JP2021004963A - Antireflection film - Google Patents

Abstract

To provide an antireflection film excellent in optical characteristics such as haze while maintaining antireflection property, surface hardness and anti-static property.SOLUTION: The antireflection film of the present invention includes a base material (I), an anti-static layer (II), a hard coat layer (III), and an antireflection layer (IV) in this order. (1) The anti-static layer (II) contains conductive particles of 40-90 weight% and has a thickness of 30-120 nm, (2) the hard coat layer (III) contains a resin component (A) obtained by curing urethane acrylate (A1) with three functions or less and urethane acrylate (A2) with four functions or more, and has a thickness of 1-3 μm, and (3) the antireflection layer (IV) contains a low refractive index layer (IV-L).SELECTED DRAWING: Figure 1

Description

The present invention relates to an antireflection film provided to prevent external light from being reflected on the surface of a window, display, or the like. In particular, the present invention relates to an antireflection film provided on the front panel of an optical display device such as a CRT display, a liquid crystal display (LCD), or a plasma display (PDP).

Generally, antireflection property is obtained by forming an antireflection layer having a multi-layer structure with a repeating structure of a high refractive index layer and a low refractive index layer on a transparent base material. Further, in the case of the antireflection film in which these antireflection layers are provided on the transparent base material, since the surface thereof is relatively flexible, in order to impart surface hardness typified by scratch resistance. , A method is used in which a hard coat layer formed by curing an acrylic material is provided and an antireflection layer is formed on the hard coat layer (Patent Document 1).
Since the hard coat layer obtained by curing the acrylic material has high insulating properties, it is easily charged, and there is a problem that stains are generated due to adhesion of dust or the like to the surface of the antireflection film provided with the hard coat layer. In order to prevent this, it is required to add antistatic property to the antireflection film. Therefore, in order to impart antistatic properties to the antireflection film provided with the hard coat layer and the antireflection layer, a method of adding conductive particles to the hard coat layer has been proposed (Patent Document 2).

However, the thickness of the hard coat layer needs to be several μm in order to obtain a predetermined surface hardness. It can be said that this is a much thicker layer than the antireflection layer having a thickness of at most 200 to 300 nm. Further, in order for the conductive particles in the hard coat layer to exhibit antistatic property (surface resistivity), it is necessary to secure the density of the conductive particles in the hard coat layer. Therefore, the method of adding the conductive particles into the hard coat layer has a drawback that the amount of the conductive particles used increases due to the relationship between the thickness of the hard coat layer and the density of the conductive particles. When the amount of conductive particles used is large, there is an adverse effect that the transmittance of the antireflection film is lowered.

International Publication No. 2013/018187 International Publication No. 2010/038709

Therefore, an object of the present invention is to provide an antireflection film having excellent optical characteristics such as haze and hue while maintaining antireflection, surface hardness, and antistatic property.
The present inventors maintain antistatic properties by providing an antistatic layer (II) having a thickness of several tens of nm to several hundreds of nm between the base material (I) and the hard coat layer (III). However, it has been found that the amount of conductive particles used can be suppressed. As a result, they have found that the obtained antireflection film is excellent in antireflection property, surface hardness, antistatic property and optical properties, and completed the present invention.

That is, the present invention is an antireflection film containing a base material (I), an antistatic layer (II), a hard coat layer (III) and an antireflection layer (IV) in this order.
(1) The antistatic layer (II) is a layer having a thickness of 10 to 200 nm containing 40 to 90% by weight of conductive particles.
(2) The hard coat layer (III) is a layer having a thickness of 1 to 3 μm containing a resin component (A) obtained by curing a urethane acrylate (A1) having a trifunctionality or less and a urethane acrylate (A2) having a trifunctionality or higher. And
(3) The antireflection layer (IV) includes a low refractive index layer (IV-L).
The antireflection film.

The antireflection film of the present invention is excellent in antireflection, surface hardness, antistatic property, and also excellent optical characteristics such as haze and hue. Since the antireflection film of the present invention contains conductive particles at a high concentration in the thin antistatic layer (II), it is excellent in antistatic property (surface resistivity). In the antireflection film of the present invention, since the thick hard coat layer (III) does not contain conductive particles, the conductive particles do not have a tint, which adversely affects optical characteristics such as visual average reflectance, haze, and hue. Less is. Further, the thickness of the hard coat layer (III) can be made relatively thin as 1 to 3 μm, and the total light transmittance and the visual average transmittance absorption loss can be suppressed.

