TW201303347A - Method for manufacturing anti-reflection film, anti-reflection film, polarizing plate, and image display device - Google Patents

Abstract

The present invention provides a method for easily manufacturing an anti-reflection film, an anti-reflection film, a polarizing plate and an image display device obtained by using the film. The anti-reflection film has excellent anti-reflection property, excellent scratch resistance and stain resistance, and inhibits the occurrence of slight whitening which has not been answered until now. The method for manufacturing the anti-reflection film contains three steps in order. The step (1) is coating the component for forming a low-refraction layer on the transparent substrate and forming the coating film, wherein the component at least includes fluorine containing compounds, particles, and binder resin. The step (2) is phase-separating the coating film into a low-refraction phase and a stain-resistance phase. The step (3) is heating the low-refraction phase and the stain-resistance phase, or irradiating the low-refraction phase and the stain-resistance phase by the ionization radiation, and then forming the low-refraction layer and the stain-resistance layer covering the whole surface of the low-refraction layer. The anti-reflection film has at least the transparent substrate, the low-refraction layer and the stain-resistance layer in order. The ratio of fluorine atom and carbon atom measured by X-ray photoelectron spectrometry (XPS) from the side of the stain-resistance layer is 0.6 to 1.0, and the ratio of silicon atom and carbon atom is less than 0.25. The average surface roughness (Ra') of the stain-resistance layer is less than or equal to 10 nm.

Description

Antireflection film manufacturing method, antireflection film, polarizing plate and 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 device.

Conventionally, on the surface of displays such as liquid crystal displays (LCDs), plasma display panels (PDPs), and cathode tube display devices (CRTs), in order to impart high surface hardness or to prevent external light sources from incandescent lamps, fluorescent lamps, and the like. The anti-reflective property of the reflection caused by the light is set, and the anti-reflection film is provided. 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 antireflection. Further, as a method for achieving a low reflectance, for example, it is known to form a laminated layer having a higher refractive index of a medium refractive index layer, a high refractive index layer or the like on the hard coat layer as a film, and to form the above low refractive index. The method of the rate layer. Further, for example, Patent Document 1 discloses an antireflection film containing specific fine particles in a refractive index suppression layer.

On the other hand, the performance required for the antireflection film may be, for example, the above-mentioned abrasion resistance of the surface of the display, or it is not easily stained by fingerprints, sebum, a mic, etc., and it is easy to wipe even if such dirt is adhered. That is, antifouling. As a method of imparting antifouling properties to the 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 order to suppress the deterioration of the performance due to the white turbidity of the antifouling agent-containing composition, the patent document 1 improves the mutual solubility with each component in the composition, that is, it is necessary to use a low molecular weight having a weight average molecular weight of less than 5,000. The fluorine-containing antifouling agent cannot be said to have sufficient antifouling properties.

As a method of imparting antifouling property, it is also proposed to use a fluorine-containing compound having a perfluoroalkyl group in the antifouling layer provided on the surface thereof in the relationship with a lanthanum element, a carbon element, and a fluorine element. A method in which a specific amount of a fluorine atom is present (for example, Patent Document 2). It is known that, as used in Patent Document 2, a fluorine-containing compound having a perfluoroalkyl group or the like is excellent in antifouling property, but has poor miscibility with other materials forming an antifouling layer, such as a binder resin. If a resin composition containing the fluorine-containing compound is to be applied to form an antifouling layer, it may be difficult to form a stable antifouling layer or a whitening problem may occur.

From this point of view, in Patent Document 2, the mutual solubility with other components is remarkably deteriorated, and the relationship with the lanthanum element, the carbon element, and the fluorine element is not caused in order to cause adverse effects such as depression, unevenness, and whitening of the coated surface. In the case where a specific amount of fluorine atoms are present, a certain mutual solubility is obtained to form an antifouling layer, and it is desired to form a stable antifouling layer or to suppress whitening (Patent Document 2, paragraph [0039]).

In recent years, along with the high performance of the above-described display, the antireflection film has also been expected to have high performance, and in particular, to increase the requirements for whitening. In the past, if whitening is a whitening that can be recognized at a glance and reduces the transparency of the film, the pursuit is to reduce this whitening. However, in recent years, in addition to the previous whitening, it is also required to suppress the slight whitening which has never been asked until now. The slight whitening is considered to be a film having high transparency at first glance, and those having ordinary knowledge in the technical field can barely recognize it. In the case of Patent Document 2, the case where the coating film surface is not uniform and the warpage is somewhat warped may not be sufficiently fully matched.

In addition, as a means of imparting antifouling properties to the film, there are proposals in the setting. On the transparent film substrate of the antireflection layer, a perfluoropolyether group-containing decane coupling agent is vapor-deposited to form an antifouling layer (for example, Patent Document 3). The method described in Patent Document 3 is because the fluorine-containing compound having a perfluoroalkyl group or the like as described above is inferior in compatibility with other materials which generally form an antifouling layer, and it is difficult to apply the resin composition containing the fluorine-containing compound. An antifouling layer is formed, and a so-called vapor deposition method in which a layer is formed without using other materials is attempted, and an antifouling layer containing the fluorine-containing compound is to be formed into a film. However, since the layer is formed by evaporation, and other materials such as a binder resin cannot be used, since the layer strength of the antifouling layer or the adhesion to the transparent film substrate is deteriorated, the factor is wiped to cause the antifouling layer to be self-contained. The film is peeled off and the antifouling property is remarkably lowered, and since the vapor deposition must be performed at a high temperature of several hundred degrees, the transparent film substrate shrinks due to heating, or in the accelerated deterioration test for the product before circulation, due to the high temperature Problems such as decomposition of the substrate which is subjected to thermal damage by vapor deposition.

The antifouling layer is generally made to have a thickness which is very thin in the order of nm. In addition to excellent antifouling properties, it is necessary to suppress the occurrence of slight whitening. In order to satisfy these conditions at the same time, it is considered that in addition to the mutual solubility of each other, formation prevention The composition of the stain must be further developed to achieve.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-152311

[Patent Document 2] International Publication No. 2008/38714

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-188102

The object of the present invention is provided under such circumstances, and the article can be easily manufactured. Method for producing antireflection film, excellent anti-reflection property, excellent abrasion resistance and antifouling property, and suppressing occurrence of slight whitening which has never been solved so far, antireflection film, and polarizing plate and image using the same Display device.

In order to achieve the above object, the inventors of the present invention have repeatedly studied intensively, and as a result, found that when the antifouling layer is formed according to the method of Patent Document 2, the cured product of the composition forming the antifouling layer on the surface thereof is unevenly distributed or uneven. A circular or elliptical hole is distributed, and the island structure exposed under the substrate or the like can be seen. The formation of the structure hinders the formation of a stable antifouling layer, and the slight whitening has never been asked. That is, the technique disclosed in Patent Document 2 obtains a certain mutual solubility by presenting a specific amount of fluorine atoms, and improves the easiness of forming an antifouling layer, but pursues higher performance of the antireflection film. In the case where there is a uniform formation of the antifouling layer, whether or not the island structure is generated, and slight whitening occurs, there is room for further review.

Therefore, the present inventors have not attempted to improve the mutual solubility as in the past, and a composition for forming a low refractive index layer containing a specific fluorine-containing compound containing a plurality of fluorine atoms having poor miscibility is intentionally used, and the composition is applied after coating the composition. In the separation method, a layer is formed so as to cover the entire surface of the film, and it has been found that the above problem can be solved by suppressing the formation of the sea-island structure as described above and the uniform low-refractive-index layer having a uniform average surface roughness.

Further, although the fluorine-containing compound having a large fluorine atom content is excellent in antifouling property, it is poorly miscible, and has never been considered to be contained in a resin composition. It is used, however, the fluorine-containing compound can be used in the invention of the present invention, and excellent antifouling properties can be obtained. The present invention has been completed based on this finding.

That is, the present invention provides: [1] A method for producing an antireflection film, which comprises the following steps (1) to (3) in sequence, the antireflection film having at least a transparent substrate and a low refractive index layer in sequence And an antifouling layer, the fluorine atom/carbon atom ratio measured by X-ray photoelectron spectroscopy (XPS) from the side of the antifouling layer is 0.6 to 1.0, and the germanium atom/carbon atom ratio is less than 0.25, the antifouling layer The step (1) is a step of forming a coating film by coating 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, wherein the average surface roughness (Ra') is 10 nm or less. Step (2) a step of separating the coating film into a low refractive index phase and an antifouling phase, and step (3) heating the low refractive index phase and the antifouling phase, or the low refractive index phase and the antifouling phase a step of irradiating free radiation to form a low-refractive-index layer and a comprehensive anti-staining layer covering the low-refractive-index layer; [2] an anti-reflection film which is produced by the anti-reflection film according to [1] above Manufactured; [3] a polarizing plate having an anti-reflection film on at least one side of the polarizing film, the anti-reflection film The film is the antireflection film described in the above [2]; and [4] an image display device having an antireflection film or a polarizing plate on the outermost surface of the display, the polarizing plate being at least one side of the polarizing film The antireflection film is the antireflection film described in the above [2].

According to the present invention, it is possible to easily obtain an antireflection film having excellent antireflection characteristics, excellent rub resistance and antifouling property, and suppressing the occurrence of slight whitening which has never been solved so far, and obtaining polarized light using the antireflection film. Board and image display device.

[Formation of the Invention] [Method of Manufacturing Antireflection Film]

The method for producing an antireflection film of the present invention comprises the steps of: step (1) applying a composition for forming a low refractive index layer containing at least a fluorine-containing compound, fine particles and a binder resin to a transparent substrate to form a coating film. And (2) the step of separating the coating film into a low refractive index phase and an antifouling phase, and the step (3) heating the low refractive index phase and the antifouling phase, or the low refractive index phase and the prevention The step of irradiating the free radiation to form a low refractive index layer and a comprehensive antifouling layer covering the low refractive index layer, and manufacturing at least a transparent substrate, a low refractive index layer, and an antifouling layer, from the antifouling The average side surface roughness (Ra') of the antifouling layer is determined by X-ray photoelectron spectroscopy (XPS) with a fluorine atom/carbon atom ratio of 0.6 to 1.0 and a germanium atom/carbon atom ratio of less than 0.25. A method of antireflection film of 10 nm or less.

The low refractive index phase and the antifouling phase formed in the step (2) are phases formed in a coating film on which the composition for forming a low refractive index layer is applied, and the binder resin in the composition for forming a low refractive index layer is not In the state of hardening, in addition, the solvent preferably contained in the composition is evaporated when the phase separation is substantially completed. State. On the other hand, these phases are formed by the step (3), in which the binder resin is in a hardened state, and the solvent is evaporated to be largely absent, thereby forming a low refractive index layer and an antifouling layer. Therefore, in the present invention, the state existing in the coating film is referred to as a low refractive index phase and an antifouling phase, and is referred to as a low refractive index layer and an antifouling layer, respectively, through the step (3). Further, in the present invention, the uncured state means a state in which the composition for forming a low refractive index layer has a physical fluidity, that is, a state in which the viscosity is measured, and the state in which the state of the hardened state means that the composition for forming a low refractive index layer does not have The state of physical fluidity, that is, the state of viscosity cannot be measured.

The following describes each step.

(step 1))

The step (1) is a coating film forming step of forming 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 to form a coating film.

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

(Preparation of a composition for forming a low refractive index layer)

The composition for forming a low refractive index layer is prepared by uniformly mixing a fluorine-containing compound, fine particles, a binder resin, a preferably used fluorine-containing polymer or various additives, which will be described later, and dissolving in a solvent as needed.

The composition for forming a low refractive index is preferably a liquid which is dissolved in a solvent in consideration of productivity. The viscosity of the composition for forming a liquid low refractive index layer is not particularly limited as long as the viscosity of the coating film can be formed on the surface of the transparent substrate by a coating method to be described later.

(formation of coating film)

The coating film is formed on the surface of the transparent substrate, and the thickness after hardening is set to a thickness as described later. The composition for forming a low refractive index layer prepared as described above is applied by gravure coating, bar coating, and roll. A known method such as coating, back roll coating, doctor blade coating, and die casting coating is preferably applied by gravure coating or die casting coating.

