and commercially available products include, for example, "Macromonomer (trade name)" manufactured by Toagosei Co., Ltd.

In the present invention, an ultraviolet ray curable resin or an electron ray curable resin can be preferably used as the ionizing radiation curable resin.

When an ultraviolet ray curable resin is used as the ionizing radiation curable resin, the photopolymerization initiator is preferably added in an amount of 0.5 to 10 parts by mass based on 100 parts by mass of the ultraviolet ray curable resin, more preferably 1 to 5 parts by mass. The photopolymerization initiator can be appropriately selected from conventionally used conventionally, and is not particularly limited. For example, as the polymerizable monomer having a radically polymerizable unsaturated group in the molecule and the polymerizable oligomer, there may be mentioned acetophenone, benzophenone, benzo And a photopolymerization initiator such as phosphorous, ketal, anthraquinone, disulfide, thioxanthone, thiuram, and fluoroamine. Either one of them may be used alone, or both of them may be used in combination. These photopolymerization initiators are commercially available and are commercially available, for example, from Irgacure 184 (trade name), Irgacure 907 (trade name), Irgacure 127 (trade name) ), And the like.

The content of the binder resin is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, based on 100 parts by mass of the total solid content in the composition for forming a low refractive index layer. When the content of the binder resin is within the above range, excellent scratch resistance can be obtained and the fluorine-containing compound can be phase-separated efficiently.

(Fluorine-containing polymer)

The composition for forming a low refractive index layer used in the present invention preferably contains a fluorine-containing polymer from the viewpoint of lowering the refractive index. Examples of the fluorine-containing polymer include (meth) acrylic acid moieties and fully fluorinated alkyl, alkenyl, aryl esters, fully or partially fluorinated vinyl ethers, fully or partially fluorinated vinyl esters, and fully or partially fluorinated vinyl ketones. .

The fluorine-containing polymer preferably contains silicon in addition to fluorine, and is preferably a silicon-containing vinylidene fluoride copolymer containing a silicone component in the copolymer. Examples of the silicone component in this case include (poly) dimethylsiloxane, (poly) diethylsiloxane, (poly) diphenylsiloxane, (poly) methylphenylsiloxane, alkyl modified (poly) dimethylsiloxane, Silicon-containing silicon, alkoxy group-containing silicon, phenolic group-containing silicon, methacrylic modified silicone, alkylene oxide-modified silicone, fluorine-containing silicone, Silicone modified silicone, acryl modified silicone, amino modified silicone, carboxylic acid modified silicone, carbinol modified silicone, epoxy modified silicone, mercapto modified silicone, fluorine modified silicone, polyether modified silicone and the like. Among them, those having a dimethylsiloxane structure are preferable.

In addition to the above, a compound having at least one isocyanato group and fluorine in the molecule and a compound having at least one functional group reactive with an isocyanato group such as an amino group, a hydroxyl group or a carboxyl group in the molecule is reacted ; A compound obtained by reacting a fluorine-containing polyol such as a fluorine-containing polyether polyol, a fluorine-containing alkylpolyol, a fluorine-containing polyesterpolyol and a fluorine-containing? -Caprolactone-modified polyol with a compound having an isocyanato group may also be used as a fluorine-containing polymer .

The fluorine-containing polymer preferably has a refractive index of 1.37 to 1.45. When the refractive index is 1.37 or more, good solubility in a solvent is obtained and handling is easy. If it is 1.45 or less, the refractive index of the low refractive index layer to be formed can be reduced to a desired range.

Such a fluorine-containing polymer is available as a commercially available product. Examples of such a fluorine-containing polymer include Obsta TU2181-6, Obsuter TU2181-7, Obsuter TU2202, Obsuter JN35, Obsuter TU2224 manufactured by JSR, Optol AR110 manufactured by Daikin Industries, AR100, and the like.

The content of the fluorine-containing polymer is preferably 1 to 30 parts by mass, and more preferably 5 to 25 parts by mass, based on 100 parts by mass of the total solid content in the composition for forming a low refractive index layer. When the content of the fluorine-containing polymer is within the above range, the refractive index can be effectively lowered.

(Fluorine-containing monomer)

The composition for forming a low refractive index layer used in the present invention preferably contains a fluorine-containing monomer from the viewpoint of lowering the refractive index. It is preferable that the fluorine-containing monomer has two or more reactive functional groups in one molecule from the viewpoint of efficiently curing to form a low refractive index layer and obtaining an excellent hardness. Examples of the fluorine-containing monomer include a fluorine-containing monomer having a pentaerythritol skeleton, a fluorine-containing monomer having a dipentaerythritol skeleton, a fluorine-containing monomer having a trimethylolpropane skeleton, a fluorine-containing monomer having a cyclohexyl skeleton, And the like can be preferably used. Among these, compounds having a pentaerythritol skeleton are preferable.

The fluorine-containing monomer preferably has a refractive index of 1.35 to 1.48, more preferably 1.37 to 1.45. When the refractive index of the fluorine-containing monomer is 1.35 or more, good solubility in a solvent is obtained and handling is easy. If it is 1.48 or less, the refractive index of the low refractive index layer to be formed can be reduced to a desired range.

Such fluorine-containing monomers are commercially available, and examples thereof include LINC3A having a pentaerythritol skeleton made by Kyoeisha Chemical Co., Ltd. and LINC series such as LINC102A having a cyclohexyl skeleton.

The content of the fluorine-containing monomer is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the total solid content in the composition for forming a low refractive index layer. When the content of the fluorine-containing monomer is within the above range, the refractive index can be effectively lowered.

(Various additives)

In the composition for forming a low refractive index layer used in the present invention, various additives are blended according to desired properties. Examples of additives include additives such as weather resistance improvers, abrasion resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, adhesion improvers, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, defoaming agents, fillers, .

(solvent)

The solvent preferably used in the composition for forming a low refractive index layer is not particularly limited, and examples thereof include alcohols such as methanol, ethanol and isopropyl alcohol (IPA); Ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Esters such as ethyl acetate and butyl acetate; Halogenated hydrocarbons; Aromatic hydrocarbons such as toluene and xylene; Glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and dipropylene glycol monoethyl ether, and mixtures thereof. Among them, ketones and glycol ethers having high affinity with the fluorine-containing compound are preferable, and particularly preferable solvents are methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate. By using these alone or in combination, it is possible to maintain the dispersibility of each compound in the composition, and in the phase separation step (2), the phase separation between the low refractive index phase and the antifouling phase can be preferably completed.

When a solvent other than ketones or glycol ethers is used, it is preferable that ketones or glycol ethers contain at least 50% or more, preferably 70% or more of the total solvent amount. In particular, when ketones are used, the coating property of the composition for forming a low refractive index layer is improved and the drying rate of the solvent after application of the composition is appropriate, so that uneven drying is unlikely to occur and, Since the fluorine-containing compound can be phase-separated, a uniform and constant large-area coating film (antifouling layer) can be easily obtained.

The amount of the solvent is appropriately adjusted so that the respective components can be uniformly dissolved and dispersed and that the composition does not aggregate at the time of preservation after production and is not too lean at the time of coating. The content of the solvent in the composition for forming a low refractive index layer is preferably 50 to 99.5 mass%, more preferably 70 to 98 mass%. Such a content makes it possible to obtain a composition which is excellent in dispersion stability and suitable for long-term storage. Further, the solvent used in the composition for forming a low refractive index layer is evaporated by drying or curing after the composition is applied, so that it hardly exists in the low refractive index layer.

(Step (2))

The step (2) is a step of phase-separating the coating film formed in the step (1) into a low refractive index image and a defective image. As a method for promoting the phase separation, for example, a method of heating a coating film in air, a method of holding it in steam or in an autoclave, and the like can be preferably used. Further, it may be simply left until the phase separation without heating or the like.

In the present invention, after the composition for forming a low refractive index layer is coated and before the binder resin in the composition is cured, the fluorine-containing compound in the composition is heated (On the side opposite to the transparent substrate). As a result, it was found that the coating film of the composition for forming a low refractive index layer exhibited a stain-resistant film exhibiting antifouling property with a relatively large content of the fluorine-containing compound and a low refractive index film exhibiting a low refractive index with a relatively small content of the fluorine- Excellent antifouling properties can be obtained by phase separation and heating the spark formed on the outermost surface side or by irradiating ionizing radiation to form an antifouling layer covering the entire surface of the low refractive index layer. That is, in the present invention, when the composition for forming a low refractive index layer is applied to form a coating film, it is separated into two phases in the coating film, and the coating film has a low refractive index phase and a defective phase, The low refractive index layer and the antifouling layer are formed in the two phases, that is, the low refractive index layer having the antifouling layer is formed.