It is a figure which shows an example of the layer structure of the antireflection film of this invention.

<Base material (I)>
The base material (I) is preferably made of a transparent resin having excellent impact resistance and not hindering the visibility. The total light transmittance of the base material (I) at a wavelength of 380 to 780 nm is preferably 85% or more, more preferably 90% or more, still more preferably 92% or more. From the viewpoint of transparency and impact resistance, the base material (I) is preferably formed of at least one resin selected from the group consisting of acrylic resin, polycarbonate resin, polyethylene terephthalate resin and triacetyl cellulose resin. A laminated base material in which these resins are laminated may be used. For example, a laminated base material of a polycarbonate resin and a polymethylmethacrylate resin may be used.
The thickness of the base material (I) is appropriately selected and designed from the required transparency and impact resistance, but is usually in the range of 0.2 to 2.0 mm. The upper limit of the thickness of the base material (I) is preferably 1.0 mm, more preferably 1.5 mm, and even more preferably 2 mm.

<Antistatic layer (II)>
The antistatic layer (II) is a layer having a thickness of 10 to 200 nm containing 40 to 90% by weight of conductive particles.
The thickness of the antistatic layer (II) is 10 to 200 nm. The thickness is preferably 20 to 150 nm, more preferably 30 to 100 nm, and even more preferably 40 to 80 nm.

[Conductive particles]
Conductive particles include indium oxide, indium tin oxide (ITO), tin oxide, antimony-doped tin oxide (ATO), phosphorus-doped tin oxide (PTO), fluorine-doped tin oxide (FTO), zinc oxide, and aluminum-doped zinc oxide (ATO). AZO), gallium-doped zinc oxide (GZO) and the like can be preferably used.
Among them, tin oxide-based conductive particles have positively correlated absorption with respect to wavelength, and the light transmission absorption loss of the formed antireflection film should be facilitated as Q ₄₅₀ <Q ₅₅₀ <Q _650. Can be done.
That is, by adding tin oxide-based conductive particles to the antistatic layer (II), the antireflection film is made into a polarizing plate, and a set of polarizing plates is arranged so that the polarizing layers are parallel to each other. The hue can be neutralized, and a transmissive liquid crystal display having good color reproducibility can be obtained. The antistatic layer (II) is at least one conductive particle selected from the group consisting of indium oxide-tin oxide (ITO), antimony-doped tin oxide (ATO), phosphorus-doped tin oxide (PTO), and fluorine-doped tin oxide (FTO). Is preferably contained. Organic conductive particles can also be used.

The content of the conductive particles is 40 to 90% by weight. The content is preferably 50 to 90% by weight, more preferably 55 to 90% by weight, still more preferably 60 to 85% by weight.
The particle size of the conductive particles is preferably 1 nm to 100 nm. The particle size is preferably 1 to 50 nm, more preferably 1 to 30 nm, and even more preferably 1 to 15 nm.

[Resin component (a)]
The resin component (a) of the antistatic layer (II) has a function as a binder for forming the antistatic layer (II), and is preferably formed by curing a tetrafunctional or higher functional urethane acrylate (a2).
As a tetrafunctional or higher functional urethane acrylate (a2), pentaerythritol tri (meth) acrylate was reacted with both-terminal isocyanates (for example, trihexadiethylene diisocyanate), and three (meth) acryloyl groups were added to each of the molecular chain ends. Examples thereof include a hexafunctional urethane acrylate (a2) having.

[Formation of antistatic layer (II))]
The method of forming the antistatic layer (II) will be described. In the antistatic layer (II), a coating liquid containing conductive particles and a monomer or oligomer for forming the resin component (a) is applied onto the base material (I) to form a coating film on the base material (I). The coating film is dried as necessary, and then the antistatic layer is subjected to a curing reaction of the monomer or oligomer for forming the resin component (a) by irradiating the coating film with ionizing radiation such as ultraviolet rays and electron beams. It can be (II).

As the monomer or oligomer for forming the resin component (a), a tetrafunctional or higher functional urethane acrylate (a2) is preferable. Examples of the tetrafunctional urethane acrylate (a2) include those obtained by reacting pentaerythritol di (meth) acrylate with a terminal isocyanate compound and introducing two (meth) acryloyl groups at both ends of the isocyanate compound. As a hexafunctional urethane acrylate (a2), pentaerythritol tri (meth) acrylate is reacted with both terminal isocyanates (for example, trihexadiethylene diisocyanate) to form three (meth) acryloyl groups at each end of the molecular chain. The ones that have been introduced can be mentioned.