Hereinafter, each component which forms a transparent base material and a composition for forming a low refractive index layer is demonstrated.

(transparent substrate)

The transparent substrate to be used in the present invention is not particularly limited as long as it is generally used as a substrate of the antireflection film. However, it is preferable to appropriately select a plastic film or a plastic sheet depending on the application.

As such a plastic film or a plastic sheet, various synthetic resins are mentioned. Examples of the synthetic resin include a polyethylene resin, an ethylene alpha olefin copolymer, a polypropylene resin, a polymethylpentene resin, a polybutene resin, an ethylene-propylene copolymer, a propylene-butene copolymer, and an olefin thermoplastic elastomer. a linear or cyclic polyolefin resin such as a mixture of such or the like; polyethylene terephthalate resin (PET), polybutylene terephthalate resin, polyethylene naphthalate- Polyester resin such as isophthalic acid copolymer resin or polyester thermoplastic elastomer; poly(methyl) methacrylate resin, poly(methyl) acrylate resin, poly(meth) butyl acrylate resin, etc. Acrylic resin; polyamide resin represented by nylon 6 or nylon 66; triethylenesulfonyl cellulose resin (TAC), diethyl cellulose, cellulose acetate butyrate, celluloid, etc. Cellulose resin; cyclic polyene obtained from a cyclic olefin such as decene, dicyclopentadiene or tetracyclododecene Hydrocarbon resin; polystyrene resin; polycarbonate resin; polyarylate resin; or polyimine resin.

The transparent substrate may be used alone or in combination of two or more kinds of the above-mentioned plastic film or plastic sheet, and from the viewpoint of mechanical strength, polyethylene terephthalate resin or acrylic acid is preferred. The resin is preferably a triethylenesulfonyl cellulose resin or a cyclic polyolefin from the viewpoint of optical anisotropy.

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

(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. The components are explained below.

(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 in the antireflection film of the present invention. The fluorine-containing compound used in the present invention is preferably a compound having a reactive group and a perfluoropolyether group, and particularly preferably a decane unit having a reactive group and a decane having a perfluoropolyether group. a compound of a unit. In the present invention, since the fluorine-containing compound can be easily combined with other components in the composition by having a reactive group, a stronger layer can be formed, and as a result, both thin and abrasion resistance can be obtained. Excellent layer. Further, in the present invention, the anti-reflective film is excellent in the abrasion resistance at the outermost surface, and is also excellent in the adhesion of the outermost layer to the lower layer. that is, The fluorine-containing compound in the composition for forming a low refractive index layer is present in a large amount in the anti-fouling phase in the low refractive index phase and the antifouling phase, and is hardened in the step (3) described later. By reacting the reactive groups in the fluorine-containing compound contained in each phase with each other, very excellent adhesion between the low refractive index layer and the antifouling layer can be obtained. Further, by the reaction of the reactive group of the fluorine-containing compound with the reactive group of the binder resin or the curing of the binder resin itself, the adhesion of the antifouling layer is further improved, and the hardness is increased, thereby becoming a comprehensive A layer that is very excellent in abrasion resistance.

Further, the compound containing a decane unit as described above has an affinity for microparticles contained in a low refractive index phase, and when an antifouling phase is formed on the surface of the low refractive index phase, comprehensive wettability throughout the surface can be imparted, and It is important to maintain the wettability even in a state where the solvent is almost evaporated from the phase, and it is important to obtain a uniform antifouling layer on the entire surface. Furthermore, since this compound is very soft, a layer excellent in abrasion resistance can be obtained by improving the slidability. Further, since the infiltibility can be stably obtained by the affinity, it is possible to suppress the occurrence of slight whitening due to the occurrence of depression or formation of a sea-island structure when the solvent evaporates. Further, by using a fluorine-containing compound having a decane unit and a perfluoroether group in the same molecule, phase separation of the decane unit and the perfluoropolyether can be suppressed, and a uniform surface can be more easily obtained. Here, the decane unit is a unit represented by the following general formula (1).

In the 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 contains a monovalent group of a reactive group or a perfluoropolyether group. Organic base. Fluorine-containing compound used in the present invention, for example, system having R ¹ is a silicon oxide units a monovalent organic group to include a reactive group, and R ¹ is comprises silicon oxide units by a monovalent organic group of the perfluoropolyether group, also system may have a monovalent organic group comprising R ¹ is a reactive group, and R ² is alkoxy containing silicon by means a monovalent perfluoropolyether group of the organic group. Further, in the plural decane unit, R ¹ , R ² and X are independently, that is, the fluorine-containing compound of the present invention contains at least a decane unit having a reactive group and a decane unit having a perfluoropolyether group. It can also be a person having multiple decane units.

In the present invention, these decane units are preferably units having a decane skeleton. That is, it is preferred that X in the above formula (1) is an oxygen atom. Since the fluorine-containing compound has a rhodium skeleton, the affinity with the fine particles contained in the low refractive index layer as described above becomes good, and thus an antifouling layer which is uniform and has excellent antifouling properties can be obtained, and slight whitening is less likely to occur.

The weight average molecular weight of the fluorine-containing compound (the weight average molecular weight in terms of polyethylene measured by the GPC method) is preferably 5,000 or more, more preferably 5,000 to 100,000, 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 properties can be obtained, and if it is 100,000 or less, good solubility in an organic solvent can be obtained, and a uniform surface can be easily obtained.

The reactive group is preferably a reactive group having an ethylenically unsaturated double bond group such as a (meth)acryl fluorenyl group or a vinyl group, or an epoxy group, a carboxyl group, an amine group or a hydroxyl group. (meth) propylene A reactive group of an ethylenically unsaturated double bond group such as a mercapto group or a vinyl group is preferred. When the reactive group is the above-mentioned group, it can be more easily bonded to other components in the composition for forming a low refractive index layer, so that a layer having a stronger adhesion between the low refractive index layer and the antifouling layer as described above can be formed. A layer which is both thin and excellent in abrasion resistance can be 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, which may be the same or different. a to d is preferably an integer in the range of the weight average molecular weight of the perfluoropolyether group represented by the formula (2) in the range of 200 to 6,000, and preferably e is 0 to 2. Further, xa, xb, xc, and xd are integers of 1 to 4, which 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 from 5 to 80 parts by mass, more preferably from 10 to 70 parts by mass, still more preferably from 20 to 60 parts by mass. When the content of the fluorine atom in the fluorine-containing compound is 5 parts by mass or more, excellent antifouling properties can be obtained, and if it is 80 parts by mass or less, good solubility in a solvent can be obtained, and thus a uniform surface can be easily obtained.

The content of the solid content of the fluorine-containing compound is a total amount of the fine particles and the binder resin (including those in the case of using the fluorine-containing monomer and the fluorine-containing polymer) in the composition for forming the low-refractive-index layer. The solid content is 100 parts by mass, preferably 5 to 30 parts by mass. Further, although the fluorine-containing compound, the fine particles, and the binder resin can be obtained as a commercial product, It is generally sold in the form contained in a solvent. The amount of such solid components in this case is the amount after the solvent is removed from the total amount of the commercial product. Further, for example, the photopolymerization initiator is one of any solid components contained in the composition, and the content of the fluorine-containing compound is not counted.

When the content of the fluorine-containing compound is 5 parts by mass or more, the surface of the fluorine-containing compound can be uniformly covered with a uniform antifouling layer, and no island structure or slight whitening can occur. In addition, when the amount is 30 parts by mass or less, the coating film surface is not flat, and the surface of the coating film such as unevenness is not roughened, and a uniform antifouling layer can be obtained, and slight whitening can be prevented, and excellent rubbing resistance can be obtained. Sex. That is, by setting the content of the fluorine-containing compound within the above range, a uniform and smooth antifouling layer having an average surface roughness (Ra') of 10 nm or less can be obtained.

For the same reason, the content of the fluorine-containing compound is more preferably 5 to 20 parts by mass and 5 to 15 parts by mass, and more preferably 10 parts by mass as the maximum content. By setting the maximum content to 10 parts by mass, the average surface roughness (Ra') to be described later can be further made 5 nm or less, and the surface becomes smoother and the abrasion resistance is also good.

(microparticles)

The composition for forming a low refractive index layer contains fine particles. The microparticles are intended to reduce the refractive index of the layer, that is, to enhance the antireflection properties.

As the fine particles, any of the inorganic or organic systems can be used without limitation, and from the viewpoint of improving the surface resistance and ensuring good surface hardness, it is preferable from the viewpoint of the material. Stone fine particles, magnesium fluoride fine particles, etc., preferably from the viewpoint of shape A microparticle having a spherical shape and having a void itself is used. Further, in the case of having a void, alumina fine particles having a high refractive index generally higher than that of the cured film of the binder resin may be used.

Among these, from the viewpoint of the material, it is preferable to consider the fine particles of the fine particles in consideration of durability against wet heat. In the present invention, the combination of the materials forming the layers such as the antifouling layer covering the low refractive index layer is one of the important conditions. Since the fine particles are present in a state of being substantially finely packed in 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 of the microparticles contained in the low refractive index layer with the material forming the antifouling layer, the easier the antifouling layer can be formed to cover the entire surface of the low refractive index layer. This is because when the antifouling phase is phase-separated from the low refractive index phase, the antifouling phase becomes fully wettable on the surface of the low refractive index phase, and the wettability can be maintained until the completion of the step (3). From this point of view, the fine particles are fine particles of vermiculite having a vermiculite as a material, a fluorine-containing compound-based decane unit, and further a combination of a fluorinated compound having a fluorinated atom unit, that is, a fluorinated compound containing a ruthenium atom.

The fine particles having voids themselves have a small refractive index on the outside or inside, and are filled with a gas such as air having a refractive index of 1.0, and have a characteristic that their refractive index is low. Examples of such fine particles having voids include inorganic or organic porous fine particles and hollow fine particles. For example, porous vermiculite, hollow vermiculite fine particles, or porous polymer fine particles such as acrylic resin are preferably used. Or hollow polymer microparticles. Examples of the inorganic fine particles include voids prepared by the technique disclosed in JP-A-2001-233611. As a fine example of the fine particles of the organic type, hollow polymer fine particles prepared by the technique disclosed in Japanese Laid-Open Patent Publication No. 2002-80503, etc. are mentioned as a preferable example.

The vermiculite or porous vermiculite having a void as described above has a refractive index of about 1.20 to 1.44. From the viewpoint of the low refractive index of the low refractive index layer, the refractive index is lower than the refractive index of about 1.45. Generally, fine particles of vermiculite are preferred.

Further, as the fine particles, fine particles having a nanoporous structure can be formed in at least a part of the inside and/or the surface by the form, structure, aggregation state, and dispersion state inside the film.

Examples of such fine particles include the above-described vermiculite fine particles, or a purpose of producing a lifting specific surface area, and a material for absorbing various chemical substances in the porous portion of the filling column and the surface, and used for fixing the catalyst. The porous fine particles or a dispersion or agglomerate of hollow fine particles for the purpose of using a heat insulating material or a low dielectric material. Specific examples include "NIPSIL (product name)" and "NIPGEL (product name)": manufactured by Japan Shishi Industrial Co., Ltd.; or "COLLOID SILICA UP series (trade name)": Nissan Chemical Industry Co., Ltd. Company, etc.

The average particle diameter of the primary particles of the fine particles is preferably from 5 to 200 nm, more preferably from 5 to 100 nm, still more preferably from 10 to 80 nm. When the average particle diameter of the fine particles is 5 nm or more, an excellent refractive index lowering effect can be obtained, and if it is 200 nm or less, the transparency of the low refractive index layer 3 can be prevented, and a fine dispersion state of fine particles can be obtained. Further, in the present invention, as long as the average particle diameter is within the above range, the fine particles may be connected to form a chain. here The average particle size of the primary particles of the microparticles is obtained by observing any three fields of view by using a transmission electron microscope (TEM) on the cross section of the antireflection film, and actually measuring any 20 particles existing in the profile on the photograph (three The diameter of the field of view is 60 particles in total, as the average particle diameter.