The time for heating or simply leaving the fluorine-containing compound is usually about 1 to 30 seconds, as long as the fluorine-containing compound floats on the outermost surface side of the coating film.

The solvent preferably contained in the composition for forming a low refractive index layer may be evaporated by heating or simply left standing as described above, or actively dried for evaporation of the solvent. The temperature for drying in this case is preferably in the range of 20 to 120 ° C, more preferably 40 to 100 ° C, and the drying time is preferably 10 to 180 seconds, more preferably 15 to 90 seconds. The upper limit temperature of the drying temperature is appropriately selected depending on the material of the transparent substrate to be used. On the other hand, the lower limit temperature of 20 占 폚 is preferably selected from the viewpoint of forming the antifouling layer by rapidly separating the fluorine-containing compound from the outermost surface reliably. Further, from the viewpoint of stably separating the spark phase to form a stainproof layer, 40 DEG C or more is more preferably selected.

(Step (3))

The step (3) is a step of heating the coated film after phase separation or irradiating the coating film with ionizing radiation to form the low refractive index layer and the scattering phase in the coating film into the low refractive index layer and the antifouling layer, respectively. Here, the low refractive index layer is a layer having antireflection properties because of the presence of fine particles in the layer, and the antifouling layer is a layer having antifouling properties because the fluorine-containing compound is present in the layer. In this specification, for the sake of convenience, the layer containing a relatively small amount of the fluorine-containing compound is referred to as a low refractive index layer (on the low refractive index layer before irradiation with heating or ionizing radiation) because it has more excellent antireflection properties, Is called an antifouling layer (a defective phase before irradiation with heating or ionizing radiation) because it has more excellent antifouling properties.

Whether the coating film is heated or irradiated with ionizing radiation is selected according to the binder resin contained in the composition for forming a low refractive index layer. When a thermosetting resin is employed as the binder resin, a heating process is selected. The heating conditions can be appropriately set in accordance with the curing temperature of the thermosetting resin to be used, and can be set to, for example, 60 to 100 占 폚.

When an ionizing radiation curable resin is used as the binder resin, the coating film may be irradiated with ionizing radiation. When the electron beam is used as the ionizing radiation when curing the coating film, the acceleration voltage thereof can be suitably selected according to the resin to be used and the thickness of the layer. Usually, the coating film is cured at an acceleration voltage of about 70 to 300 kV .

Further, in the irradiation of the electron beam, the higher the acceleration voltage is, the higher the permeability is. Therefore, when a base material deteriorated by the electron beam is used as the base material, By selecting the voltage, it is possible to suppress the irradiation of the extra electron beam to the substrate, and the deterioration of the substrate due to the excessive electron beam can be minimized.

The irradiation dose is preferably such that the crosslinking density of the curable resin in the low refractive index layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

The electron beam source is not particularly limited, and various electron beam accelerators such as a Cocloth Walton type, a Bandegraph type, a resonant transformer type, an insulating core transformer type, or a linear type, a dynamictron type and a high frequency type can be used have.

When ultraviolet rays are used as the ionizing radiation, for example, ultraviolet ray emitted from an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp or the like is used. The irradiation dose of the energy source is preferably about 50 to 500 mJ / cm 2 as an integrated exposure dose at ultraviolet wavelength 365 nm.

From the viewpoint of preventing oxygen inhibition on the surface of the resin composition for a low refractive index layer, irradiation with ultraviolet rays is preferably performed under an atmosphere of nitrogen, for example, in an atmosphere having an oxygen concentration of 1000 ppm or less. In the present invention, ultraviolet irradiation is most preferable in that after the phase separation, the low refractive index phase and the scattered phase can be stably and rapidly cured.

Further, by the curing of the step (3), the solvent is almost completely evaporated and dried, and hardly exists in the layer. It is considered that the solvent almost evaporates in the step (2), but the solvent remaining in the layer at the end of the step (2) is almost completely evaporated in the step (3).

[Antireflection Film]

The antireflection film of the present invention is obtained by the production method of the present invention and more specifically includes at least a transparent substance, a low refractive index layer and an antifouling layer covering the entire surface of the low refractive index layer in this order, Refractive index layer containing the fluorine-containing compound, the fine particles and the binder resin, wherein the refractive index layer and the stainproofing layer are made of a composition for forming a low refractive index layer containing a fluorine atom / carbon Wherein the atomic ratio is 0.6 to 1.0, the silicon atom / carbon atom ratio is less than 0.25, and the average surface roughness (Ra ') of the antifouling layer is 10 nm or less.

The antireflection film of the present invention will be described with reference to Figs. 1 to 3. Fig. FIG. 1 is a schematic view showing a cross section of the antireflection film of the present invention, and FIGS. 2 and 3 are schematic diagrams showing a cross section of the antireflection film of the present invention, taking an example of a preferable layer structure as an example. The antireflection film 1 shown in FIG. 1 has a low refractive index layer 3 and an antioxidant layer 8 on a transparent substrate 2. The antireflection film 1 shown in Fig. 2 has a hard coat layer 4, a high-refractive-index layer 7 and a low-refractive-index layer 3 in this order on a transparent substrate 2, The antireflection film 1 shown includes a hard coat layer 4, a medium refractive index layer 5, a high refractive index layer 6, a low refractive index layer 3 and a scattering layer 8 on a transparent substrate 2, Respectively. The layer structure of the antireflection film 1 of the present invention is not particularly limited as long as it has the low refractive index layer 3 and the antioxidant layer 8 on the transparent substrate 2 in this order. A transparent substrate / a hard coat layer / a medium refractive index layer / a high refractive index layer / a low refractive index layer / an antifouling layer / a transparent substrate / a hard coat layer / a low refractive index layer / A layer structure of a high refractive index layer / a medium refractive index layer / a low refractive index layer / a scattering layer, and a transparent substrate / a high refractive index layer / a low refractive index layer / a scattering layer. Although not shown, a functional layer such as an antistatic layer described later may be further provided on the transparent substrate side of the low refractive index layer.

(The low refractive index layer 3 and the antifouling layer 8)

The low refractive index layer 3 and the antioxidant layer 8 are layers formed using a composition for forming a low refractive index layer containing a fluorine-containing compound, fine particles and a binder resin. These layers are formed by applying a layer formed by the above-described method for producing an antireflection film of the present invention, that is, a composition for forming the low refractive index layer, onto a transparent substrate to form a coating film, Refractive index layer 3 and the antioxidant layer 8 by forming a low refractive index phase and a sparkling phase as two phases in the coating film and heating these films or irradiating ionizing radiation. The content of the fluorine-containing compound contained in the low refractive index layer 3 is relatively small as compared with the content of the fluorine-containing compound contained in the antifouling layer 8, and conversely, the content of the fluorine-containing compound is relatively large The antifouling layer (8) is the same as the above-described layer in which the antifouling property is more strongly expressed.

(Low refractive index layer 3)

It is most preferable that the refractive index of the low refractive index layer ³ is N ^1/2 when the refractive index of the layer formed immediately below the refractive index is N and the refractive index of the air is 1, (Meth) acrylic ionizing radiation curable resin, it is preferable that the hard coat layer has an N of 1.49 to 1.53. When the hard coat layer is formed by using a general-purpose polyfunctional (meth) acrylic ionizing radiation curable resin, N is preferably 0.01, and the refractive index is 1.48 to 1.52. The refractive index is preferably as low as possible, but is preferably from 1.25 to 1.45, more preferably from 1.25 to 1.35 from the viewpoint of balance between antireflection property and surface hardness. This refractive index can be easily controlled by the type and content of the fine particles, the amount of the fluorine-containing compound used, and the like.

In order to obtain the most antireflection effect, it is preferable that the film thickness and the refractive index of the low refractive index layer 3 satisfy the relationship calculated from the following formula (I).

In the formula (I), n _A represents the refractive index of the low refractive index layer, m represents a positive odd number, preferably 1 (air), lambda is a wavelength, preferably in the range of 480 to 580 nm . Therefore, in the present invention, it is preferable that m = 1 in the above formula (I) and λ is calculated from the following formula (II), in which the wavelength is 480 to 580 nm, The refractive index and the film thickness are preferable from the viewpoint of reducing the refractive index.

When the refractive index is in the above preferred range of 1.25 to 1.45, it is preferable that the film thickness is about 80 nm to 120 nm. However, since the refractive index is lower than that of the lower layer to obtain an antireflection effect, the film thickness may be about 120 nm to 1 占 퐉 which is outside this range. In the present invention, it is preferable that the total thickness of the low refractive index layer and the antifouling layer is in the above range.