A solvent and various additives can be added to the coating liquid, if necessary. Solvents include aromatic hydrocarbons such as toluene, xylene, cyclohexane and cyclohexylbenzene, hydrocarbons such as n-hexane, dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, dioxane, dioxolane and trioxane. , Tetras such as tetrahydrofuran, anisole and phenetol, and ketones such as methylisobutylketone, methylbutylketone, acetone, methylethylketone, diethylketone, dipropylketone, diisobutylketone, cyclopentanone, cyclohexanone, methylcyclohexanone, and methylcyclohexanone. , Also esters such as ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-pentyl acetate, and γ-petitolactone, as well as methyl cellosolves, cellosolves, etc. It is appropriately selected from among cellosolves such as butyl cellosolve and cellosolve acetate in consideration of coating suitability and the like. Further, as an additive, a surface adjusting agent, a refractive index adjusting agent, an adhesion improving agent, a curing agent and the like can be added to the coating liquid.
Above all, the solvent of the coating liquid for forming the antistatic layer (II) preferably contains a solvent that dissolves or swells the base material (I). The adhesion between the antistatic layer (II) formed by the coating liquid containing a solvent that dissolves or swells the base material (I) and the base material (I) can be improved.

As a coating method, a roll coater, a reverse roll coater, a gravure coater, a micro gravure coater, a knife coater, a bar coater, a wire bar coater, a die coater, and a dip coater can be used.

Further, when the coating liquid for forming the antistatic layer (II) is cured by ultraviolet rays, it is preferable to add a photopolymerization initiator to the coating liquid for forming the antistatic layer (II). The photopolymerization initiator may be any one that generates radicals when irradiated with ultraviolet rays, and for example, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, and thioxanthones may be used. Can be done. The amount of the photopolymerization initiator added is preferably 1 to 10 parts by weight, more preferably 1 to 7 parts by weight, based on 100 parts by weight of the tetrafunctional or higher functional urethane acrylate (a2).

<Hard coat layer (III)>
The hard coat layer (III) formed on the antistatic layer (II) is a resin component (A) formed by curing a trifunctional or lower functional urethane acrylate (A1) and a tetrafunctional or higher functional urethane acrylate (A2). It is a layer having a thickness of 1 to 3 μm containing.
The thickness of the hard coat layer (III) is 1 to 3 μm. That is, if this thickness is too thin, it becomes difficult to secure the basic physical properties (for example, hardness and strength) of the hard coat layer (III), and if it is excessively thick, it becomes a base material (I). This is because the difference in physical properties (for example, flexibility and elongation) becomes large, and as a result, molding defects such as cracks are likely to occur. The thickness of the hard coat layer (III) is preferably 1.2 to 2.5 μm, more preferably 1.5 to 2 μm.
The hard coat layer (III) contains a resin component (A), a silane coupling component (B), and silica particles (A) obtained by curing a urethane acrylate (A1) having a trifunctionality or less and a urethane acrylate (A2) having a trifunctionality or higher. It preferably contains C) and the metal chelate compound (D).

[Resin component (A)]
The resin component (A) has a function as a binder for forming the hard coat layer (III). As such a binder, a urethane acrylate (A1) having a trifunctionality or less and a urethane acrylate (A2) having a tetrafunctionality or higher are used in combination. That is, the urethane acrylate (A1) having trifunctionality or less forms a relatively flexible portion by curing, and the urethane acrylate (A2) having four or more functionalities forms a hard portion by curing. When used in combination, a film having an appropriate density and high hardness can be formed.
Urethane acrylate is obtained by further reacting a hydroxyl group-containing (meth) acrylate with a terminal isocyanate compound obtained by reacting a polyhydric isocyanate compound with a polyol compound having a plurality of hydroxyl groups, and is contained in urethane acrylate. The (meth) acryloyl group is a functional group, for example, a urethane acrylate having two (meth) acryloyl groups is bifunctional, and one having three is trifunctional.