Further, the fine particles used in the present invention are preferably surface treated. As the surface treatment, a surface treatment using a decane coupling agent is preferred, and a surface treatment using a decane coupling agent having a (meth) acrylonitrile group is preferred. By subjecting the fine particles to a surface treatment, the affinity with the binder resin to be described later is enhanced, the dispersion of the fine particles is uniform, and aggregation of the fine particles is less likely to occur, so that the transparency of the low refractive index layer due to the large particle size can be suppressed from being lowered. The coating property of the composition for forming a low refractive index layer or the decrease in the coating film strength of the composition. Further, in the case where the decane coupling agent has a (meth) acrylonitrile group, since the decane coupling agent has free radiation curability and is easily reacted with a binder resin to be described later, the coating film for the composition for forming a low refractive index layer The fine particles are fixed by the binder resin. That is, the fine particles have a function as a crosslinking agent in the binder resin. Thereby, the compact effect of the entire coating film can be obtained, and the adhesive resin can retain the original softness and impart excellent surface hardness to the low refractive index layer. Therefore, the low refractive index layer is deformed by utilizing its own flexibility, and has an absorption force or a restoring force against an external impact, thereby suppressing the occurrence of scratches and becoming a high surface hardness having excellent abrasion resistance.

As the decane coupling agent preferably used in the present invention, 3-(meth)acryloxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, 3 -(methyl)acryloxypropylmethyldimethoxy Base decane, 3-(meth) propylene methoxy propyl methyl diethoxy decane, 2-(methyl) propylene methoxy propyl trimethoxy decane, 2-(methyl) propylene decyloxy Propyltriethoxydecane, and the like.

The content of the fine particles in the low refractive index layer is preferably from 10 to 95% by mass, more preferably from 20 to 90% by mass, still more preferably from 30 to 90% by mass. Here, the content of the fine particles in the low refractive index layer is the total solid content of the composition for the low refractive index layer, that is, in addition to the fluorine-containing compound, the fine particles, and the binder resin, and arbitrarily used fluorine-containing polymerization. The content of the fine particles in the total amount of the additives, the fluorine-containing monomer, or the polymerization initiator or the like (the total amount of all the compounds other than the solvent contained in the composition) is the same. When the content of the fine particles is 10% by mass or more, the effect of using the fine particles can be sufficiently obtained, and if it is 95% or less, the average surface roughness (Ra') of the antifouling layer can be lowered, and the gap between the fine particles can be made by the resin. Well filled well to obtain excellent surface hardness.

Further, in the present invention, for the purpose of improving the rubbing resistance, solid fine particles having no voids can be used at the same time. The average particle diameter of the primary particles of the solid fine particles is preferably from 1 to 200 nm, more preferably from 1 to 100 nm, still more preferably from 5 to 20 nm. When it is 1 nm or less, the contribution to the surface hardness is small, and 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 fine particles.

The content of the solid particles may be appropriately adjusted in accordance with the friction resistance, the refractive index, and the like required for the low refractive index layer. For example, the total mass of the total solid content of the composition for the low refractive index layer is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass.

From the viewpoint of abrasion resistance and transparency, it is preferred to carry out surface treatment in the same manner as the above-mentioned fine particles having voids.

As the solid particles, solid particles conventionally known for use in an antireflection film or a hard coat film can be used. As a commercial item, for example, MIBK-ST (average primary particle diameter: 12 nm) and MIBK-ST-ZL (average primary particle diameter: 88 nm) manufactured by Nissan Chemical Industries Co., Ltd., or a daily catalyst are preferably used. The product name OSCAL series (average primary particle diameter: 7 to 100 nm) manufactured by Chemical Industries Co., Ltd.

(adhesive resin)

The composition for forming a low refractive index layer contains a binder resin from the viewpoints of film formability, film strength, and the like. The binder resin is preferably one in which the fluorine-containing compound or the fine particles are used as the first component, and other components added as needed, in the layer of the low refractive index layer, to heat or irradiate the ultraviolet radiation, the electron beam, or the like. And hardened, and the resin is fixed. Further, in the present invention, it is preferred that the fluorine-containing compound be efficiently phase-separated to obtain an antifouling layer which completely covers the low refractive index layer, and a resin having low miscibility with the fluorine-containing compound.

More specifically, examples of the binder resin include thermosetting properties such as melamine-based, urea-based, epoxy-based, ketone-based, diallyl phthalate-based, unsaturated polyester-based, and phenolic resins. Resin, or free radiation curable resin. Among them, a free radiation curable resin is preferred.

The epitaxial radiation-curable resin is an energy quantum which can polymerize a molecule in an electromagnetic wave or a charged particle beam, that is, a resin which is cured by irradiation of ultraviolet rays or electron beams. Specifically, it is a polymerizable monomer which is conventionally used as a free radiation curable resin and has low polymerizability. The polymer (or even the prepolymer) is suitably selected and used.

The polymerizable monomer is preferably a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule, and a polyfunctional (meth) acrylate monomer is preferable.

The polyfunctional (meth) acrylate monomer is not particularly limited as long as it is a (meth) acrylate monomer having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, dicyclopentene di a bifunctional (meth) acrylate such as methyl acrylate or isomeric cyanurate di(meth) acrylate; trimethylolpropane tri (meth) acrylate or neopentyl alcohol III ( 3-functional (meth) acrylate such as methyl acrylate, trimeric isocyanate (propylene oxyethyl) ester; neopentyl alcohol tetra (meth) acrylate, dipentaerythritol a tetrafunctional or higher (meth) acrylate such as tetrakis(meth)acrylate, dipentaerythritol penta(meth)acrylate or dipentaerythritol hexa(meth)acrylate; the above polyfunctionality An ethylene oxide denatured product of a (meth) acrylate monomer, a caprolactone denatured product, a propionic acid denatured product, or the like.

Among these, from the viewpoint of obtaining excellent rubbing resistance, a trifunctional or higher functional (meth) acrylate is preferable. These polyfunctional (meth) acrylate monomers may be used alone or in combination of two or more. More specifically, it is preferable to obtain the effects of the antifouling property, the rubbing resistance (adhesiveness), the slight whitening property, and the like in the present invention, and it is preferably trimethylolpropane tri(meth)acrylate. a trifunctional (meth) acrylate such as pentaerythritol tri(meth) acrylate or trimeric isocyanate (propylene oxyethyl) ester; pentaerythritol tetra (meth) acrylate a tetrafunctional or higher (meth)acrylic acid such as dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate or dipentaerythritol hexa(meth)acrylate The ester is particularly preferably pentaerythritol tri(meth)acrylate.

In the present invention, in order to reduce the viscosity thereof and the like while using the above-mentioned polyfunctional (meth) acrylate monomer, it is possible to suitably use a monofunctional (meth)acrylic acid in the range which does not impair the object of the present invention. Ester monomer. Further, in order to apply coating by appropriately adjusting the viscosity and to prevent curling due to hardening shrinkage, the following polymerizable oligomer or polymer can be used.

In the following, examples of the polymerizable oligomer include oligomers having a radical polymerizable unsaturated group in the molecule, and examples thereof include an epoxy (meth) acrylate type and a urethane (meth) acrylate type. A polyester (meth) acrylate type, a polyether (meth) acrylate type oligomer, or the like.

Further, in the present invention, for example, a copolymer obtained by previously polymerizing methyl methacrylate and glycidyl methacrylate to obtain a copolymer, followed by condensing a glycidyl group of the copolymer with a carboxyl group of methacrylic acid or acrylic acid may be used. Reactive polymer. Such a reactive polymer can be obtained as a commercial product, and examples of the commercially available product include "MACROMONOMER (trade name)": manufactured by Toagosei Co., Ltd., and the like.

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

In the case of using an ultraviolet curable resin as the free radiation curable resin, it is preferred to add a photopolymerization initiator of about 0.5 to 10 parts by mass, more preferably 1 to 5, per 100 parts by mass of the ultraviolet curable resin. Parts by mass. As a photopolymerization initiator, it can be suitable from the past The polymerizable monomer or polymerizable oligomer having a radical polymerizable unsaturated group in the molecule is exemplified by an acetophenone type, a diphenyl ketone type, a benzoin system, and a ketal. Photopolymerization initiators such as lanthanum, lanthanide, disulfide, thioxanthone, thiram, and fluoroamine. These may be used alone or in combination. These photopolymerization initiators can be obtained as commercially available products, for example, "IRGACURE 184 (product name)", "IRGACURE 907 (product name)" and "IRGACURE 127 (product name)" (both Ciba Specialty Chemicals) System) and so on.

The content of the binder resin is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, per 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 rubbing resistance can be obtained, and the fluorine-containing compound can be phase-separated efficiently.

(fluoropolymer)

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. As the fluoropolymer, for example, a (meth)acrylic acid moiety and a fully fluorinated alkyl group, an alkenyl group, an aryl ester, a wholly or partially fluorinated vinyl ether, or a wholly or partially fluorinated vinyl ester may be mentioned. , wholly or partially fluorinated ketenes, etc.

Further, as the fluoropolymer, it is preferable to contain a fluorene-containing polymer, and for example, a polyfluorene-containing vinylidene fluoride copolymer containing a polyfluorene-containing component in the copolymer is preferable. Examples of the polyfluorene oxygen component in this case include (poly)dimethyloxane, (poly)diethyloxane, and (poly)di. Phenyl oxirane, (poly)methylphenyl decane, alkyl denatured (poly) dimethyl oxane, azo containing (poly) dimethyl oxane, or dimethyl poly Oxygen, phenylmethyl polyoxo, alkyl ‧ aralkyl denic polyoxyl, fluoropolyoxyl, polyether modified polyoxyl, fatty acid ester denatured polyoxyl, methyl hydrogen polyoxyl, containing a stanol-based polyoxygen, an alkoxy-containing polyoxygen, a phenol-based polyoxygen, a methacryl-based polyphosphoric acid, an acryl-based polyphosphoric acid, an amine-modified polyoxygen, Carboxylic acid-denatured polyoxo, methanol-denatured polyoxygen, epoxy-denatured polyoxygen, sulfhydryl-denatured polyoxygen, fluorine-denatured polyoxyl, polyether-denatured polyoxyl, and the like. Among them, those having a structure of dimethyloxane are preferred.

Further, in addition to the above, a compound having at least one isocyanate group and fluorine in the molecule and a compound having at least one functional group reactive with an isocyanate group such as an amine group, a hydroxyl group or a carboxyl group in the molecule may be used. a compound obtained by the reaction; a fluorine-containing polyhydric alcohol, a fluorine-containing polyether polyol, a fluorine-containing polyester polyol, a fluorine-containing ε-caprolactone denatured polyol, or the like, and a fluorine-containing polyol having an isocyanate group; The compound obtained by the reaction of the compound or the like is used as a fluoropolymer.

The refractive index of the fluoropolymer is preferably from 1.37 to 1.45. When the refractive index is 1.37 or more, since the solvent is excellent in solubility, handling is easy. Further, if it is 1.45 or less, the refractive index of the formed low refractive index layer can be reduced to a desired range.

Such a fluoropolymer can be obtained as a commercial product. For example, OPSTAR TU2181-6, OPSTAR TU2181-7, OPSTAR TU2202, OPSTAR JN35, OPSTAR TU2224, manufactured by JSR Corporation, OPTOOL AR110, OPTOOL manufactured by DAIKIN Industries Co., Ltd. are preferable. AR100 Wait.

The content of the fluoropolymer is preferably from 1 to 30 parts by mass, more preferably from 5 to 25 parts by mass, per 100 parts by mass of the total solid content in the composition for forming a low refractive index layer. If the content of the fluoropolymer is within the above range, the refractive index can be efficiently lowered.