(Antifouling layer 8)

The antifouling layer 8 exists so that the entire surface of the low refractive index layer 3 is uniformly and constantly covered with an average surface roughness (Ra ') of 10 nm or less and antifouling properties are imparted to the antireflection film of the present invention .

The average surface roughness Ra 'of the antifouling layer 8 is 10 nm or less and is a uniform and constant layer. The average surface roughness Ra 'of the antifouling layer 8 is preferably 0.1 to 10 nm, more preferably 0.1 to 7 nm, and still more preferably 0.1 to 5 nm, which is the most improved scratch resistance . Here, the average surface roughness (Ra ') is a three-dimensional extension of the centerline average roughness (Ra) defined in JIS B 0601 by applying the surface roughness to the measurement surface. Value " and is a numerical value provided by the following equation. For example, the average surface roughness (Ra ') can be calculated by observing the surface shape by an atomic force microscope (AFM) and analyzing the obtained image by using an associated analysis software (for example, SPIwin) .

Since the average surface roughness of the antifouling layer 8 is very small, uniform and constant as described above, has excellent scratch resistance and antifouling property and also has excellent antireflection characteristics as described above, the antireflection film formed on the outermost surface of the antireflection film of the present invention desirable.

The uniform and constant state of the antifouling layer 8 can be specifically confirmed not only by the average surface roughness Ra 'but also by observation with an atomic force microscope (AFM). That is, when observed with an atomic force microscope (AFM), the antifouling layer 8 has a structure in which the cured product of the composition for forming a low refractive index layer does not omnipresent on the shape and phase of the antifouling layer 8, The circular or elliptical holes are unevenly distributed in the five layers, and the lower layer such as the low refractive index layer and the transparent substrate is exposed. That is, in the state that the lower layer is formed over the entire surface of the antireflection film 1 .

The fluorine atom / carbon atom ratio measured by X-ray photoelectron spectroscopy (XPS) from the side of the antifouling layer 8 is 0.6 to 1.0, and the silicon atom / carbon atom ratio is required to be less than 0.25. Here, the fluorine atom / carbon atom ratio and silicon atom / carbon atom ratio are calculated from the composition ratio of fluorine atom, carbon atom and silicon atom as measured by X-ray photoelectron spectroscopy (XPS) from the antifouling layer side of the antireflection film Value.

In the present invention, excellent fluoride resistance is exhibited when the fluorine atoms in the antifouling layer 8 are present at a certain level or more and silicon atoms are present at a certain level or less, that is, by using predetermined fluorine-containing compounds in predetermined amounts, It is possible to obtain an antireflection film having little whitening. Further, since the antifouling layer is uniformly and uniformly formed over the entire surface, the antifouling property can be obtained by having the above-mentioned atomic ratio over the whole surface, so that the generation of minor whitening can be reduced.

From this viewpoint, the fluorine atom / carbon atom ratio is more preferably 0.7 to 1.0, and still more preferably, the silicon atom / carbon atom ratio is 0.01 to 0.2. If the fluorine atom / carbon atom ratio is less than 0.6, the antifouling property becomes insufficient. On the other hand, if it is larger than 1.0, handling of the agent used to achieve this, that is, the fluorine-containing compound becomes remarkably difficult. When the silicon atom / carbon atom ratio is 0.25 or more, the antifouling property becomes insufficient. In the present invention, the ratio is less than 0.25. However, when the silicon atom / carbon atom ratio is in this range, slidability is improved and excellent scratch resistance can be expected.

When the isothermal structure is confirmed by an atomic force microscope (AFM), or when the average surface roughness, in which a convex portion is observed in a part of the isothermal surface, is a coarse surface outside the range specified in the present invention, the X-ray photoelectron spectroscopy XPS) does not fall within the range of the atomic ratios as described above. That is, in the coating film obtained by applying the composition for forming a low refractive index layer, the low refractive index phase is phase-separated from the stain-proof phase, and furthermore, the stainproof layer is formed as a uniform and constant layer on the low refractive index layer. The above specified atomic ratio is measured, and the scattering layer is a uniform and constant layer is also confirmed by the measurement by an atomic force microscope (AFM). Therefore, the antifouling layer has an average surface roughness and an atomic ratio defined in the present invention, whereby an antireflection film is obtained in addition to excellent antifouling property, and an antireflection film which does not exhibit a slight whiteness can be obtained. In the present invention, the average surface roughness (Ra ') measured by the atomic force microscope (AFM), the shape and phase image observation, and the atomic ratio measured by X-ray photoelectron spectroscopy (XPS) Reflection film produced by the production method of the present invention or the antireflection film of the present invention. Although the presence of an antioxidant layer on the low refractive index layer may be observed by observing the TEM cross section in some cases, the above evaluation method is effective in consideration of a very thin layer. In addition, when a scattering layer is formed by a vapor deposition method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD), unlike the manufacturing method of the present invention, the scattering layer and the low refractive index layer are formed in a reactive group And thus the abrasion resistance is weakened because the adhesion is weak. That is, the difference in the manufacturing method can be confirmed by the scratch resistance evaluation. Here, the abrasion resistance evaluation was carried out by applying a load of 300 g / cm 2 or more to a steel wool (BONSTA # 0000 manufactured by Nippon Steel Wool Co., Ltd.), rubbing the surface of the antireflection film 10 times, It is by seeing.

The silicon atoms in the low refractive index layer and the antifouling layer exist in the form of SiO ₂ or C-Si-O. In the present invention, silicon atoms derived from SiO ₂ are referred to as inorganic silicon atoms and C- The silicon atom derived from Si-O is referred to as an organosilicon source. That is, in the present invention, the silicon atoms in the low refractive index layer and the antifouling layer have an organic silicon atom and an inorganic silicon atom.

It is considered that the inorganic silicon atoms and the organic silicon atoms are separated in the Si2p spectrum because the bonding energies are different. By peak separation analysis, the peak near 103 to 104 eV on the side of high bonding energy was regarded as an inorganic silicon atom, and the peak on the side of low binding energy was found near 101 to 102 eV as an organic silicon atom. The silicon atom in the above silicon atom / carbon atom ratio is the sum of the inorganic silicon atom and the organic silicon atom.

In the present invention, the organosilicon atom / carbon atom ratio measured by X-ray photoelectron spectroscopy (XPS) from the antifouling layer side is preferably 0.07 or less, more preferably 0.01 to 0.07, and still more preferably 0.02 to 0.06 to be. The inorganic silicon atom / carbon atom ratio is preferably 0.2 or less, more preferably 0.05 to 0.2, and still more preferably 0.08 to 0.18. When the ratio of the organosilicon atom / carbon atom and the inorganic silicon atom / carbon atom is within the above range, excellent anti-scratch and antifouling properties are exhibited, and an antireflection film which does not cause slight whitening can be obtained.

In the present invention, by satisfying the above-described atomic ratio, a method of phase-separating the entire surface of the low refractive index layer using a composition for forming a low refractive index layer without improving the compatibility of a conventional fluorine-containing compound By forming the antifouling layer so as to be covered with the antifouling layer, the occurrence of the sea-island structure as described above is suppressed, and the antifouling layer becomes a uniform and constant layer having a small average surface roughness.

Further, by using a composition for forming a low refractive index layer combining a fluorine-containing compound and fine particles and a binder resin, it is possible to obtain a uniform and constant antifouling layer 8, and consequently to have excellent antireflection properties, It is possible to obtain an antireflection film having antifouling property and suppressing the generation of a slight whitening.

If it is a smooth surface, it is theoretically impossible for the contact angle of hexadecane to exceed 90 ° by the organic compound forming the antifouling layer. Therefore, the contact angle and the angle of inclination can be measured by a commercially available contact angle meter and a tilting angle meter using hexadecane as the measurement liquid.

When the outermost surface of the antireflective film (1) of the present invention is an antifouling layer (8), the contact angle of the surface with respect to hexadecane is preferably 55 to 90 °, more preferably 60 to 90 °, Also, the angle of inclination of the surface with respect to hexadecane is preferably 1 to 25 deg., More preferably 1 to 20 deg., And the outermost surface thereof is uniform and constant, that is, the antifouling layer 8 has a smooth structure . Since the fluorine-containing compound contained in the antifouling layer 8 covers the surface, the contact angle and the falling angle are in the above-mentioned ranges. On the other hand, if the surface can not be uniformly and uniformly covered by forming the sea water structure, The falling angle deviates from the above range.