Therefore, the urethane acrylate (A1) having trifunctionality or less has at most three (meth) acryloyl groups. For example, a terminal isocyanate compound is reacted with pentaerythritol mono (meth) acrylate. A urethane acrylate in which one (meth) acryloyl group is introduced into each of both ends is used as a bifunctional urethane acrylate (A1).
Further, pentaerythritol mono (meth) acrylate and pentaerythritol di (meth) acrylate are reacted with a terminal isocyanate compound to introduce one (meth) acryloyl group at one end of the isocyanate compound, and the other end. Introduced with two (meth) acryloyl groups is used as a trifunctional urethane acrylate (A1).

Further, pentaerythritol di (meth) acrylate is reacted with a terminal isocyanate compound, and two (meth) acryloyl groups are introduced at both ends of the isocyanate compound, which is used as a tetrafunctional urethane acrylate (A2). Will be done.
Of course, the above example is an example, and other urethane acrylates can be used as long as they are trifunctional or less. For example, hydroxyl group-containing (meth) acrylic acid esters such as ethylene glycol, diethylene glycol, and monoesters of (meth) acrylic acids of trihydric or higher polyhydric alcohols, and diesters are used to obtain the desired number of (meth) acryloyl groups. By introducing it, urethane acrylate (A1) having trifunctionality or less can be obtained.

The same applies to urethane acrylates (A2) having four or more functionalities. For example, by reacting pentaerythritol tri (meth) acrylate with both-terminal isocyanates (for example, trihexadiethylenediisocyanate), three at each end of the molecular chain A hexafunctional urethane acrylate (A2) having a (meth) acryloyl group can be obtained.

In the present invention, the trifunctional or lower urethane acrylate (A1) and the tetrafunctional or higher functional urethane acrylate (A2) have a weight ratio of 2/98 to 70/30, particularly 10/90 to 60/40 (A1 /). It is preferably used in A2). If the amount of the trifunctional or less functional urethane acrylate (A1) used is too large, the hardness of the obtained hard coat layer (III) may be impaired, and the basic performance of the hard coat layer (III) may deteriorate.

[Silane coupling component (B)]
The hard coat layer (III) preferably contains a silane coupling component (B). The silane coupling component (B) stably disperses and retains the silica particles (C) described later in the hard coat layer (III) without falling off, and at the same time, the antistatic layer (II) and the antireflection layer (IV). ) Is a component used to ensure adhesion.

That is, this component (B) is based on the following general formula (1);
R _{n −} Si (OR ₁ ) _4-n (1)
In the formula, R is an alkyl or alkenyl group, R ₁ is an alkyl group, an alkoxyalkyl group, an acyloxy group or a halogen atom, and n is a number of 1 or 2.
It is preferably a compound represented by (silane coupling agent) or a hydrolyzate thereof.
Examples of the group R in the general formula (1) include an alkyl group such as a methyl group, an ethyl group and a propyl group, and an alkenyl group such as a vinyl group, and the alkyl group includes a halogen atom such as chlorine, a mercapto group and an amino group. It may be substituted with a functional group such as a group, a (meth) acryloyl group, or an oxylan ring-containing group.
Further, the group R ₁ is an alkyl group, an alkoxyalkyl group, an acyloxy group or a halogen atom, and the group OR ₁ bonded to the silicon atom is a hydrolyzable group.

Specific examples of the silane coupling agent as described above include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and γ- (meth) acryloxipropyl. Trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ- Aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ- (N-styrylmethyl-β-aminoethylamino) propyltrimethoxysilane Examples thereof include hydrochloride, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane and the like.
The hydrolyzate (B) of such a silane coupling agent is polycondensed at the same time as hydrolysis to form a polymer connected in a network by a Si—O—Si bond. Therefore, by using the hydrolyzate (B) of such a silane coupling agent, the hard coat layer (III) can be made dense.

In the present invention, the content ratio of the above compound or its hydrolyzate (B) in the hard coat layer (III) is preferably 1 to 30 parts by weight per 100 parts by weight of the resin component formed from the above-mentioned urethane acrylate. More preferably, it is set in the range of 10 to 20 parts by weight. That is, if the content of this compound or its hydrolyzate (B) is larger than necessary, the basic performance (hardness, scratch resistance, etc.) of the hard coat layer (III) is impaired, and this content becomes high. If the amount is too small, the adhesion to the antistatic layer (II) and the antireflection layer (IV) is impaired, and the hard coat layer (III) is likely to be peeled off.