(fluorinated 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. From the viewpoint of efficiently curing the low refractive index layer and obtaining excellent hardness, the fluorine-containing monomer preferably has two or more reactive functional groups in one molecule. Preferred examples of such a fluorine-containing monomer include a fluorine-containing monomer having a pentaerythritol skeleton, a fluorine-containing monomer having a dipentaerythritol skeleton, and a fluorine-containing monomer having a trimethylolpropane skeleton. A fluorine-containing monomer having a cyclohexyl skeleton, a fluorine-containing monomer having a linear skeleton, or the like. Among these, a compound having a neopentyl alcohol skeleton is preferred.

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

Such a fluorine-containing monomer can be obtained as a commercial product, and examples thereof include LINC 3A having a pentaerythritol skeleton manufactured by Kyoei Chemical Co., Ltd., LINC 3A having a cyclohexyl skeleton, and the like.

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

(various additives)

The composition for forming a low refractive index layer used in the present invention can be blended with various additives in accordance with desired physical properties. Examples of the additive include a weather resistance improver, an abrasion resistance enhancer, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an adhesion promoter, an antioxidant, a leveling agent, a shake imparting agent, and a coupling agent. , plasticizer, defoamer, filler, solvent, etc.

(solvent)

Further, the solvent to be preferably used in the composition for forming a low refractive index layer is not particularly limited, and preferably, for example, an alcohol such as methanol, ethanol or isopropyl alcohol (IPA); methyl ethyl ketone; a ketone such as methyl isobutyl ketone or cyclohexanone; an ester of ethyl decanoate or butyl phthalate; a halogenated hydrocarbon; an aromatic hydrocarbon such as toluene or xylene; propylene glycol monomethyl ether and propylene glycol A glycol ether such as ethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate or dipropylene glycol monoethyl ether, or a mixture thereof. Among these, ketones and glycol ethers having high affinity with a fluorine-containing compound are preferred, and particularly preferred solvents are methyl ethyl ketone, methyl isobutyl ketone, and propylene glycol monomethyl ether. Propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate. The dispersibility of each compound in the composition can be maintained by using these or the like alone or in combination, and phase separation of the low refractive index phase from the antifouling phase can be desirably completed in the phase separation step (2).

Further, in the case of using a solvent other than a ketone or a glycol ether, it is preferred to contain at least 50% or more, preferably 70% or more of the total amount of the ketone or the glycol ether. In particular, in the case of using a ketone, the coating property of the composition for forming a low refractive index layer is improved, and since the evaporation rate of the solvent after application of the composition is moderate, drying unevenness is unlikely to occur, and evaporation of the solvent may be accompanied. The fluorine-containing compound is efficiently phase-separated, and a uniform large-area coating film (antifouling layer) can be easily obtained.

The amount of the solvent is suitably adjusted so that the components can be uniformly dissolved and dispersed, and the concentration is not excessively concentrated at the time of storage after the preparation of the composition, and the coating is not too thin. The content of the solvent in the composition for forming a low refractive index layer is preferably from 50 to 99.5% by mass, and more preferably from 70 to 98% by mass. By setting it as such a content, it is possible to obtain a composition which is excellent in dispersion stability and is suitable for long-term storage. Further, the solvent used for the composition for forming a low refractive index layer is hardly evaporated by drying or hardening after the composition is applied, and is hardly present in the low refractive index layer.

(Step (2))

The step (2) is a step of separating the coating film formed in the above step (1) into a low refractive index phase and an antifouling phase. As a method of promoting phase separation, for example, a method of heating a coating film in air, a method of holding it in a vapor or an autoclave, or the like is preferably used. Further, it is also possible to simply place it until the phase is separated without heating or the like.

In the present invention, after the composition for forming a low refractive index layer is applied, and before the binder resin in the composition is cured, the fluorine in the composition is heated in this step or simply placed in this step. The compound will easily float on the most surface side of the coating film (phase with the transparent substrate) Reverse side). As a result, in the coating film of the composition for forming a low refractive index layer, the antifouling phase which exhibits an antifouling property with a relatively large content of the fluorine-containing compound is phase-separated, and the content of the fluorine-containing compound is relatively small to exhibit a low refractive index. The low refractive index phase and the antifouling phase formed on the outermost surface side by heating or irradiating the free radiation form a comprehensive antifouling layer covering the low refractive index layer, and excellent antifouling property can be obtained. In other words, in the present invention, when a composition for forming a low refractive index layer is applied to form a coating film, two phases are separated in the coating film, and the coating film has a low refractive index phase and an antifouling phase, which will be described later. In the step (3), the two phases each form a low refractive index layer and an antifouling layer, and further, it can be said that a low refractive index layer having an antifouling layer is formed.

The heating or the time of standing alone may be as long as the fluorine-containing compound floats on the outermost surface side of the coating film, and is usually about 1 to 30 seconds.

In addition, the solvent preferably contained in the composition for forming a low refractive index layer may be evaporated by heating or simply by the above, or may be actively dried by evaporating the solvent. The drying temperature condition 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 can be appropriately selected depending on the material of the transparent substrate to be used. On the other hand, the lower limit temperature of 20 ° C is preferably selected from the viewpoint of rapidly and surely separating the fluorine-containing compound on the outermost surface to form an antifouling layer. Further, from the viewpoint of phase separation of the antifouling phase after stabilization and formation of the antifouling layer, it is more preferably selected to be 40 ° C or higher.

(Step (3))

The step (3) is a step of heating the phase-separated coating film or irradiating the coating film with free radiation so that the low refractive index phase and the antifouling phase in the coating film each become a low refractive index layer and an antifouling layer. 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 due to the presence of a fluorine-containing compound in the layer. In the present specification, for the sake of convenience, a layer containing a relatively small fluorine-containing compound is referred to as a low refractive index layer (a low refractive index phase before heating or irradiating free radiation) because of having excellent antireflection properties. A layer containing a relatively large amount of a fluorine-containing compound is called an antifouling layer (an antifouling phase before heating or irradiating free radiation) because it has superior antifouling properties.

Whether the film is heated or irradiated with free radiation is selected depending on the binder resin contained in the composition for forming a low refractive index layer. In the case where a thermosetting resin is used as the binder resin, a heating step 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, for example, 60 to 100 °C.

Further, in the case where the free radiation curable resin is used as the binder resin, it is sufficient that the coating film is irradiated with free radiation. When the coating film is cured, an electron beam is used as the free radiation, and the accelerating voltage can be appropriately selected depending on the thickness of the resin or layer to be used, and it is usually preferred to harden the coating film at an acceleration voltage of about 70 to 300 kV.

In addition, in the irradiation of the electron beam, the penetration ability can be increased as the accelerating voltage is higher, and the penetration depth of the electron beam and the coating film can be made by using a substrate which is deteriorated by the electron beam as a substrate. The thickness is substantially equal, and the acceleration voltage is selected to suppress excessive irradiation of the electron beam on the substrate, and the deterioration of the substrate caused by the excess electron beam can be minimized. limit.

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

Further, as the electron beam source, there is no particular limitation, and for example, a Kirklaw-Walton type, a Vandergrave type, a tuning transformer type, an insulating nuclear transformer type, or a linear type, a dinas type, or a high type can be used. Various electron beam accelerators such as frequency type.

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

The ultraviolet ray irradiation is preferably carried out in an atmosphere of a nitrogen atmosphere, for example, an oxygen concentration of 1000 ppm or less, from the viewpoint of preventing oxygen barrier on the surface of the resin composition for a low refractive index layer. In the present invention, after phase separation, ultraviolet light irradiation is preferred from the viewpoint of allowing the low refractive index phase and the antifouling phase to be rapidly and stably cooled.

Further, by the hardening of the step (3), the solvent is almost completely evaporated and dried, and is hardly present in the layer. The solvent has substantially evaporated in the step (2), and the solvent remaining in the layer at the completion of the step (2) can be considered to be almost completely evaporated in the step (3).

[Anti-reflective film]

The antireflection film of the present invention is obtained according to the above-described manufacturing method of the present invention, and more specifically, characterized in that it has at least a transparent substrate, a low refractive index layer and a comprehensive antifouling layer covering the low refractive index layer, wherein the low refractive index layer and the antifouling layer are formed of a composition for forming a low refractive index layer containing a fluorine-containing compound, fine particles, and a binder resin. The average surface roughness of the antifouling layer is determined by X-ray photoelectron spectroscopy (XPS) from the side of the antifouling layer to a fluorine atom/carbon atom ratio of 0.6 to 1.0 and a germanium atom/carbon atom ratio of less than 0.25. Ra') is 10 nm or less.

The antireflection film of the present invention will be described using the first to third embodiments. Fig. 1 is a schematic view showing a cross section of an antireflection film of the present invention, and Figs. 2 and 3 are views showing a cross section of a preferred layer structure of the antireflection film of the present invention. The antireflection film 1 shown in Fig. 1 has a low refractive index layer 3 and an antifouling layer 8 on a transparent substrate 2. The antireflection film 1 shown in Fig. 2 has a hard coat layer 4, a medium-high refractive index layer 7, and a low refractive index layer 3 in this order on the transparent substrate 2, and the antireflection film 1 shown in Fig. 3 is used. The hard substrate 4, the medium refractive index layer 5, the high refractive index layer 6, the low refractive index layer 3, and the antifouling layer 8 are sequentially provided on the transparent substrate 2. 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 antifouling layer 8 on the transparent substrate 2, and for example, a transparent substrate/low refractive index is preferable. Layer/antifouling layer, transparent substrate/hard coat layer/low refractive index layer/antifouling layer, transparent substrate/hard coat layer/medium index layer/high refractive index layer/low refractive index layer/antifouling layer, A layer structure of a transparent substrate/hard coat layer/high refractive index layer/medium refractive index layer/low refractive index layer/antifouling layer, transparent substrate/medium high refractive index layer/low refractive index layer/antifouling layer. Further, although not shown, it may be closer to the transparent substrate side than the low refractive index layer, and may further have a functional layer such as an antistatic layer to be described later.

(low refractive index layer 3 and antifouling layer 8)

The low refractive index layer 3 and the antifouling layer 8 are layers in which a composition for forming a low refractive index layer containing a fluorine-containing compound, fine particles, and a binder resin is used. These layers are layers formed by the above-described method for producing an antireflection film of the present invention, that is, by coating the composition for forming a low refractive index layer on a transparent substrate, forming a coating film, and forming the coating film. Separating, and forming a low refractive index phase and an antifouling phase as two phases in the coating film, respectively, by heating or irradiating the coating film, the low refractive index layer 3 and the antifouling layer are formed. 8 layers. Further, 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, as described above, and conversely, the fluorine-containing compound The antifouling layer 8 having a relatively large content is a layer which exhibits strong antifouling properties.

(low refractive index layer 3)

The low refractive index layer 3 is preferably such that the refractive index of the layer disposed directly below is N, and when the refractive index of air is 1, the refractive index is a layer of N ^1/2 , for example, the positive refractive index layer 3 The lower layer is a hard coat layer formed by using a general-purpose polyfunctional (meth)acrylic free radiation curable resin. If the N of the hard coat layer is 1.49 to 1.53, it is preferably a ratio. The N is 0.01 lower and the refractive index is 1.48 to 1.52. Further, the lower the refractive index, the more preferable, and the balance between the antireflection property and the surface hardness is preferably 1.25 to 1.45, more preferably 1.25 to 1.35. The refractive index can be easily controlled by the kind of the fine particles, the content thereof, or the amount of the fluorine-containing compound used.

Further, in order to obtain the best antireflection effect, the film thickness and refractive index of the low refractive index layer 3 preferably satisfy the relationship calculated from the following formula (I).

d _A =mλ/(4n _A ) (I)

In the formula (I), n _A represents the refractive index of the low refractive index layer, and m represents a positive odd number, and is preferably expressed as a value of 1 (air), λ-based wavelength, preferably 480 to 580 nm. Therefore, in the present invention, from the viewpoint of lowering the refractive index, it is preferable to make m=1 in the above formula (I) and to make λ the most dazzling wavelength of 480 to 580 nm, from the following formula. (II) Calculated refractive index and film thickness.

120<n _A d _A <145 (II)

In the case where the refractive index is in the preferred range of 1.25 to 1.45 as described above, the film thickness is preferably about 80 nm to 120 nm. However, in order to make the refractive index lower than that of the lower layer to obtain an antireflection effect, the film thickness may be about 120 nm to 1 μm which is outside the 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.