The total thickness of the low refractive index layer 3 and the scattering layer 8 varies depending on the desired refractive index, but is preferably about 80 to 120 nm as described above from the viewpoint of reducing the reflectance in the visible light region. More preferably, it is 100 to 120 nm.

It is assumed that the thickness of only the antifouling layer 8 is in the range of 1 to 3 nm. Atoms contained in the fine particles in the low refractive index layer are also detected by the above-described X-ray photoelectron spectroscopy (XPS), and considering that the depth of information obtained by X-ray photoelectron spectroscopy (XPS) is 1 to 3 nm , It is reasonable to assume that it is in the range of 1 to 3 nm.

(Hard coat layer 4)

The antireflection film (1) of the present invention may have the hard coat layer (4) for the purpose of improving the surface hardness performance such as scratch resistance on the antireflection film (1). Here, the term "hard coat" refers to a performance showing a hardness of "H" or higher in the pencil hardness test prescribed in JIS 5600-5-4: 1999.

The hard coat layer is preferably obtained by crosslinking and curing an ionizing radiation curable resin. The ionizing radiation curable resin for forming the hard coat layer 4 is appropriately selected from the ionizing radiation curable resins used for the binder resin in the above composition for forming a low refractive index layer. The photopolymerization initiation system used when the ionizing radiation curable resin is an ultraviolet ray curable resin is appropriately selected from those exemplified above and used. In addition, various additives used in the composition for forming a low refractive index layer described above can be similarly used.

The thickness of the hard coat layer 4 after curing is preferably in the range of 0.1 to 100 탆, more preferably in the range of 0.8 to 20 탆, further preferably in the range of 1 to 8 탆, more preferably in the range of 1.5 to 4 Mu m is preferable. When the film thickness is within the above range, a sufficient hard coat performance is obtained, and it is difficult to break against external impacts. Further, in the present invention, even if the hard coat layer 4 has the function of the medium refractive index layer 5 or the high refractive index layer 6 as described below, or the function of the antistatic layer do.

(Medium refractive index layer 5 and high refractive index layer 6)

The antireflection film (1) of the present invention may preferably have a medium refractive index layer (5) and a high refractive index layer (6) for the purpose of improving antireflection performance. The medium refractive index layer 5 and the high refractive index layer 6 need not be formed simultaneously with the medium refractive index layer 5 and the high refractive index layer 6 in the form of the antireflection film 1 For example, as a first-layer refractive index layer 7 as shown in Fig.

The refractive index of the medium refractive index layer 5, the high refractive index layer 6 or the middle refractive index layer 7 (hereinafter sometimes referred to as the refractive index layer) may be desirably set within a range of 1.5 to 2.00. That is, the medium refractive index layer 5 is at least higher in refractive index than the low refractive index layer 3 and lower in refractive index than the high refractive index layer 6, and the refractive index is relatively high. The refractive indexes of the medium refractive index layer 5 and the high refractive index layer 6 are relatively as described above but the refractive index of the medium refractive index layer 5 is usually in the range of 1.5 to 1.8 and the refractive index of the high refractive index layer 6 is 1.6 To 2.0.

These refractive index layers can be formed of, for example, a binder resin and fine particles having a particle diameter of 100 nm or less and a predetermined refractive index. Specific examples of the fine particles having a predetermined refractive index (indicating the refractive index in parentheses) include ZnO (1.90), TiO ₂ (2.3 to 2.7), CeO ₂ (1.95), indium tin oxide (abbreviated to ITO; Doped tin oxide (abbreviated as ATO; 1.80), Y ₂ O ₃ (1.87), and ZrO ₂ (2.0). The binder resin is appropriately selected from among the above-mentioned binder resins.

The refractive index of the fine particles is preferably higher than the refractive index of the cured film of the binder resin alone. Since the refractive index of these refractive index layers is generally determined by the content of the fine particles, the refractive index of the refractive index layer increases as the amount of the fine particles added increases. Therefore, it is possible to form a refractive index layer having a predetermined refractive index by adjusting the addition ratio of the binder resin and the fine particles. If the fine particles have conductivity, the refractive index layer formed by using such fine particles has antistatic properties. The refractive index layer may be a vapor-deposited film of inorganic oxide having a high refractive index such as titania or zirconia formed by a vapor deposition method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD), or may be an inorganic oxide fine particle having a high refractive index such as titania It is possible to obtain a resin cured film using a resin composition appropriately dispersed in a binder resin.

The film thickness of these refractive index layers is preferably in the range of 10 to 300 nm, more preferably in the range of 30 to 200 nm. The hard coat layer 4 is formed on the transparent substrate 2 and the hard coat layer 4 and the low refractive index layer 4 are formed on the transparent substrate 2, (3).

(Antistatic layer)

The antireflection film (1) of the present invention has an antistatic effect in view of preventing the adhesion of dust or the conductivity or electromagnetic wave shielding effect when the antireflection film of the present invention is used for an image display device, . It is preferable that the antistatic layer be formed between the transparent substrate 2 and the low refractive index layer 3 and that the hard coat layer 4, the medium refractive index layer 5 or the high refractive index layer 6 is formed It is preferable to form the low refractive index layer 3 on the outermost surface and to contact the low refractive index layer 3.

The antistatic layer is not particularly limited and, for example, those formed by a composition for an antistatic layer containing a resin and an antistatic agent are preferably used.

The antistatic agent is not particularly limited, and examples thereof include cationic compounds such as quaternary ammonium salts, pyridinium salts, and primary to tertiary amino groups; Anionic compounds such as sulfonic acid bases, sulfuric acid ester bases, phosphoric acid ester bases, and phosphonic acid bases; Amphoteric, aminosulfuric ester or the like; Nonionic compounds such as amino alcohol type, glycerin type, and polyethylene glycol type; Organometallic compounds such as tin and alkoxide of titanium; A metal chelate compound such as an acetylacetonate salt of the organometallic compound, and the like. A compound obtained by high-molecular weight compound as described above can also be used.

As the antistatic agent, a polymerizable compound such as an organometallic compound having a tertiary amino group, a quaternary ammonium group or a metal chelate moiety, and a monomer capable of being polymerized by ionizing radiation or an oligomer or a coupling agent having a functional group, . These antistatic agents may be ionic liquids.

As the antistatic agent, a conductive polymer is also preferably used. The conductive polymer is not particularly limited, and examples thereof include poly (paraphenylene) of an aromatic conjugated system, polypyrrole of a heterocyclic conjugated system, polythiophene, polyacetylene of an aliphatic conjugated system, polyaniline of a heteroatom- A conjugated system poly (phenylenevinylene), a conjugated system of a conjugated system having a plurality of conjugated chains in the molecule, and a conductive complex which is a polymer obtained by grafting or block copolymerizing the above conjugated polymer chain with a saturated polymer.

As the antistatic agent, conductive metal oxide fine particles are also preferable. As the conductive metal oxide fine particles is not particularly limited, for example, ZnO (refractive index 1.90, or less, the value in parentheses will both represent the refractive _{index), Sb 2 O 2 (1.71} ), SnO 2 (1.997), CeO 2 (1.95 ), Indium tin oxide (abbreviated as ITO; 1.95), In ₂ O ₃ (2.00), Al ₂ O ₃ (1.63), antimony doped tin oxide (abbreviated as ATO; 2.0), aluminum doped zinc oxide .

The content of the antistatic agent in the composition for an antistatic layer is not particularly limited so long as it can fully enjoy the effect of containing the antistatic agent and can be suitably compounded within a range that does not impair the effect obtained in the optical laminate produced by the present invention .

The resin in the antistatic layer, that is, the resin used for the composition for the antistatic layer is not particularly limited and, for example, an ionizing radiation curing type resin which is a resin curable by ultraviolet rays or electron rays similar to the resins described in the hard coat layer A resin, a mixture of an ionizing radiation curable resin and a solvent drying type resin, or a thermosetting resin.

The antistatic layer is formed by applying a composition for an antistatic layer prepared by using each of the above-mentioned materials onto a light-transmitting base material or the like and drying it if necessary and curing it by ionizing radiation or heating .

[Polarizer]

The polarizing plate of the present invention is characterized in that the polarizing film has an antireflection film on at least one side of the polarizing film and the antireflection film is one obtained by the production method of the present invention, that is, at least the transparent substrate, the low refractive index layer and the entire surface Wherein the low refractive index layer and the antifouling layer are made of a composition for forming a low refractive index layer containing a fluorine-containing compound, a fine particle and a binder resin, and the X- (XPS) of 0.6 to 1.0, a silicon atom / carbon atom ratio of less than 0.25, and an average surface roughness (Ra ') of the antifouling layer of 10 nm or less. With such a constitution, the polarizing plate of the present invention is provided with an antireflection function excellent in physical strength and light resistance, and further, the cost can be reduced considerably and the display device can be made thinner.