[Silica particles (C)]
The hard coat layer (III) preferably contains silica particles (C). The silica particles (C) in the hard coat layer (III) preferably have a particle size of 5 to 500 nm and a refractive index in the range of 1.44 to 1.5. That is, by using such oxide fine particles, it is possible to uniformly impart basic characteristics such as hardness over the entire hard coat layer (III). Further, the silica particles (C) are solid particles (for example, their density is 1.9 or more), unlike the hollow silica particles used for forming the antireflection layer (IV) described later. Since it has a particle size and a refractive index similar to those of hollow silica particles, it enhances the adhesion to the antireflection layer (IV) using the hollow silica particles, and enhances the adhesion to the hard coat layer (III) and the antireflection layer (IV). ) Can be effectively prevented, and further, the antireflection layer (IV) can be formed by utilizing the optical characteristics of the antireflection layer (IV).

The content of such silica particles (C) is preferably 10 to 80 parts by weight, more preferably 30 to 60 parts by weight, per 100 parts by weight of the resin component (A) formed from the urethane acrylate described above. By including the silica particles (C) in the hard coat layer (III) in such a range, the silica particles (C) can be combined with the antireflection layer (IV) while maintaining the basic characteristics of the hard coat layer (III). Adhesion can be improved and cracks and the like can be effectively prevented.

[Metal chelate compound (D)]
The hard coat layer (III) preferably contains the metal chelate compound (D). The metal chelate compound (D) is used to introduce a crosslinked structure into the hard coat layer (III) to make the hard coat layer (III) denser. That is, the crosslinked structure is also formed in the resin component (A) made of the urethane acrylate described above, but the denseness is lowered by using the low-functional urethane acrylate (A1) in order to impart flexibility. .. That is, in order to compensate for the decrease in the density of the metal chelate compound (D) without impairing the flexibility of the hard coat layer (III), in other words, the hardness and the like affected by the density of the film are mechanical. It is used to adjust the properties. Further, since such a metal chelate compound is also contained in the antireflection layer (IV), the use of the metal chelate compound (D) causes the hard coat layer (III) to adhere to the antireflection layer (IV). The properties are further enhanced, and cracks and the like during molding can be effectively prevented.

As such a metal chelate compound (D), a compound of titanium, zirconium, aluminum, tin, niobium, tantalum or lead containing a bidentate ligand is suitable.
A bidentate ligand is a chelating agent having two coordination denticities, that is, two atoms that can coordinate to a metal, and generally has a 5- to 7-membered ring depending on O, N, and S atoms. Form to form a chelate compound. Examples of these bidentate ligands are acetylacetonato, ethylacetacetate, diethylmalonato, dibenzoylmethanato, salicylate, glycolat, catecholat, salicylaldehidat, oxyacetphenonato, biphenolato, pyromeconato, oxynaphthoquino. Nato, Oxyanthraquinonato, Tropolonato, Binokichirat, Glycinato, Alaninato, Antroninato, Picolinato, Aminophenorato, Ethanolaminoto, Mercaptoethylaminoto, 8-oxyquinolinato, Salicylargiminato, Benzoinoxymato, Salicylaldoxymato, Oxy Examples thereof include azobenzenato, phenylazonaftrat, β-nitroso-α-naphtholto, diazoaminobenzenato, biuretato, diphenylcarbazonat, diphenylthiocarbazonato, biguanidato, and dimethylglioxymate.

The metal chelate compound (D) preferably used in the present invention is described in the following general formula (2):
M (Li) _k (X) _mk (2)
In the formula, M is titanium, zirconium, aluminum, tin, niobium, tantalum or lead.
Li is a bidentate ligand,
X is a monovalent group, preferably a hydrolyzable group.
m is the valence of the metal M,
k is a number of 1 or more within a range not exceeding the valence of the metal M.
It is represented by.

Among these, the metal M is preferably titanium, zirconium, or aluminum, and the group X is preferably an alkoxy group. Specific examples of such a metal chelate compound include the following Ti chelate compounds, Zr chelate compounds, and Al chelate compounds.