(anti-fouling layer 8)

The antifouling layer 8 is a layer having an average surface roughness (Ra') of 10 nm or less and uniformly covering the entire surface of the low refractive index layer 3, and imparting antifouling properties to the antireflection film of the present invention.

The antifouling layer 8 is a layer having an average surface roughness (Ra') of 10 nm or less, and is a uniform layer. Further, 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 excellent in friction resistance. Here, the average surface roughness (Ra') is a three-dimensional expansion applied to the measurement surface by the center line average roughness (Ra) defined by JIS B0601, and "the deviation from the reference surface to the specified surface" is expressed. The absolute value is averaged," the value given in the following formula. For example, the average surface roughness (Ra') is as long as it can be represented by atomic force. The microscopic mirror (AFM) observes the surface shape and obtains the image obtained by image analysis using an attached analysis software (for example, SPIwin).

Ra': average surface roughness (nm)

S _o : Assume that the measurement surface is ideally flat

The area of the time (| X _R -X _L | x | Y _T -T _B |)

F(X, Y): at the height of the measuring point (X, Y)

X: X coordinate

Y: Y coordinate

X _L ~X _R : the range of the X coordinate of the measurement surface

Y _B ~Y _T : the range of the Y coordinate of the measurement surface

Z _o : measure the average height in the plane

Since the average surface roughness of the antifouling layer 8 is extremely small and uniform as described above, it has excellent rubbing resistance and antifouling property, and has excellent antireflection properties, and is preferably provided in the antireflection of the present invention. The outermost surface of the film.

The uniform state of the antifouling layer 8 is specifically confirmed not only by the average surface roughness (Ra') but also by atomic force microscopy (AFM). In other words, when the antifouling layer 8 is observed by an atomic force microscope (AFM), the cured product of the composition for forming a low refractive index layer is not unevenly distributed in the shape and phase diagram, or is formed in the cured product. The anti-fouling layer does not unevenly distribute the circular or elliptical holes, so that the lower layer of the low refractive index layer or the transparent substrate is exposed, that is, the island structure is not present, but is formed over the entire antireflection film 1 State.

The fluorine atom/carbon atom ratio determined by X-ray photoelectron spectroscopy (XPS) from the side of the antifouling layer must be 0.6 to 1.0, and the germanium atom/carbon atom ratio must be less than 0.25. Here, fluorine atom/carbon atom ratio, germanium atom/carbon atom ratio The antifouling layer side of the antireflection film is measured by X-ray photoelectron spectroscopy (XPS), and is calculated based on the composition ratio of fluorine atoms, carbon atoms, and ruthenium atoms.

In the present invention, the fluorine atom in the antifouling layer 8 is present in a certain amount or more, and the ruthenium atom is present in a certain amount or less, that is, by using a predetermined fluorine-containing compound in a fixed amount, excellent antifouling properties can be obtained without A slightly whitened anti-reflective film. Further, since the antifouling layer is formed over the entire surface and uniformly, the above-mentioned atomic ratio is comprehensively distributed, whereby more excellent antifouling properties can be obtained and the occurrence of slight whitening can be reduced.

From this point of view, the fluorine atom/carbon atom ratio is more preferably 0.7 to 1.0, and the germanium atom/carbon atom ratio is more preferably 0.01 to 0.2. If the fluorine atom/carbon atom ratio is less than 0.6, the antifouling property may be insufficient. On the other hand, if it is more than 1.0, the treatment of the reagent used to achieve this value, that is, the treatment of the fluorine-containing compound, becomes significantly difficult. In addition, when the ruthenium atom/carbon atom ratio is 0.25 or more, the antifouling property is insufficient, and in the present invention, the ratio is made less than 0.25, but in such a range, excellent resistance due to slidability improvement can be expected. Frictional.

For example, when the sea-island structure is confirmed by atomic force microscopy (AFM), or a convex portion is observed in a part thereof, the average surface roughness is a rough surface outside the range specified by the present invention, from the side of the anti-fouling layer. The atomic ratio measured by X-ray photoelectron spectroscopy (XPS) is not in the range of the atomic ratio as described above. That is, in the coating film obtained by coating the composition for forming a low refractive index layer, phase separation into a low refractive index phase and an antifouling phase, and further, the antifouling layer is a uniform layer on the low refractive index layer. The formation can be confirmed by measuring the atomic ratio specified in the present invention; the antifouling layer is a uniform layer, and can also be confirmed by measurement by atomic force microscopy (AFM). Therefore, since the antifouling layer has the average surface roughness and the atomic ratio defined by the present invention, it can be said that in addition to the excellent antifouling property, the rubbing resistance can be obtained, and the antireflection which is not slightly whitened or expressed can be obtained. film. In the present invention, an atomic ratio measured by X-ray photoelectron spectroscopy (XPS) according to an average surface roughness (Ra') of the atomic force microscope (AFM) or a shape diagram and a phase diagram observation may be used. It is judged whether it is the antireflection film manufactured by the manufacturing method of this invention, or the evaluation method of the antireflection film of this invention. The presence of the antifouling layer on the low refractive index layer may be observed by TEM cross-section observation. However, considering the extremely thin layer, the above evaluation method is effective. Further, in the case where the antifouling 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, since the antifouling layer and the low refractive index layer are not in accordance with The reactive groups of the materials of the respective layers react and weaken the friction resistance due to weak adhesion. That is to say, the difference in the manufacturing method can be confirmed by the evaluation of the abrasion resistance. Here, the abrasion resistance was evaluated by applying a load of 300 g/cm ² or more to steel wool (BONSTAR #0000 manufactured by Nippon Steel Wool Co., Ltd.), rubbing the surface of the antireflection film back and forth 10 times, and visually causing the surface. The number of scars.

The germanium atom in the low refractive index layer and the antifouling layer exists in the form of SiO ₂ or C-Si-O. In the present invention, the germanium atom derived from SiO ₂ is referred to as an inorganic germanium atom, and will be derived from C-Si- The germanium atom of O is called an organic germanium atom. That is, in the present invention, the ruthenium atom in the low refractive index layer and the antifouling layer contains an organic ruthenium atom and an inorganic ruthenium atom.

Inorganic germanium atoms and organic germanium atoms, due to different binding energies, are expected to appear separately in the Si2p spectrum. By peak separation analysis, the peak near 103~104eV on the high bond junction side is defined as an inorganic germanium atom, and the peak near 101~102eV on the low bond junction side is defined as an organic germanium atom. The ruthenium atom in the above ruthenium atom/carbon atom ratio is defined as the total amount of the inorganic ruthenium atom and the organic ruthenium atom.

In the present invention, the organic ruthenium atom/carbon atom measured by X-ray photoelectron spectroscopy (XPS) from the side of the antifouling layer is preferably 0.07 or less, more preferably 0.01 to 0.07, still more preferably 0.02 to 0.06. Further, the inorganic ruthenium atom/carbon atom is preferably 0.2 or less, more preferably 0.05 to 0.2, still more preferably 0.08 to 0.18. When the ratio of the organic ruthenium atom/carbon atom to the inorganic ruthenium atom/carbon atom is within the above range, an antireflection film which exhibits excellent abrasion resistance and antifouling property without slight whitening can be obtained.

In the present invention, by satisfying the above atomic ratio, it is not necessary to improve the mutual solubility of the fluorine-containing compound as in the prior art, and it is possible to cover the entire surface of the low refractive index layer by using a composition for forming a low refractive index layer. The antifouling layer is formed as a layer which suppresses the occurrence of the above-described sea-island structure and has a uniform average surface roughness and uniformity.

Further, by using a composition for forming a low refractive index layer in which a fluorine-containing compound and fine particles and a binder resin are combined, not only a uniform antifouling layer 8 can be obtained, but also excellent antireflection properties can be obtained as a result. Anti-reflective film that resists abrasion and stain resistance and suppresses the occurrence of slight whitening.

As long as it is a smooth surface, it is theoretically impossible for an organic compound such as an antifouling layer to cause a contact angle of hexadecane of more than 90°. therefore, The contact angle and the drop angle can be measured using hexadecane as a measurement liquid by various commercially available contact angle angle meters and drop angle angle meters.

In the anti-reflection film 1 of the present invention, when the outermost surface is defined as the anti-staining layer 8, the contact angle with respect to the surface of hexadecane is preferably 55 to 90, more preferably 60 to 90, and for the surface. The falling angle of hexadecane is preferably from 1 to 25°, more preferably from 1 to 20°, and the outermost surface thereof is uniform, that is, the antifouling layer 8 has a smooth structure. The fluorine-containing compound contained in the anti-fouling layer 8 covers the surface, and the contact angle and the falling angle are in the above range. On the other hand, if the sea-island structure is formed and the surface cannot be uniformly covered, the contact angle and the falling angle are obtained. Will deviate from the above range.

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

Only the thickness of the antifouling layer 8 is presumed to be in the range of 1 to 3 nm. When the X-ray photoelectron spectroscopy (XPS) analysis is considered, the atoms contained in the fine particles in the low refractive index layer can also be detected, and the depth of the information obtained by X-ray photoelectron spectroscopy (XPS) is 1~. 3nm, it is presumed that it is more appropriate in the range of 1~3nm.

(hard coating 4)

The antireflection film 1 of the present invention may have a hard coat layer 4 for the purpose of improving the surface hardness of the antireflection film 1 such as abrasion resistance. Here, the hard coating refers to a property of exhibiting a hardness of "H" or more in a pencil hardness test prescribed in JIS 5600-5-4:1999.

The hard coat layer is preferably a cross-linked hardened free radiation curable resin. . The free radiation curable resin forming the hard coat layer 4 can be suitably selected from among the free radiation curable resins used for the binder resin in the composition for forming a low refractive index layer. The photopolymerization initiator used in the case where the free radiation curable resin is an ultraviolet curable resin may be appropriately selected from those exemplified above. Further, various additives used in the above composition for forming a low refractive index layer can also be used.

The film thickness after hardening of the hard coat layer 4 is preferably in the range of 0.1 to 100 μm, more preferably in the range of 0.8 to 20 μm, still more preferably in the range of 1 to 8 μm, and particularly preferably in the range of 1.5 to 4 μm. As long as the film thickness is within the above range, sufficient hard coat performance can be obtained, and the punch from the outside is not easily broken. Further, in the present invention, the hard coat layer 4 may have a function of a medium refractive index layer 5 or a high refractive index layer 6 as described below, or a function of an antistatic layer.

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

The antireflection film 1 of the present invention preferably has a medium refractive index layer 5 and a high refractive index layer 6 for the purpose of improving antireflection performance. Here, the medium refractive index layer 5 and the high refractive index layer 6 are in the form of the antireflection film 1 described above, and it is not necessary to provide the medium refractive index layer 5 and the high refractive index layer 6 at the same time, and may be, for example, as shown in FIG. The medium-high refractive index layer 7 is provided in one layer.

The refractive index of the medium refractive index layer 5, the high refractive index layer 6, or the medium-high refractive index layer 7 (hereinafter also referred to as such a refractive index layer) is preferably set arbitrarily within the 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 has a lower refractive index than the high refractive index layer 6, and the refractive index is relatively high. Folding of the medium refractive index layer 5 and the high refractive index layer 6 The emissivity is as described above, but it is generally preferred that the refractive index of the medium refractive index layer 5 is in the range of 1.5 to 1.8, and the refractive index of the high refractive index layer 6 is in the range of 1.6 to 2.0.

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

It is preferred that the refractive index of the fine particles is higher than the refractive index of the cured film of the binder resin monomer. Since the refractive index of these refractive index layers is generally determined by the content ratio of the fine particles, the larger the amount of the fine particles added, the higher the refractive index of the refractive index layer. Therefore, by adjusting the addition ratio of the binder resin to the fine particles, a refractive index layer having a specified refractive index can be formed. As long as the fine particles are electrically conductive, the refractive index layer formed using such fine particles has both antistatic properties. The refractive index layer may be a vapor deposited film of an inorganic oxide having a high refractive index of titanium dioxide or zirconium oxide formed by a vapor deposition method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD), or A cured film of a resin which is a resin composition of a suitable binder resin, such as inorganic oxide fine particles having a high refractive index of titanium dioxide, is used.