Usually, the polarizing plate forms a protective film on both sides of the polarizing film, whereas the polarizing plate of the present invention is provided with the antireflection film of the present invention on at least one side thereof. In the present invention, the antireflection film of the present invention can be formed on one side or both sides of the polarizing film. In the case of forming the film on one side, it is preferable that the film is an optical compensation film (phase difference film) having an optical compensation layer including an optically anisotropic layer on the other side from the viewpoint of improving the viewing angle characteristics of the liquid crystal display screen.

When the antireflection film of the present invention is used as a protective film, it is particularly preferable to use a triacetylcellulose film as the transparent support. In this case, it is preferable that the transparent support of the protective film using the antireflection film is bonded to the polarizing film through an adhesive layer or the like comprising polyvinyl alcohol if necessary. Further, as described above, a protective film, preferably the optical compensation film (retardation film) described above, is also preferably provided on the other side of the polarizing film. And a pressure-sensitive adhesive layer may be provided on the surface of the other protective film opposite to the polarizing film. With such a configuration, the polarizing plate of the present invention can improve the contrast in the bright room of the liquid crystal display device, and the viewing angle of up and down and right and left.

[Image display device]

The image display device of the present invention is characterized in that it has an antireflection film or a polarizing plate having an antireflection film on at least one side of a polarizing film on the outermost surface of the display and the antireflection film is one obtained by the production method of the present invention, A low refractive index layer and an antioxidant layer covering the entire surface of the low refractive index layer in this order, wherein the low refractive index layer and the antioxidant layer each comprise a fluorine-containing compound, fine particles and a binder resin, Wherein the fluorine atom / carbon atom ratio measured by X-ray photoelectron spectroscopy (XPS) is 0.6 to 1.0, the silicon atom / carbon atom ratio is less than 0.25, and the average surface roughness (Ra ') is 10 nm or less.

Examples of the display include a liquid crystal display (LCD), a plasma display panel (PDP), a cathode ray tube display (CRT), an inorganic and organic electroluminescence display, a rear projection display, a fluorescent display tube (VFD) A display such as a PC or an electronic paper, and the like. Further, as the image display apparatus, an apparatus provided with these displays, for example, a personal computer, a portable information terminal, a game machine, a digital camera, a digital video camera and the like are preferably used.

Example

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited at all by this example.

(Assessment Methods)

1. Lowest Reflectance (Evaluation of Antireflection Characteristics)

For each of the antireflection films obtained in each of the Examples and Comparative Examples, a black tape for preventing the back reflection of the film was attached to the side of the transparent substrate on which the low refractive index layer was not formed, and the surface of the low refractive index layer was subjected to regular reflection The reflectance was measured using a spectrophotometer ("UV-2550 (model number)" manufactured by Shimadzu Corporation) equipped with a device, and the minimum value at 380 to 780 nm in the wavelength range was defined as the lowest reflectance. The smaller the minimum reflectance, the more excellent the antireflection film has.

2. Evaluation of application surface

A black tape was attached to the surface of the film on which the low refractive index layer was not formed, and the surface of the low refractive index layer was observed with naked eyes by a three-wavelength lamp.

?: The surface of the low refractive index layer was uniform and constant.

?: A slight distortion was observed on the surface of the low refractive index layer as compared with the above evaluation of?.

X: The surface of the low refractive index layer was slightly white.

3. Evaluation of surface abrasion resistance and adhesion

The antireflection film obtained in each of the Examples and Comparative Examples was subjected to 10 reciprocating rubs by applying a load of 300 g / cm 2 to a steel wool (BONSTA # 0000 manufactured by Nippon Steel Wool Co., Ltd.) Respectively. The smaller the scratches, the better the scratch resistance and the adhesion between the low refractive index layer and the antifouling layer.

○: No scratches at all

?: The number of scratches was 1 to 5

X: Number of scratches was 6 or more

4. Evaluation of antifouling property

(1) Antifouling property against fingerprint

After attaching the fingerprints to the surface of the antireflection film obtained in each of the Examples and Comparative Examples, the film was wiped with MAKOTE M-3 (manufactured by Asahi Kasei Kabushiki Kaisha), visibility of wiping was visually confirmed, Respectively.

○: The fingerprints were easily wiped.

△: Fingerprint was wiped.

X: The fingerprint is not wiped

(2) The state of the antireflection film obtained in each of the examples and the comparative example was visually observed when the state was painted with oil magic and wiped off with a cloth, and evaluated by the following criteria.

◎: Ink was repelled by spherical shape and wiped easily

○: Since the ink repelled and the line became thinner, it was easy to wipe off

X: ink marks remain after wiping

5. Measurement of atomic ratio by X-ray photoelectron spectroscopy of low refractive index layer

The surface of the antireflection film (antifouling layer) obtained in each of the Examples and Comparative Examples was analyzed by X-ray photoelectron spectroscopy (XPS) to determine the degree of separation of the fluorine-containing compound to form the antioxidant layer The compassion was obtained by the following method.

The used device is an XPS device ("ESCALAB 220i-XL", manufactured by Thermo Scientific Co., Ltd.), and has an X-ray output of 10 kV and 16 mA (160 W) (FOV = open, AA = open, measurement area: 700 탆, optoelectronic angle: 90 degrees (placing the input lens on the sample normal), neutralization charge: electron neutralization total +4 ㎃), and neutralization assist metal mask. The fluorine atom / carbon atom ratio and silicon atom / carbon atom ratio were calculated using the atomic composition of carbon atoms, nitrogen atoms, oxygen atoms, fluorine atoms and silicon atoms on the surface of the antireflection film obtained by this measurement. As to silicon atoms, an inorganic silicon component (SiO ₂ ) whose peak is detected in the vicinity of 103 to 104 eV and an organic silicon component (C-Si (Si) in which a peak is detected in the vicinity of 101 to 102 eV) -O), and the atomic composition was measured, and the ratio of inorganic silicon atoms / carbon atoms and organic silicon atoms / carbon atoms was calculated.

6. Evaluation of surface condition (measurement of contact angle and angle of inclination)

The antireflection film obtained in each of the Examples and Comparative Examples was subjected to measurement using a hexadecane as a measurement liquid and measuring the contact angle with use of a measuring device (DM-500 (model number), manufactured by Kyowa Kaimen Kagaku Kabushiki Kaisha) And angle of inclination were measured. The amount of droplet was 2 μl.

7. Evaluation of Surface Condition (Evaluation of Surface Observation by Atomic Force Microscope)

The surface of the antireflection film obtained in each of the examples and the comparative examples was measured in dynamic force mode using an atomic force microscope (AFM) ("L-trace", manufactured by SII Nanotechnology Co., Ltd.) : 0.4 to 1.0 Hz, and a scanning range of 3 占 퐉. The cantilever used was "OMCL-AC160TS-C2 (model no.)" (Manufactured by KS Olympus Corporation, spring constant: 42 N / m). Here, a cantilever used for observation was always a new one so that there is no degradation in resolution due to probe contamination. Further, in order to prevent wear deterioration at the time of observation, the measurement was performed under a condition that the load applied to the probe was as small as possible within a range not sacrificing the resolution, and observation was made at a resolution of 512 pixels x 256 pixels. After the observation, the inclination of the data was corrected by the software of the accessory.

By this surface observation, it is possible to confirm a uniform and constant state when the anti-scattering layer is formed on the entire surface of the low refractive index layer and the anti-scattering layer is not formed on the whole surface of the surface In this case, the surface can be identified as the shape of a stain due to the phase separated portion and the phase not separated portion. Here, in the case of a uniform and constant state, it can be said that there is no slight whitening on the naked eye or roughness of the coated surface, and the low refractive index layer and the antifouling layer are preferably formed.

○: The stratum corneum was uniform and constant

?: There was no sea structure in the antifouling layer, but a slight distortion was observed in comparison with the above evaluation of?.

X: The omnidirectional layer exhibits a sea-island structure, and slight roughness of the whiteness or the coated surface is observed with the naked eye

8. Measurement of Average Surface Roughness (Ra ')

The surface morphology was observed by the atomic force microscope (AFM), and image analysis was performed using analysis software (SPIwin) to obtain an average surface roughness (Ra ').