Ti chelate compound;
Triethoxy mono (acetylacetonato) titanium tri-n-propoxymono (acetylacetonato) titanium tri-i-propoxymono (acetylacetonato) titanium tri-n-butoxymono (acetylacetonato) titanium tri- sec-Butoxy Mono (Acetylacetonato) Titanium Tri-t-Butoxymono (Acetylacetonato) Titanium Diethoxybis (Acetylacetonato) Titanium Di-n-Propoxybis (Acetylacetonato) Titanium Di-i- Propoxy bis (acetylacetonato) titanium di-n-butoxy bis (acetylacetonato) titanium di-sec-butoxy bis (acetylacetonato) titanium di-t-butoxy bis (acetylacetonato) titanium monoethoxy -Tris (Acetylacetonato) Titanium Mono-n-Propoxy Tris (Acetylacetonato) Titanium Mono-i-Propoxy Tris (Acetylacetonato) Titanium Mono-n-Butoxy Tris (Acetylacetonato) Titanium Mono-sec -Butoxy Tris (Acetylacetonato) Titanium Mono-t-Butoxy Tris (Acetylacetonato) Titanium Tetrakiss (Acetylacetonato) Titanium Triethoxy Mono (Ethylacet Acetato) Titanium Tri-n-Propoxy Mono (Eethylacetate) Acetato) Titanium Tri-i-propoxymono (ethylacetacetate) Titanium Tri-n-butoxymono (ethylacetacetate) Titanium Tri-sec-Butoxymono (ethylacetacetate) Titanium Tri-t- Butoxy Mono (Ethylacet Acetato) Titanium Diethoxy Bis (Ethylacet Acetato) Titanium Di-n-Propoxy Bis (Ethylacet Acetato) Titanium Di-i-Propoxy Bis (Ethylacet Acetato) Titanium Di- n-Butoxy bis (Ethylacet acetato) Titanium Di-sec-Butoxy bis (Ethylacet acetato) Titanium Di-t-Butoxy bis (Ethylacet acetato) Titanium Monoethoxy Tris (Ethylacet acetato) Titanium Mono-n-Propoxy Tris (Ethylacet Acetato) Titanium Mono-i-Propoxy Tris (Ethylacet Acetato) Titanium Mono-n-Butoxy Tris (Ethylacet Acetato) Titanium Mono-sec-Butoxy Tris (Ethylacet acetato) Titanium mono-t-butoxy tris (Ethylacetoneacetate) Titanium Tetrakis (Ethylacetoneacetate) Titanium Mono (Acetylacetoneto) Tris (Ethylacetoneacetato) Titanium Bis (Acetylacetonato) Bis (Ethylacetoneacetato) Titanium Tris (Acetylacetoneat) Mono (Ethylacetoneacetate) Titanium

Zr chelate compound;
Triethoxy mono (acetylacetonato) zirconium Tri-n-propoxymono (acetylacetonato) zirconium Tri-i-propoxymono (acetylacetonato) zirconium Tri-n-butoxymono (acetylacetonato) zirconium tri- sec-butoxy mono (acetylacetonato) zirconium trit-butoxymono (acetylacetonato) zirconium diethoxy bis (acetylacetonato) zirconium di-n-propoxybis (acetylacetonato) zirconium di-i- Propoxy bis (acetylacetonato) zirconium di-n-butoxy bis (acetylacetonato) zirconium di-sec-butoxy bis (acetylacetonato) zirconium di-t-butoxy bis (acetylacetonato) zirconium monoethoxy Tris (acetylacetonato) zirconium mono-n-propoxytris (acetylacetonato) zirconium mono-i-propoxytris (acetylacetonato) zirconium mono-n-butoxy tris (acetylacetonato) zirconium mono-sec -Butoxy tris (acetylacetonato) zirconium mono-t-butoxy tris (acetylacetonato) zirconium tetrakis (acetylacetonato) zirconium triethoxy mono (ethylacetacetato) zirconium tri-n-propoxymono (ethylacetate) Acetato) Zirconium Tri-i-propoxymono (ethylacetacetate) zirconium Tri-n-butoxymono (ethylacetacetate) zirconium tri-sec-butoxymono (ethylacetacetate) zirconium tri-t- Butoxy mono (ethylacetacetate) zirconium diethoxybis (ethylacetacetate) zirconium di-n-propoxybis (ethylacetacetate) zirconium di-i-propoxybis (ethylacetacetate) zirconium di- n-butoxy bis (ethylacetacetate) zirconium di-sec-butoxy bis (ethylacetacetate) zirconium di-t-butoxy bis (ethylacetacetate) zirconium monoethoxy tris (ethylacetacetate) Zirconium Mono-n-Propoxy Tris (Ethylacet Acetato) Zirconium Mono-i -Propoxy Tris (Ethylacet Acetato) Zirconium Mono-n-Butoxy Tris (Ethylacet Acetato) Zirconium Mono-sec-Butoxy Tris (Ethylacet Acetato) Zirconium Mono-t-Butoxy Tris (Ethylacetacetate) Tato) Zirconium Tetraquis (Ethylacetacetate) Zirconium Mono (Acetylacetonato) Tris (Ethylacetacetato) Zirconium Bis (Acetylacetonato) Bis (Ethylacetacetato) Zirconium Tris (Acetylacetonato) Mono (Ethylacetacet) Tato) Zirconium