The film thickness of the refractive index layers is preferably in the range of 10 to 300 nm, more preferably in the range of 30 to 200 nm. The above refractive index layer (medium refractive index layer, high refractive index layer) may be directly disposed on the transparent substrate 2, however, it is preferable to provide the hard coat layer 4 on the transparent substrate 2, in the hard coat layer 4 and the low refractive index layer 3. Set between.

(antistatic layer)

The antireflection film 1 of the present invention can be preferably obtained from the viewpoint of preventing the adhesion of dust by the antistatic effect or the conductivity or electromagnetic wave shielding effect in the case where the antireflection film of the present invention is used in an image display device. The ground has an antistatic layer. Preferably, the antistatic layer is disposed between the transparent substrate 2 and the low refractive index layer 3, and is provided with the hard coat layer 4, the medium refractive index layer 5, or the high refractive index layer 6, preferably low refractive index The rate layer 3 is disposed on the outermost surface and is disposed adjacent to the low refractive index layer 3.

The antistatic layer is not particularly limited, and for example, it is preferably formed of a composition for an antistatic layer containing a resin and an antistatic agent.

The antistatic agent is not particularly limited, and examples thereof include a cationic compound such as a quaternary ammonium salt, a pyridinium salt, or a mono- to tertiary amino group; a sulfonic acid base, a sulfate base, a phosphate base, a phosphonic acid base, and the like. Anionic compound; amphoteric compound such as amino acid or amine sulfate; nonionic compound such as amino alcohol, glycerol or polyethylene glycol; alkoxide such as tin and titanium An organometallic compound; a metal chelate compound such as an ethyl acetonide salt of the organometallic compound. Compounds which polymerize the above-listed compounds can also be used.

As the antistatic agent, an organic substance such as a monomer or oligomer having a tertiary amino group, a quaternary ammonium group or a metal chelate portion and polymerizable by free radiation or a coupling agent having a functional group may also be preferably exemplified. A polymerizable compound such as a metal compound. These antistatic agents are only required to be ionic liquids.

As the antistatic agent, a conductive polymer is also preferably exemplified. The conductive polymer is not particularly limited, and examples thereof include an aromatic conjugated poly(p-phenylene), a heterocyclic conjugated polypyrrole, a polythiophene, and an aliphatic group. a conjugated polyacetylene, a polyaniline containing a hetero atom conjugated system, a poly-p-phenylene ethylene having a mixed conjugated system, a conjugated system having a plurality of conjugated chains in a molecule, and a conjugated system A conductive composite of a polymer in which the conjugated polymer chain is grafted or block copolymerized with a saturated polymer.

As the antistatic agent, conductive metal oxide fine particles are also preferably used. The conductive metal oxide fine particles are not particularly limited, and examples thereof include ZnO (refractive index 1.90, the values in the parentheses below all indicate the refractive index), Sb ₂ O ₂ (1.71), SnO ₂ (1.997), and CeO _{2 .} (1.95), indium tin oxide (abbreviated as ITO; 1.95), In ₂ O ₃ (2.00), Al ₂ O ₃ (1.63), tin oxide doped with antimony (abbreviated as ATO; 2.0), zinc oxide doped with aluminum ( Referred to as AZO; 2.0) and so on.

The content of the antistatic agent in the composition for an antistatic layer is preferably such that the effect of containing the antistatic agent can be sufficiently enjoyed, and the effect obtained by the optical layered body produced according to the present invention is not inhibited. Blending.

The resin in the antistatic layer, that is, the resin used as the composition for the antistatic layer, is not particularly limited, and examples thereof include the same as those described above for the hard coat layer, and are cured by ultraviolet rays or electron beams. A mixture of a free radiation curable resin of a resin, a free radiation curable resin and a solvent drying resin, or a thermosetting resin.

The antistatic layer may be coated on the above-mentioned light-transmitting substrate or the like by applying the above-mentioned antistatic layer composition prepared using each material, and dried as needed, by irradiation with free radiation or It is formed by hardening such as heating.

[Polarizer]

The polarizing plate of the present invention has an antireflection film on at least one side of the polarizing film, and the antireflection film is obtained according to the manufacturing method of the present invention described above, that is, characterized in that it has at least a transparent substrate and a low refractive index. a layer and a comprehensive antifouling layer covering the low refractive index layer, wherein the low refractive index layer and the antifouling layer are formed using a composition for forming a low refractive index layer containing a fluorine-containing compound, fine particles, and a binder resin. The average surface roughness of the antifouling layer is determined by X-ray photoelectron spectroscopy (XPS) from the side of the antifouling layer to a fluorine atom/carbon atom ratio of 0.6 to 1.0 and a germanium atom/carbon atom ratio of less than 0.25. Ra') is 10 nm or less. With such a configuration, the polarizing plate of the present invention has an anti-reflection function excellent in physical strength and light resistance, and can significantly reduce the cost and make the display device lighter and thinner.

Usually, the polarizing plate is provided with a protective film on both sides of the polarizing film. However, 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 may be provided on one side or both sides of the polarizing film. In the case of being provided on one side, from the viewpoint of improving the visibility angle characteristics of the liquid crystal display screen, it is preferable that the other surface has an optical compensation film (phase difference film) including an optical compensation layer of an optically anisotropic layer.

When the antireflection film of the present invention is used as a protective film, it is particularly preferable to use a triethylenesulfonated cellulose film as a transparent support. In this case, the transparent support using the protective film of the antireflection film is preferably passed through a polarizing film through an adhesive layer containing polyvinyl alcohol or the like as needed. Further, as described above, it is preferable that the other side of the polarizing film has a protective film, preferably the optical compensation film (phase difference film) described above. The side opposite to the polarizing film of the other protective film may also have Adhesive layer. By setting it as such, the polarizing plate of the present invention can improve the contrast of the liquid crystal display device in the bright room, and the viewing angles of the upper, lower, left and right sides.

[Image display device]

The image display device of the present invention has an antireflection film or a polarizing plate on the outermost surface of the display, and the polarizing plate has an antireflection film on at least one side of the polarizing film, and the antireflection film is manufactured according to the present invention described above. The method obtained, that is, characterized by having at least a transparent substrate, a low refractive index layer, and a comprehensive antifouling layer covering the low refractive index layer, the low refractive index layer and the antifouling layer containing a fluorine-containing compound a composition for forming a low refractive index layer of fine particles and a binder resin, and a fluorine atom/carbon atom ratio of 0.6 to 1.0 as measured by X-ray photoelectron spectroscopy (XPS) from the side of the antifouling layer, and a germanium atom/carbon The atomic ratio is less than 0.25, and the average surface roughness (Ra') of the antifouling layer is 10 nm or less.

As the display, for example, a liquid crystal display (LCD), a plasma display panel (PDP), a cathode tube display device (CRT), an inorganic and organic electroluminescence display, a rear projection type display, and a fluorescent display tube (VFD) are preferable. , touch panels, mobile computers, electronic paper and other displays. Further, as the video display device, a device including such a display, such as a personal computer, a personal digital assistant (PDA), a game machine, a digital camera, a digital camera, or the like, is preferable.

[Examples]

Hereinafter, the present invention will be described in further detail based on the examples, but the present invention is not limited by the examples.

(evaluation method) 1. Minimum reflectance (evaluation of anti-reflection characteristics)

For the antireflection film obtained in each of the examples and the comparative examples, a black tape for preventing back reflection of the film was attached to the side of the transparent substrate where the low refractive index layer was not provided, and the surface of the low refractive index layer was used. A spectrometer ("UV-2550 (model)": manufactured by Shimadzu Corporation) manufactured by a 5 degree specular reflection measuring device measures the reflectance, and the minimum value among the wavelength regions of 380 to 780 nm is the lowest reflectance. The smaller the minimum reflectance, the more excellent the antireflection property of the antireflection film.

2. Evaluation of coated surface

A black tape was attached to the surface of the film on the side where the low refractive index layer was not formed, and the surface of the low refractive index layer was formed, and visually observed with a three-wavelength lamp, and the results were evaluated based on the following criteria.

○: The faces of the low refractive index layer were uniform.

△: The surface of the low refractive index layer was slightly warped as compared with the evaluation of the above ○.

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

3. Evaluation of surface abrasion resistance and adhesion

For the antireflection film obtained in each of the examples and the comparative examples, steel wool (BONSTAR #0000 manufactured by Nippon Steel Wool Co., Ltd.) was rubbed back and forth 10 times with a load of 300 g/cm ² , and the visual results were evaluated based on the following criteria. . The less the number of scratches, the more excellent the abrasion resistance and the adhesion of the low refractive index layer to the antifouling layer.

○: No damage was caused at all.

△: The number of scars is 1 to 5.

×: The number of scars is six or more.

4. Evaluation of antifouling (1) Antifouling properties for fingerprints

After the fingerprint was attached to the surface of the antireflection film obtained in each of the examples and the comparative examples, the film was wiped with BEMCOT M-3 (manufactured by Asahi Kasei Co., Ltd.), and the ease of wiping was visually confirmed, and evaluated according to the following criteria.

○: The fingerprint can be easily wiped.

△: The fingerprint can be wiped.

×: The fingerprint cannot be wiped.

(2) The surface of the antireflection film obtained in each of the examples and the comparative examples was visually confirmed, and the state in which it was drawn with an oil-based stylus pen and the state after wiping with a cloth were evaluated based on the following criteria.

◎: The ink is gathered into a spherical shape and wiped easily.

○: The ink does not stick to the surface, the lines become thinner, and the wiping is easy.

×: A trace of ink remains after wiping.

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

The surface of the antireflection film (antifouling layer) obtained in each of the examples and the comparative examples was analyzed by X-ray photoelectron spectroscopy (XPS), and the atomic ratio was obtained according to the following method, and the atomic ratio of the fluorine-containing compound phase was separated. And form an indicator of the antifouling layer.

The device is an XPS device ("ESCALAB 220i-XL (model)", manufactured by THERMOFISHER SCIENTIFIC), using X-ray output power: 10kV‧16mA (160W), lens: Large Area XL (magnetic field lens), aperture opening: FOV =open, AA=open, measurement area: 700μm Photoelectron receiving angle: 90 degrees (input lens is placed on the sample normal line), neutralization and charging: electron neutralization gun +4 (V) ‧0.08 (mA), and analysis under the use of neutral and auxiliary metal mask. The atomic ratio of a carbon atom, a nitrogen atom, an oxygen atom, a fluorine atom, and a ruthenium atom on the surface of the antireflection film obtained by the measurement was used to calculate a fluorine atom/carbon atom ratio and a ruthenium atom/carbon atom ratio. Further, for the germanium atom, the peak composition of the Si2p spectrum is separated and analyzed, and the inorganic germanium component (SiO ₂ ) which detects the peak near 103 to 104 eV and the organic germanium component which detects the peak near 101 to 102 eV (C- Si-O), the atomic composition was measured, and an inorganic germanium atom/carbon atom ratio and an organic germanium atom/carbon atom ratio were calculated.

6. Evaluation of surface state (measurement of contact angle and drop angle)

For the antireflection film obtained in each of the examples and the comparative examples, hexadecane was used as the measurement liquid, and the contact angle and the drop angle were measured by a protractor ("DM-500 (model)", manufactured by Kyowa Interface Science Co., Ltd.). The amount of droplets was set to 2 μl.