Preparation Example 1: Preparation of Composition 1 for Low Refractive Index Layer

The following composition was mixed at the following mass ratio to prepare a composition 1 for forming a low refractive index layer.

Composition 1 for forming a low refractive index layer

Pentaerythritol triacrylate (PETA): 0.10 parts by mass

Fluorine-containing compound ^{* 1} : 1.23 parts by mass

Dispersion of hollow silica particles ^{* 2} : 6.69 parts by mass

Dispersion of solid silica particles ^{* 3} : 0.74 parts by mass

Fluorine-containing polymer ^{* 4} : 2.79 parts by mass

Fluorine-containing monomer ^{* 5} : 2.23 parts by mass

Photopolymerization initiator ^{* 6} : 0.08 parts by mass

Methyl isobutyl ketone: 57.03 parts by mass

Propylene glycol monomethyl ether acetate: 29.1 parts by mass

(Solvent: methyl isobutyl ketone, photo-curable reactor: (meth) acryloyl group, reactive silane unit (meth) acrylate unit And a fluorine-containing compound having a silane unit having a perfluoropolyether group)

* 2, the content of the hollow silica particles in the dispersion was 20 mass%, and the content of the solvent (methyl isobutyl ketone) was 80 mass%. The average particle diameter of the hollow silica particles is 60 nm, and has a photo-curable reactor by surface treatment.

* 3, "MIBK-SD (trade name)", average primary particle diameter: 12 nm, solids content: 30 mass%, solvent: methyl isobutyl ketone, solid silica particles were subjected to surface treatment to obtain a photocurable reacting methacryloyl group I have.

* 4, "Obstar JN35 (trade name)", 20% by mass solution (solvent: methyl isobutyl ketone) manufactured by JSR,

* 5, "LINC3A (trade name)": a fluorine-containing monomer having a pentaerythritol skeleton, a 20 mass% solution (solvent: methylisobutylketone) made by Kyowa Chemical Co.,

* 6, "Irgacure 127 (trade name)": manufactured by Ciba Specialty Chemicals Co., Ltd.

Production Example 2: Preparation of composition 1 for hard coat layer formation

The following composition was mixed at the following mass ratio to prepare a composition 1 for hard coat layer formation.

Composition 1 for forming a hard coat layer

Urethane acrylate ^{* 7} : 15 parts by mass

Isocyanuric acid EO-modified triacrylate ^{* 8} : 15 parts by mass

Polymerization initiator ^{* 9} : 2 parts by mass

Methyl ethyl ketone: 70 parts by mass

* 7, " UV1700B (trade name) ", manufactured by Nippon Kosei Kagaku Co.,

* 8, " M315 (trade name) ", manufactured by Toagosei Co.,

* 9, "Irgacure 184 (trade name)": manufactured by Ciba Specialty Chemicals Co.,

Example 1

The composition for forming a hard coat layer 1 was coated on a triacetylcellulose (TAC) resin film having a thickness of 80 탆 by bar coating and dried at 50 캜 for 1 minute to remove the solvent. Then, an ultraviolet ray irradiation apparatus And a hard coat layer having a thickness of about 10 mu m was obtained by irradiating ultraviolet rays at an irradiation dose of 30 mJ / cm < 2 >

Subsequently, a coating film was formed on the obtained hard coat layer by bar coating the low refractive index layer forming composition 1 prepared in Production Example 1 (step (1)) and heat treatment was performed at 50 占 폚 for 1 minute, (Step (2)), ultraviolet rays are irradiated at an irradiation dose of 200 mJ / cm 2 to be cured to form a low refractive index layer and an antifouling layer (step (3)), ), A transparent substrate, a hard coat layer, a low refractive index layer and an antifouling layer. During curing, the solvent was almost completely evaporated, and the total thickness of the low refractive index layer and the antifouling layer was about 100 nm. In addition, atoms contained in the fine particles in the low refractive index layer were also detected during the measurement of the atomic ratio by X-ray photoelectron spectroscopy (XPS). Considering that the thickness of the X-ray photoelectron spectroscopy (XPS) scattering layer is 1 to 3 nm, it is presumed that the thickness of the obtained scattering layer is in the range of 1 to 3 nm.

The obtained antireflection film was evaluated by the above evaluation method, and the results are shown in Table 1. Further, an atomic force microscope (shaped image and gastric image) is shown in Fig.

Example 2

An antireflection film was obtained in the same manner as in Example 1 except that the composition for forming a low refractive index layer 1 was changed to the composition for a low refractive index layer 2 described below. The obtained antireflection film was evaluated by the above evaluation method, and the results are shown in Table 1. In addition, the atomic force microscope images (shaped image and stomata image) are shown in Fig.

Composition 2 for forming a low refractive index layer

Pentaerythritol triacrylate (PETA): 1.32 parts by mass

Fluorine-containing compound ^{* 1} : 1.32 parts by mass

Dispersion of hollow silica particles ^{* 2} : 6.61 parts by mass

Photopolymerization initiator ^{* 6} : 0.07 parts by mass

Methyl isobutyl ketone: 61.03 parts by mass

Propylene glycol monomethyl ether acetate: 29.1 parts by mass

Example 3

An antireflection film was obtained in the same manner as in Example 1 except that the composition for forming a low refractive index layer 1 was changed to the composition for a low refractive index layer 3 described below. The obtained antireflection film was evaluated by the above evaluation method, and the results are shown in Table 1. In addition, the atomic force microscope images (shaped image and stomata image) are shown in Fig.

Composition 3 for forming a low refractive index layer

Pentaerythritol triacrylate (PETA): 0.12 parts by mass

Fluorine-containing compound ^{* 1} : 2.07 parts by mass

Dispersion of hollow silica particles ^{* 2} : 6.28 parts by mass

Dispersion of solid silica particles ^{* 3} : 0.7 parts by mass

Fluorine-containing polymer ^{* 4} : 2.62 parts by mass

Fluorine-containing monomer ^{* 5} : 2.09 parts by mass

Photopolymerization initiator ^{* 6} : 0.07 parts by mass

Methyl isobutyl ketone: 56.96 parts by mass

Propylene glycol monomethyl ether acetate: 29.1 parts by mass

Production Example 3: Production Example of composition for forming a high refractive index layer

10 parts by mass of rutile type titanium oxide ("TTO51 (C) (trade name)", manufactured by Ishihara Sangyo K.K., primary particle diameter: 0.01 to 0.03 μm), 10 parts by mass of anionic group- 2 parts by mass, manufactured by BICKEMI Japan) and 48 parts by mass of methyl isobutyl ketone were mixed in a mayonnaise bottle to prepare a mixture. The obtained mixture was stirred for 10 hours by using a paint shaker using zirconia beads (φ 0.3 mm) about 4 times its amount, to prepare a composition for forming a high refractive index layer.

Production Example 4: Production Example of Composition for Forming a Medium-Refractive Index Layer

In the production example of the composition for forming a high refractive index layer, the rutile titanium oxide was changed to antimony doped tin oxide ("SN-100P (trade name)" manufactured by Ishihara Sangyo Kikai Co., Ltd.) 111 (trade name) "(manufactured by BICKEMI Japan), a composition for forming a medium refractive index layer was prepared in the same manner as in the production example of the composition for forming a high refractive index layer.

Example 4

The composition for forming a hard coat layer 1 was coated on a triacetyl cellulose (TAC) resin film having a thickness of 80 mu m and dried at 50 DEG C for 1 minute to remove the solvent. Thereafter, an ultraviolet irradiator (Fusion UV System Japan Manufactured by Takara Shuzo Co., Ltd.) was irradiated with ultraviolet rays at an irradiation dose of 30 mJ / cm < 2 > to be hardened to obtain a hard coat layer having a thickness of about 10 mu m.

On the obtained hard coat layer, a composition for forming a medium refractive index layer obtained in Production Example 4 was bar coated and cured by ultraviolet irradiation at an irradiation dose of 200 mJ / cm 2 to form a high refractive index layer having a thickness of about 120 nm, The composition for forming a high refractive index layer obtained in 3 was coated on the bar and cured by ultraviolet irradiation at an irradiation dose of 200 mJ / cm 2 to form a high refractive index layer having a thickness of about 60 nm. Subsequently, the composition for forming a low refractive index layer 4 is applied to form a coating film (step (1)), and the coating film is subjected to heat treatment at 50 占 폚 for one minute to separate the coating film into a low refractive index phase and a superficial phase, After the solvent is removed (step (2)), ultraviolet rays are irradiated at an irradiation dose of 200 mJ / cm 2 to be cured to form a low refractive index layer and an antifouling layer (step (3)), Reflection layer having a low refractive index layer, a high refractive index layer, a low refractive index layer and an antifouling layer. Upon curing, the solvent was almost completely evaporated, and the total thickness of the low refractive index layer and the antifouling layer was about 100 nm. In addition, atoms contained in the fine particles in the low refractive index layer were also detected during the measurement of the atomic ratio by X-ray photoelectron spectroscopy (XPS). Considering that the thickness of the X-ray photoelectron spectroscopy (XPS) scattering layer is 1 to 3 nm, it is presumed that the thickness of the obtained scattering layer is in the range of 1 to 3 nm.

The obtained antireflection film was evaluated by the above evaluation method, and the results are shown in Table 1. 7 shows the atomic force microscope image (the topographic image and the topographic image).

Composition 4 for forming a low refractive index layer

Pentaerythritol triacrylate (PETA): 0.32 parts by mass

Fluorine-containing compound ^{* 1} : 0.71 parts by mass

Dispersion of hollow silica particles ^{* 2} : 6.42 parts by mass

Dispersion of solid silica particles ^{* 3} : 1.43 parts by mass

Fluorine-containing polymer ^{* 4} : 3.21 parts by mass

Fluorine-containing monomer ^{* 5} : 0.54 parts by mass

Photopolymerization initiator ^{* 6} : 0.07 parts by mass

Methyl isobutyl ketone: 58.2 parts by mass

Propylene glycol monomethyl ether acetate: 29.1 parts by mass

Example 5

An antireflection film was obtained in the same manner as in Example 1 except that the composition for forming a low refractive index layer 1 was changed to the composition for a low refractive index layer 5 described below. The obtained antireflection film was evaluated by the above evaluation method, and the results are shown in Table 1. Fig. 8 shows the atomic force microscopic images (the topographic image and the topographic image).

Composition 5 for forming a low refractive index layer

Pentaerythritol triacrylate (PETA): 0.10 parts by mass

Fluorine-containing compound ^{* 10} : 1.23 parts by mass

Dispersion of hollow silica particles ^{* 2} : 6.69 parts by mass

Dispersion of solid silica particles ^{* 3} : 0.74 parts by mass

Fluorine-containing polymer ^{* 4} : 2.79 parts by mass

Fluorine-containing monomer ^{* 5} : 2.23 parts by mass

Photopolymerization initiator ^{* 6} : 0.08 parts by mass

Methyl isobutyl ketone: 57.04 parts by mass

Propylene glycol monomethyl ether acetate: 29.1 parts by mass

(Solvent: a mixture of methyl isobutyl ketone and methyl ethyl ketone, photo-curable reactor: (meth) acryloyl group (meth) acrylate, , A fluorine-containing compound having a reactive silane unit and a perfluoropolyether group-containing silane unit)

Example 6

An antireflection film was obtained in the same manner as in Example 1 except that the composition for forming a low refractive index layer 1 was changed to the composition for a low refractive index layer 6 described below. The obtained antireflection film was evaluated by the above evaluation method, and the results are shown in Table 1.

Composition 6 for forming a low refractive index layer

Dipentaerythritol hexaacrylate (DPHA): 1.32 parts by mass

Fluorine-containing compound ^{* 1} : 1.32 parts by mass

Dispersion of hollow silica particles ^{* 2} : 6.61 parts by mass

Photopolymerization initiator ^{* 6} : 0.07 parts by mass

Methyl isobutyl ketone: 61.03 parts by mass

Propylene glycol monomethyl ether acetate: 29.1 parts by mass

Example 7

An antireflection film was obtained in the same manner as in Example 1 except that the composition for forming a low refractive index layer 1 was changed to the composition for a low refractive index layer 7 described below. The obtained antireflection film was evaluated by the above evaluation method, and the results are shown in Table 1.

Composition 7 for forming a low refractive index layer

Pentaerythritol triacrylate (PETA): 0.10 parts by mass

Fluorine-containing compound ^{* 1} : 2.93 parts by mass

Dispersion of hollow silica particles ^{* 2} : 5.86 parts by mass

Dispersion of solid silica particles ^{* 3} : 0.65 parts by mass

Fluorine-containing polymer ^{* 4} : 2.44 parts by mass

Fluorine-containing monomer ^{* 5} : 1.95 parts by mass

Photopolymerization initiator ^{* 6} : 0.07 parts by mass

Methyl isobutyl ketone: 56.89 parts by mass

Propylene glycol monomethyl ether acetate: 29.1 parts by mass

Example 8

An antireflection film was obtained in the same manner as in Example 1 except that the composition for forming a low refractive index layer 1 was changed to the composition for a low refractive index layer 8 described below. The obtained antireflection film was evaluated by the above evaluation method, and the results are shown in Table 1.

Composition 8 for forming a low refractive index layer

Pentaerythritol triacrylate (PETA): 1.32 parts by mass

Fluorine-containing compound ^{* 1} : 1.32 parts by mass

Dispersion of hollow silica particles ^{* 2} : 6.61 parts by mass

Photopolymerization initiator ^{* 6} : 0.07 parts by mass

Methyl isobutyl ketone: 61.03 parts by mass

Toluene: 29.1 parts by mass

Example 9

An antireflection film was obtained in the same manner as in Example 1 except that the composition for forming a low refractive index layer 1 was changed to the composition for a low refractive index layer 9 described below. The obtained antireflection film was evaluated by the above evaluation method, and the results are shown in Table 1.

Composition 9 for forming a low refractive index layer

Pentaerythritol triacrylate (PETA): 0.11 parts by mass

Fluorine-containing compound ^{* 11} : 0.25 parts by mass

Dispersion of hollow silica particles ^{* 2} : 6.69 parts by mass

Dispersion of solid silica particles ^{* 3} : 0.74 parts by mass

Fluorine-containing polymer ^{* 12} : 2.79 parts by mass

Fluorine-containing monomer ^{* 5} : 2.23 parts by mass

Photopolymerization initiator ^{* 6} : 0.08 parts by mass

Methyl isobutyl ketone: 58.01 parts by mass

Propylene glycol monomethyl ether acetate: 29.1 parts by mass

* 11, " 5101X (trade name) ": a fluorine-containing compound having no silane unit, manufactured by Solvay Specialty Polymers Japan, a tetrafunctional methacrylate-modified perfluoropolyether compound,

* 12, "Obstar TU2224 (trade name)", 20% by mass solution (solvent: methyl isobutyl ketone) manufactured by JSR,

Comparative Example 1

An antireflection film was obtained in the same manner as in Example 1 except that the composition for forming a low refractive index layer 1 was changed to the composition for forming a low refractive index layer 10 described below. The obtained antireflection film was evaluated by the above evaluation method, and the results are shown in Table 2. In addition, the atomic force microscope images (shaped image and stomata image) are shown in Fig.

Composition 10 for forming a low refractive index layer

Pentaerythritol triacrylate (PETA): 0.12 parts by mass

Fluorine-containing compound ^{* 1} : 0.52 parts by mass

Dispersion of hollow silica particles ^{* 2} : 7.04 parts by mass

Dispersion of solid silica particles ^{* 3} : 0.78 parts by mass

Fluorine-containing polymer ^{* 4} : 2.93 parts by mass

Fluorine-containing monomer ^{* 5} : 2.35 parts by mass

Photopolymerization initiator ^{* 6} : 0.08 parts by mass

Methyl isobutyl ketone: 57.09 parts by mass

Propylene glycol monomethyl ether acetate: 29.1 parts by mass

Comparative Example 2

An antireflection film was obtained in the same manner as in Example 1 except that the composition for forming a low refractive index layer 1 was changed to the composition for a low refractive index layer 11 described below. The obtained antireflection film was evaluated by the above evaluation method, and the results are shown in Table 2. Fig. 10 shows the atomic force microscope images (shaped image and stomata image).

Composition for forming a low refractive index layer 11

Pentaerythritol triacrylate (PETA): 0.09 parts by mass

Fluorine-containing compound ^{* 1} : 3.79 parts by mass

Dispersion of hollow silica particles ^{* 2} : 5.44 parts by mass

Dispersion of solid silica particles ^{* 3} : 0.6 parts by mass

Fluorine-containing polymer ^{* 4} : 2.27 parts by mass

Fluorine-containing monomer ^{* 5} : 1.81 parts by mass

Photopolymerization initiator ^{* 6} : 0.06 parts by mass

Methyl isobutyl ketone: 56.82 parts by mass

Propylene glycol monomethyl ether acetate: 29.1 parts by mass

Comparative Example 3

An antireflection film was obtained in the same manner as in Example 1 except that the composition for forming a low refractive index layer 1 was changed to the composition for a low refractive index layer 12 described below. The obtained antireflection film was evaluated by the above evaluation method, and the results are shown in Table 2. Fig. 11 shows the atomic force microscope image (the topographic image and the topographic image).