7. Evaluation of surface state (evaluation by surface observation by atomic force microscopy)

Atomic force microscope (AFM) ("L-trace (model)", manufactured by SII NANOTECHNOLOGY Co., Ltd.), the number of vibrations in the dynamic mode (Dynamic Force Mode): 0.4 to 1.0 Hz, scanning range: 3 μm, and various examples were observed. And the shape and phase diagram of the surface of the antireflection film obtained in the comparative example. For the cantilever system, "OMCL-AC160TS-C2 (model)" (manufactured by KS OLYMPUS Co., Ltd., elastic constant: 42 N/m) was used. Here, in order to reduce the resolution due to contamination of the probe by the cantilever used for observation, a brand new product is always used. Further, in order to prevent deterioration of wear during observation, the observation was performed at a resolution of 512 pixels × 256 pixels without sacrificing the range of the resolution and reducing the load on the probe as much as possible. Observe the tilt of the data using the attached software after observation.

By the surface observation, in the case where the surface of the low refractive index layer is completely phase-separated and an antifouling layer is formed, a uniform state can be confirmed, and on the other hand, the antifouling layer is not completely separated on the surface, and it can be confirmed. The surface of the island pattern is an uneven pattern of a portion separated from the phase and an unseparated portion. Here, as long as it is in a uniform state, it can be said that even if it is visually observed, it is not slightly whitened or the coated surface is rough, and the low refractive index layer and the antifouling layer are favorably formed.

○: The antifouling layer is uniform.

△: Although there was no island structure in the antifouling layer, slight deformation was observed as compared with the evaluation of ○ above.

×: The antifouling layer exhibited an island structure, and slight whitening or roughening of the coated surface was visually observed.

8. Determination of average surface roughness (Ra')

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

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

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

Low refractive index layer forming composition 1

Neopentyl alcohol triacrylate (PETA): 0.10 parts by mass

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

Hollow vermiculite particle dispersion ^*2 : 6.69 parts by mass

Solid vermiculite particle dispersion ^*3 : 0.74 parts by mass

Fluoropolymer ^*4 : 2.79 parts by mass

Fluorinated 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

*1, "X-71-1203M (trade name)": 20% by mass solution manufactured by Shin-Etsu Chemical Co., Ltd. (solvent: methyl isobutyl ketone, photocurable reactive group: (methyl) acrylonitrile group, A fluorine-containing compound containing a reactive decane unit and a decane unit having a perfluoropolyether group.

*2, the hollow vermiculite particle content in the dispersion was 20% by mass, and the solvent (methyl isobutyl ketone) content was 80% by mass. Further, the hollow vermiculite particles have an average particle diameter of 60 nm and have a photocurable reactive group by surface treatment.

*3, "MIBK-SD (trade name)", average primary particle diameter: 12 nm, solid content: 30% by mass, solvent: methyl isobutyl ketone, solid vermiculite particles having photohardenability by surface treatment The methacryl oxime group of the reactive group.

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

*5, "LINC 3A (trade name)": a fluorine-containing monomer having a neopentyl alcohol skeleton and a 20% by mass solution (solvent: methyl isobutyl ketone), manufactured by Kyoeisha Chemical Co., Ltd.

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

Preparation Example 2: Preparation of Composition 1 for Hard Coating Formation

A hard coat layer was prepared by mixing the components of the following composition in the following mass ratio Composition 1 was used.

Hard coating forming composition 1

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 Synthetic Chemical Co., Ltd.

*8, "M315 (trade name)", manufactured by East Asia Synthetic Co., Ltd.

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

Example 1

On a triacetonitrile-based cellulose (TAC) resin film having a thickness of 80 μm, the bar was coated with the composition 1 for forming a hard coat layer, dried at 50 ° C for 1 minute, and after removing the solvent, a UV irradiation device (FUSION UV SYSTEMS JAPAN) was used. The light source H-BULB manufactured by the company was hardened by ultraviolet irradiation at a radiation dose of 30 mJ/cm ² to obtain a hard coat layer having a thickness of about 10 μm.

Next, the obtained low-refractive-index layer-forming composition 1 prepared in Preparation Example 1 was applied onto the obtained hard coat layer to form a coating film (step (1)); heat treatment was performed at 50 ° C for 1 minute to make The coating film phase is separated into a low refractive index phase and an antifouling phase, and after removing the solvent (step (2)); ultraviolet irradiation is performed at a radiation dose of 200 mJ/cm ² to harden it to form a low refractive index layer and an antifouling layer (step (3)) An antireflection film having a transparent substrate, a hard coat layer, a low refractive index layer, and an antifouling layer is obtained. The solvent evaporated almost completely at the time of hardening, and the total thickness of the low refractive index layer and the antifouling layer was about 100 nm. Further, when the atomic ratio is measured by X-ray photoelectron spectroscopy (XPS), atoms of the fine particles contained in the low refractive index layer are also detected. Considering that the thickness of the X-ray photoelectron spectroscopy (XPS) antifouling layer is 1 to 3 nm, the thickness of the obtained antifouling layer is estimated to be in the range of 1 to 3 nm.

The results of evaluation of the obtained antireflection film according to the above evaluation method are shown in Table 1. In addition, an atomic force microscope (shape drawing and phase diagram) is shown in Fig. 4.

Example 2

An antireflection film was obtained in the same manner as in Example 1 except that the composition 1 for forming a low refractive index layer in Example 1 was replaced by the composition 2 for forming a low refractive index layer described below. The results of evaluation of the obtained antireflection film according to the above evaluation method are shown in Table 1. Further, an atomic force microscope diagram (shape diagram and phase diagram) is shown in Fig. 5.

Low refractive index layer forming composition 2

Neopentyl alcohol triacrylate (PETA): 1.32 parts by mass

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

Hollow vermiculite particle dispersion ^*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 1 for forming a low refractive index layer in Example 1 was replaced by the composition 3 for forming a low refractive index layer described below. For the resulting antireflective film, The results of the evaluation by the above evaluation methods are shown in the first table. Further, an atomic force microscope diagram (shape diagram and phase diagram) is shown in Fig. 6.

Low refractive index layer forming composition 3

Neopentyl alcohol triacrylate (PETA): 0.12 parts by mass

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

Hollow vermiculite particle dispersion ^*2 : 6.28 parts by mass

Solid vermiculite particle dispersion ^*3 : 0.7 parts by mass

Fluoropolymer ^*4 : 2.62 parts by mass

Fluorine 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

Preparation Example 3: Preparation Example of Composition for Forming High Refractive Index Layer

Injected and mixed rutile-type titanium oxide in a cannabis bottle ("TTO51(C) (trade name)", manufactured by Ishihara Sangyo Co., Ltd., primary particle size: 0.01 to 0.03 μm): 10 parts by mass, containing anionic group Dispersing agent ("DISPERBYK-163 (trade name)", manufactured by BYK CHEMIE JAPAN Co., Ltd.): 2 parts by mass and methyl isobutyl ketone: 48 parts by mass to prepare a mixture. About 4 times the amount of zirconia beads are used relative to the resulting mixture ( 0.3 mm) A composition for forming a high refractive index layer was prepared by stirring for 10 hours with a paint shaker.

Preparation Example 4: Preparation Example of Medium Refractive Index Layer Forming Composition

In addition to the preparation example of the composition for forming a high refractive index layer, the rutile-type titanium oxide is replaced by tin oxide doped with antimony ("SN-100P (trade name)", manufactured by Ishihara Sangyo Co., Ltd.), Containing anions The medium-refractive-index layer-forming composition was prepared in the same manner as in the preparation example of the composition for forming a high refractive index layer, except that the dispersing agent was a "DISPERBYK-111 (trade name)" (manufactured by BYK CHEMIE JAPAN Co., Ltd.).

Example 4

The above-mentioned hard-coat layer-forming composition 1 was applied to a triacetonitrile-based cellulose (TAC) resin film having a thickness of 80 μm, dried at 50 ° C for 1 minute, and after removing the solvent, a UV irradiation device (FUSION UV SYSTEMS) was used. A light source H-BULB manufactured by JAPAN Co., Ltd. was irradiated with ultraviolet rays at a radiation dose of 30 mJ/cm ² to obtain a hard coat layer having a thickness of about 10 μm.

On the obtained hard coat layer, the rod was coated with the composition for forming a refractive index layer obtained in Preparation Example 4, and irradiated with ultraviolet rays at a radiation 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 Preparation Example 3 was applied and cured by ultraviolet irradiation at a radiation dose of 200 mJ/cm ² to form a high refractive index layer having a thickness of about 60 nm. Next, the following composition for forming the low refractive index layer is applied to the rod to form a coating film (step (1)); heat treatment is performed at 50 ° C for 1 minute to phase separate the coating film into a low refractive index phase and an antifouling phase. And removing the solvent (step (2)); curing with ultraviolet radiation at a radiation dose of 200 mJ/cm ² to form a low refractive index layer and an antifouling layer (step (3)), thereby obtaining a transparent substrate, hard coating An antireflection film of a layer, a medium refractive index layer, a high refractive index layer, a low refractive index layer, and an antifouling layer. The solvent evaporated almost completely at the time of hardening, and the total thickness of the low refractive index layer and the antifouling layer was about 100 nm. Further, when the atomic ratio is measured by X-ray photoelectron spectroscopy (XPS), atoms of the fine particles contained in the low refractive index layer are also detected. Considering that the thickness of the X-ray photoelectron spectroscopy (XPS) antifouling layer is 1 to 3 nm, the thickness of the obtained antifouling layer is estimated to be in the range of 1 to 3 nm.

The results of evaluation of the obtained antireflection film according to the above evaluation method are shown in Table 1. Further, an atomic force microscope diagram (shape diagram and phase diagram) is shown in Fig. 7.

Low refractive index layer forming composition 4

Neopentyl alcohol triacrylate (PETA): 0.32 parts by mass

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

Hollow vermiculite particle dispersion ^*2 : 6.42 parts by mass

Solid vermiculite particle dispersion ^*3 : 1.43 parts by mass

Fluoropolymer ^*4 : 3.21 parts by mass

Fluorine 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 1 for forming a low refractive index layer in Example 1 was replaced with the composition 5 for forming a low refractive index layer described below. The results of evaluation of the obtained antireflection film according to the above evaluation method are shown in Table 1. Further, an atomic force microscope diagram (shape diagram and phase diagram) is shown in Fig. 8.

Low refractive index layer forming composition 5

Neopentyl alcohol triacrylate (PETA): 0.10 parts by mass

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

Hollow vermiculite particle dispersion ^*2 : 6.69 parts by mass

Solid vermiculite particle dispersion ^*3 : 0.74 parts by mass

Fluoropolymer ^*4 : 2.79 parts by mass

Fluorinated 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

*10, "X-71-1205 (trade name)": 20% by mass solution manufactured by Shin-Etsu Chemical Co., Ltd. (solvent: a mixture of methyl isobutyl ketone and methyl ethyl ketone, photocurable reactive group: A (meth) acrylonitrile group containing a fluorinated compound having a reactive decane unit and a decane unit having a perfluoropolyether group.

Example 6

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

Low refractive index layer forming composition 6

Dipentaerythritol hexaacrylate (DPHA): 1.32 parts by mass

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

Hollow vermiculite particle dispersion ^*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

Substituting the low refractive index layer forming composition 1 in Example 1 An antireflection film was obtained in the same manner as in Example 1 except for the composition 7 for forming a low refractive index layer described below. The results of evaluation of the obtained antireflection film according to the above evaluation method are shown in Table 1.

Low refractive index layer forming composition 7

Neopentyl alcohol triacrylate (PETA): 0.10 parts by mass

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

Hollow vermiculite particle dispersion ^*2 : 5.86 parts by mass

Solid vermiculite particle dispersion ^*3 : 0.65 parts by mass

Fluoropolymer ^*4 : 2.44 parts by mass

Fluorine 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 1 for forming a low refractive index layer in Example 1 was replaced by the composition 8 for forming a low refractive index layer described below. The results of evaluation of the obtained antireflection film according to the above evaluation method are shown in Table 1.

Low refractive index layer forming composition 8

Neopentyl alcohol triacrylate (PETA): 1.32 parts by mass

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

Hollow vermiculite particle dispersion ^*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 1 for forming a low refractive index layer in Example 1 was replaced by the composition 9 for forming a low refractive index layer described below. The results of evaluation of the obtained antireflection film according to the above evaluation method are shown in Table 1.