Composition 12 for forming a low refractive index layer

Pentaerythritol triacrylate (PETA): 0.32 parts by mass

Dispersion of hollow silica particles ^{* 2:} 6.42 parts by mass

Dispersion of solid silica particles ^{* 3} : 1.43 parts by mass

Fluorine-containing polymer ^{* 4} : 3.21 parts by mass

Fluorine-containing monomer ^{* 5} : 0.54 parts by mass

Photopolymerization initiator ^{* 6} : 0.07 parts by mass

Methyl isobutyl ketone: 58.2 parts by mass

Propylene glycol monomethyl ether acetate: 29.1 parts by mass

Comparative Example 4

An antireflection film was obtained in the same manner as in Example 1 except that the composition for forming a low refractive index layer 1 was changed to the composition for a low refractive index layer 13 described below. The obtained antireflection film was evaluated by the above evaluation method, and the results are shown in Table 2.

Composition 13 for forming a low refractive index layer

Pentaerythritol triacrylate (PETA): 2.64 parts by mass

Fluorine-containing compound ^{* 1} : 1.32 parts by mass

Photopolymerization initiator ^{* 6} : 0.07 parts by mass

Methyl isobutyl ketone: 95.42 parts by mass

Comparative Example 5

A solution of the fluorine-containing compound used in Example 1 with a solid concentration of 3% by mass diluted with meta-xylene hexafluoride was prepared as an antifouling film evaporation source.

The composition for forming a hard coat layer 1 was gravure coated on a triacetylcellulose (TAC) resin film having a width of 500 mm, a thickness of 80 m and a length of 500 m to gravure coat the following composition 13 for forming a low refractive index layer, Dried at 70 DEG C for 1 minute to remove the solvent and then cured by irradiation with ultraviolet rays at an irradiation dose of 200 mJ / cm2 to form a hard coat layer having a thickness of about 10 mu m and a low refractive index layer having a thickness of about 100 nm, / Hard coat layer / low refractive index layer.

Subsequently, the antifouling film deposition source and the laminate were set in the winding type evaporation apparatus, and the laminate was evacuated to 1e ^-4 Torr or less. Thereafter, the laminate was wound at a running speed of 5 m / min, An evaporation source was evaporated by a non-contact heating type lamp heater to form an antifouling film on the low refractive index layer side of the laminate to obtain an antireflection film. The obtained antireflection film was evaluated by the above evaluation method, and the results are shown in Table 2.

(Parts by mass) of the fluorine-containing compound to 100 parts by mass (solid content) of the binder resin (including the fluorine-containing monomer and the fluorine-containing polymer) and the fine particles. Here, the solid content does not include a polymerization initiator.

(Parts by mass) of the fluorine-containing compound to 100 parts by mass (solid content) of the binder resin (including the fluorine-containing monomer and the fluorine-containing polymer) and the fine particles. Here, the solid content does not include a polymerization initiator.

The antireflection films obtained in Examples 1 to 5 were excellent in all evaluations, had excellent antireflection characteristics, had excellent scratch resistance and antifouling property, were not whitened, and were uniform from the results of the contact angle and the angle of inclination And had a constant surface. In addition, Examples 1 to 5 have a uniform and constant surface even from the observation of the average surface roughness or the atomic force microscope, and the scattering layer is formed uniformly and uniformly so as to cover the entire surface of the low refractive index layer .

In Example 6 in which the binder resin was changed from PETA to DPHA, good physical properties were obtained, but the coated surface was roughly uniform and constant, but slightly rough and slightly abrasive. Further, it was confirmed that DPHA was replaced with trimethylolpropane triacrylate (TMPTA) and pentaerythritol tetraacrylate (PETTA) to prepare an antireflection film, and it was confirmed that almost the same results as in Example 6 were obtained. In Example 7 in which the content of the fluorine-containing compound was large, although good physical properties were obtained, the surface state was substantially uniform and constant, but slightly rough and slightly abrasive. In Example 8 in which glycol ethers were changed to toluene as a solvent, it was estimated that there was a slight influence on the dispersibility of the fine particles, and slightly poor scratch resistance was obtained, but good results were obtained. From these results, it was confirmed that it is preferable to use ketones and glycol ethers as solvents. Further, in Example 9 using the material used in Patent Document 2 as the fluorine-containing compound, there was no sea-island structure in the antifouling layer, and a good one with no slight whitening was obtained. From this, it was confirmed that the fluorine-containing compound preferably has a silane unit.

In the antireflection film obtained in the examples, it is estimated that the total thickness of the low refractive index layer and the antifouling layer is about 100 nm, and the thickness of the antifouling layer is in the range of 1 to 3 nm.

On the other hand, in Comparative Example 1 in which the content of the fluorine-containing compound was small, the antireflective properties were equivalent to those in Examples, but because the amount of silicon components was large, the antifouling property was not sufficient. In addition, the angle of inclination is not necessarily uniform and constant at 33 °, and the sea structure was confirmed from the observation result by the atomic force microscope. It is considered that this sea-island structure is caused by the fact that the outermost surface of the low refractive index layer can not be entirely covered because a small amount of the fluorine-containing silane compound is not formed and a uniform and constant oozing layer is not formed. In Comparative Example 2 in which the fluorine-containing compound was excessively contained, excessive phase separation occurred in the entire low refractive index layer, so that the entire surface of the low refractive index layer was remarkably coarse and a uniform and constant antifouling layer was not formed. It is considered that this roughness is caused by irregularities generated by the excessive fluorine-containing compound as the protruding portion of the fine particles in the low refractive index layer as a trigger, resulting in the entire surface of the layer. Further, since the average surface roughness is large and the amount of the fluorine-containing compound contained in the antifouling layer is large, the antifouling layer is softened, and scratches are formed when the antifouling property is evaluated. In Comparative Example 3 in which the fluorine atom-to-carbon atom ratio was less than 0.6 but did not contain the fluorine-containing compound, a uniform surface was obtained, but the antifouling property was not sufficient because the amount of fluorine was small. Comparative Example 4 is an example in which fine particles are not used, but due to the poor compatibility of the binder resin and the fluorine-containing compound, the entire coating film became whitish at the time of coating film drying and evaluation could not be performed. From these results, it can be seen that the action of the fine particles is indispensable in order to maintain the balance of the fluorine-containing compound having poor compatibility with the binder resin and to obtain the final target composition. Further, in Comparative Example 5 in which the antifouling layer was formed by vapor deposition, the antifouling property and the surface condition were substantially good. However, as in the present invention, any reactive functional group in the reactive functional group and the low- , The adhesion between the antifouling layer and the low refractive index layer after curing was weak and the scratch resistance was poor.

INDUSTRIAL APPLICABILITY According to the present invention, an antireflection film having excellent antireflective properties, excellent scratch resistance and antifouling property, and suppressing the occurrence of minor whitening, which has not been encountered so far, can be easily produced. The obtained antireflection film is appropriately formed in a polarizing plate and an image display apparatus.

1: Antireflection film
2: transparent substrate
3: low refractive index layer
4: Hard coat layer
5: medium refractive index layer
6: high refractive index layer
7: Pre-refractive index layer
8:

Claims (13)

(1) to (3), wherein the fluorine atoms / the low refractive index layer and the antifouling layer are in this order, and the fluorine atom / fluorine atom concentration measured by X-ray photoelectron spectroscopy (XPS) Wherein the carbon atom ratio is 0.6 to 1.0, the silicon atom / carbon atom ratio is less than 0.25, and the average surface roughness (Ra ') of the antifouling layer is 10 nm or less.
Step (1) A step of coating a transparent substrate with a composition for forming a low refractive index layer containing at least a fluorine-containing compound, fine particles and a binder resin to form a coating film
Step (2) Step of phase-separating the coating film into a low refractive index image and a retardation image
Step (3) The antireflection layer covering the entire surfaces of the low refractive index layer and the low refractive index layer is formed by heating the low refractive index image and the retardation image, or by irradiating the low refractive index image and the retardation image with ionizing radiation fair The method according to claim 1,
Wherein the fluorine-containing compound has a silane unit having a reactive group and a silane unit having a perfluoropolyether group. delete delete delete delete delete delete delete delete delete delete delete

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