Low refractive index layer forming composition 9

Neopentyl alcohol triacrylate (PETA): 0.11 parts by mass

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

Hollow vermiculite particle dispersion ^*2 : 6.69 parts by mass

Solid vermiculite particle dispersion ^*3 : 0.74 parts by mass

Fluoropolymer ^*12 : 2.79 parts by mass

Fluorinated 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)": SOLVAY SPECIALTY POLYMERS JAPAN Co., Ltd., a two-terminal tetrafunctional methacrylate modified perfluoropolyether compound, and a fluorine-containing compound having no decane unit).

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

Comparative example 1

An antireflection film was obtained in the same manner as in Example 1 except that the composition 1 for forming a low refractive index layer in Example 1 was replaced by the composition 10 for forming a low refractive index layer described below. For the resulting anti-reflective film, The results evaluated by the above evaluation methods are shown in the second table. Further, an atomic force microscope diagram (shape diagram and phase diagram) is shown in Fig. 9.

Low refractive index layer forming composition 10

Neopentyl alcohol triacrylate (PETA): 0.12 parts by mass

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

Hollow vermiculite particle dispersion ^*2 : 7.04 parts by mass

Solid vermiculite particle dispersion ^*3 : 0.78 parts by mass

Fluoropolymer ^*4 : 2.93 parts by mass

Fluorine 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 1 for forming a low refractive index layer in Example 1 was replaced by the composition 11 for forming a low refractive index layer described below. The results of evaluation of the obtained antireflection film according to the above evaluation method are shown in the second table. Further, an atomic force microscope diagram (shape diagram and phase diagram) is shown in Fig. 10.

Low refractive index layer forming composition 11

Neopentyl alcohol triacrylate (PETA): 0.09 parts by mass

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

Hollow vermiculite particle dispersion ^*2 : 5.44 parts by mass

Solid vermiculite particle dispersion ^*3 : 0.6 parts by mass

Fluoropolymer ^*4 : 2.27 parts by mass

Fluorine 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 1 for forming a low refractive index layer in the first embodiment was replaced with the composition 12 for forming the low refractive index layer described below. The results of evaluation of the obtained antireflection film according to the above evaluation method are shown in the second table. Further, an atomic force microscope diagram (shape diagram and phase diagram) is shown in Fig. 11.

Low refractive index layer forming composition 12

Neopentyl alcohol triacrylate (PETA): 0.32 parts by mass

Hollow vermiculite particle dispersion ^*2 : 6.42 parts by mass

Solid vermiculite particle dispersion ^*3 : 1.43 parts by mass

Fluoropolymer ^*4 : 3.21 parts by mass

Fluorine 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 1 for forming a low refractive index layer in Example 1 was replaced by the composition 13 for forming a low refractive index layer described below. The results of evaluation of the obtained antireflection film according to the above evaluation method are shown in the second table.

Low refractive index layer forming composition 13

Neopentyl alcohol 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

The fluorine-containing compound used in Example 1 was diluted with m-difluorotoluene to a solution having a solid concentration of 3 mass%, and was prepared as an antifouling film deposition source.

On the triacetyl cellulose (TAC) resin film having a width of 500 mm, a thickness of 80 μm, and a length of 500 m, the composition for forming a hard coat layer was gravure-coated, and the composition for forming a low refractive index layer described below was gravure-coated. 13. Drying at 70 ° C for 1 minute, removing the solvent, and curing by ultraviolet irradiation at a radiation dose of 200 mJ/cm ² to form a hard coat layer having a thickness of about 10 μm and a low refractive index layer having a thickness of about 100 nm, thereby obtaining transparency. A laminate of a substrate/hard coat layer/low refractive index layer.

Next, the anti-fouling film vapor deposition source and the laminate are provided in a coil-type vapor deposition apparatus, and after vacuum evacuation to 1 e ^-4 Torr or less, the layered body is wound up at an operation speed of 5 m/min to be non-contact heating. The anti-fouling film evaporation source is evaporated by the heating lamp tube to obtain an anti-reflection film in which an anti-fouling film is formed on the low-refractive-index layer side of the laminate. The results of evaluation of the obtained antireflection film according to the above evaluation method are shown in the second table.

*1, the amount of the fluorine-containing compound (parts by mass) with respect to 100 parts by mass (solid content) of the binder resin (including the case where the fluorine-containing monomer and the fluorine-containing polymer are used) and the total amount of the fine particles ). Here, the solid component does not contain a polymerization initiator.

The antireflection films obtained in Examples 1 to 5 were excellent in all evaluations, and had excellent antireflection properties, excellent rubbing resistance and antifouling properties, and no whitening, as a result of contact angle and drop angle. A person with a uniform surface. Further, in the examples 1 to 5, from the observation of the average surface roughness or the observation by the atomic force microscope, which is also a uniform surface, it is confirmed that the antifouling layer is a comprehensive covering on the low refractive index layer. The way is formed uniformly.

In Example 6 in which the binder resin was replaced by PETA to DPHA, substantially good physical properties were obtained. However, although the coated surface was substantially uniform, it was somewhat rough and the abrasion resistance was somewhat lowered. Further, when DPHA was replaced by trimethylolpropane triacrylate (TMPTA) and pentaerythritol tetraacrylate (PETTA) to prepare an antireflection film, 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, substantially good physical properties were obtained. However, although the surface state was substantially uniform, it was somewhat rough, and the abrasion resistance was somewhat lowered. Example 8 in which a glycol ether as a solvent was substituted with toluene was presumed to have a slight influence on the dispersibility of fine particles, and although the abrasion resistance was somewhat lowered, a substantially good result was obtained. From this result, it was confirmed that it is good to use a ketone or a glycol ether as a solvent. Further, in Example 9 in which the material used in Patent Document 2 is used as a fluorine-containing compound, although the antifouling layer has no island structure and is not slightly whitened, the smoothness of the coating film surface is obtained. It was a little inferior and confirmed to be slightly deformed. From this, it was confirmed that the fluorine-containing compound preferably has a decane unit.

Further, in the antireflection film obtained in the examples, the total thickness of the low refractive index layer and the antifouling layer was about 100 nm, and the thickness of the antifouling layer was 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 antireflection properties were the same as those in the examples. However, since the antimony component was large, the antifouling property was not sufficient, and whitening was also confirmed. Further, the drop angle of 33° is not called a uniform surface, and the sea-island structure is confirmed from the observation by atomic force microscopy. It is considered that this sea-island structure is considered to be a major cause of slight whitening due to the fact that the fluorine-containing decane compound is small and cannot completely cover the outermost surface of the low-refractive-index layer, and a uniform anti-fouling layer cannot be 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, and the entire surface of the low refractive index layer was rough and the uniform antifouling layer was not formed. It is considered that the coarse fluorine-containing compound causes the projections of the fine particles in the low refractive index layer to have irregularities as a fuse, and as a result, the entire surface of the layer is generated. 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 becomes soft, and when it is wiped when the antifouling property is evaluated, scratches are caused. Further, in Comparative Example 3 which does not contain a fluorine-containing compound and has a fluorine atom/carbon atom ratio of less than 0.6, although a uniform surface is obtained, since the amount of fluorine is small, the antifouling property is not sufficient. In Comparative Example 4, in the case where no fine particles were used, the mutual solubility of the binder resin and the fluorine-containing compound was poor, and the entire coating film became white when the coating film was dried, and the evaluation could not be performed. From this result, it is known that in order to maintain the binder resin and mutual solubility The balance of the poor fluorine-containing compound and the composition of the final purpose are necessary for the action of the fine particles. Further, in Comparative Example 5 in which the antifouling layer was formed by vapor deposition, the antifouling property and the surface state were substantially good, but there was no reaction between the reactive functional group and the low refractive index phase in the antifouling phase of the present invention. The functional group reaction hardens, and the adhesion between the antifouling layer after hardening and the low refractive index layer is weak, and the abrasion resistance is deteriorated.

[Industrial availability]

According to the present invention, it is possible to easily produce an antireflection film which has excellent antireflection characteristics, has excellent rubbing resistance and antifouling property, and suppresses the occurrence of slight whitening which has never been solved so far. The obtained antireflection film is suitably provided on a polarizing plate or an image display device.

1‧‧‧Anti-reflective film

2‧‧‧Transparent substrate

3‧‧‧Low refractive index layer

4‧‧‧hard coating

5‧‧‧Medium refractive index layer

6‧‧‧High refractive index layer

7‧‧‧Medium and high refractive index layer

8‧‧‧Antifouling layer

Fig. 1 is a schematic view showing a cross section of an antireflection film of the present invention.

Fig. 2 is a schematic view showing a cross section of the antireflection film of the present invention.

Fig. 3 is a schematic view showing a cross section of the antireflection film of the present invention.

Fig. 4 is a view showing a shape and a phase diagram of the surface of the antireflection film obtained in Example 1 by atomic force microscopy.

Fig. 5 is a view showing a shape and a phase diagram of the surface of the antireflection film obtained in Example 2 by atomic force microscopy.

Fig. 6 is a view showing a shape and a phase diagram of the surface of the antireflection film obtained in Example 3 by atomic force microscopy.

Fig. 7 is a view showing a shape and a phase diagram of the surface of the antireflection film obtained in Example 4 by atomic force microscopy.

Fig. 8 is a view showing a shape and a phase diagram of the surface of the antireflection film obtained in Example 5 by atomic force microscopy.

Fig. 9 is a view showing a shape and a phase diagram of the surface of the antireflection film obtained in Comparative Example 1 by atomic force microscopy.

Fig. 10 is a view showing a shape and a phase diagram of the surface of the antireflection film obtained in Comparative Example 2 by atomic force microscopy.

Fig. 11 is a view showing a shape and a phase diagram of the surface of the antireflection film obtained in Comparative Example 3 by atomic force microscopy.

Claims (13)

A method for producing an antireflection film, comprising the following steps (1) to (3), wherein the antireflection film has a transparent substrate, a low refractive index layer, and an antifouling layer at least sequentially, from the antifouling layer The fluorine atom/carbon atom ratio measured by X-ray photoelectron spectroscopy (XPS) is 0.6 to 1.0, and the germanium atom/carbon atom ratio is less than 0.25, and the average surface roughness (Ra') of the antifouling layer is 10 nm. Hereinafter, the step (1) is 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; and (2) separating the coating film into phases. a step of low refractive index phase and antifouling phase; step (3) heating the low refractive index phase and the antifouling phase, or irradiating the low refractive index phase and the antifouling phase with free radiation to form a low refractive index layer and covering The step of a comprehensive antifouling layer of the low refractive index layer. The method for producing an antireflection film according to claim 1, wherein the fluorine-containing compound has a reactive decane unit and a perfluoropolyether-based decane unit. The method for producing an antireflection film according to claim 2, wherein the reactive decane unit and the perfluoropolyether group-containing decane unit each have a decane skeleton. The method for producing an antireflection film according to the second or third aspect of the invention, wherein the reactive group is at least one selected from the group consisting of a (meth) acrylonitrile group and a vinyl group. The manufacture of an antireflection film according to any one of claims 1 to 4 The method wherein the fluorine-containing compound has a weight average molecular weight of 5,000 or more. The method for producing an antireflection film according to any one of claims 1 to 5, wherein the fine particles are fine particles of vermiculite. The method of producing an antireflection film according to any one of claims 1 to 6, wherein the microparticles comprise microparticles having voids. The method for producing an antireflection film according to any one of claims 1 to 7, wherein the fine particles are surface treated. The method for producing an antireflection film according to any one of claims 1 to 8, wherein the binder resin is a free radiation curable resin. The method for producing an antireflection film according to claim 9, wherein the free radiation curable resin contains a trifunctional or higher (meth) acrylate. An antireflection film produced by the method for producing an antireflection film according to any one of claims 1 to 10. A polarizing plate having an antireflection film on at least one side of a polarizing film, the antireflection film being an antireflection film according to claim 11 of the patent application. An image display device having an anti-reflection film or a polarizing plate on the outermost surface of the display; the polarizing plate having an anti-reflection film on at least one side of the polarizing film, the anti-reflection film being the eleventh item of the patent application scope Anti-reflective film.