Al chelate compound;
Diethoxy mono (acetylacetonato) aluminum monoethoxybis (acetylacetonato) aluminum di-i-propoxymono (acetylacetonato) aluminum mono-i-propoxybis (acetylacetonato) aluminum mono-i-propoxy・ Bis (ethylacetacetate) aluminum Monoethoxybis (ethylacetacetate) aluminum Diethoxy mono (ethylacetacetate) aluminum di-i-propoxymono (ethylacetacetate) aluminum

The above-mentioned metal chelate compound (D) is used in an amount of preferably 0.1 to 30 parts by weight, more preferably 0.5 to 15 parts by weight, per 100 parts by weight of the resin component (A) formed from urethane acrylate. Will be done. By using the metal chelate compound (D) within this range, the adhesion between the metal chelate compound (D) and the antireflection layer (IV) formed on the hard coat layer (III) can be improved.

The hard coat layer (III) is composed of 100 parts by weight of the resin component (A).
The following general formula (1) of 1 to 30 parts by weight;
R _{n −} Si (OR ₁ ) _4-n (1)
In the formula, R is an alkyl or alkenyl group, R ₁ is an alkyl group, an alkoxyalkyl group, an acyloxy group or a halogen atom, and n is a number of 1 or 2.
The compound represented by (B) or its hydrolyzate (B),
10 to 80 parts by weight of silica particles (C) having a particle size of 5 to 500 nm and a refractive index in the range of 1.44 to 1.5.
Formed from 0.1 to 30 parts by weight of the metal chelating compound (D),
The antireflection film according to claim 1 is preferable.

[Formation of hard coat layer (III)]
In the hard coat layer (III), a coating liquid containing a monomer or oligomer for forming a resin component (A) is applied onto the antistatic layer (II) to form a coating film on the antistatic layer (II). The coating film is dried as necessary, and then the hard coat layer (hard coat layer) is subjected to a curing reaction of the monomer or oligomer for forming the resin component (A) by irradiating the coating film with ionizing radiation such as ultraviolet rays and electron beams. III).

<Anti-reflective layer (IV)>
The antireflection layer (IV) includes a low refractive index layer (IV-L).
[Low refractive index layer (IV-L)]
The refractive index of the low refractive index layer (IV-L) is preferably less than 1.48, more preferably less than 1.47. The thickness of the low refractive index layer (IV-L) is preferably 50 to 200 nm.

And the low refractive index layer (IV-L) is
(A) Low refractive index hollow silica particles having an average particle size of 10 to 150 nm and a refractive index of 1.44 or less (hereinafter, also referred to as low refractive index hollow silica particles).
(B) Silica particles having an average particle size of 5 to 110 nm and a refractive index of 1.44 to 1.50 (hereinafter, also referred to as silica particles).
It is a layer containing (C) a silane coupling compound or a hydrolyzate thereof, and (D) a metal chelate compound, and moreover.
The low refractive index layer (IV-L) contains (A) low refractive index hollow silica particles and (B) silica particles in a blending ratio of 5 to 95% by weight: 95 to 5% by weight.
(C) A silane coupling compound or a hydrolyzate thereof and (D) a metal chelate compound are contained in a blending ratio of 60 to 99% by weight: 40 to 1% by weight.
The ratio of the total amount of (A) low refractive index hollow silica particles and (B) silica particles to the total amount of (C) silane coupling compound or its hydrolyzate and (D) metal chelate compound is 10 to 10. 50% by weight: 90 to 50% by weight,
(A) The low refractive index hollow silica particles are preferably 30 parts by weight or less based on the total amount of the low refractive index layer (IV-L).

As will be described later, when the antireflection layer (IV) is composed of a plurality of antireflection layers, the low refractive index layer (IV-L) is an antireflection layer that is the outermost layer (visual field side).
The low index of refraction layer (IV-L) has a refractive index of less than 1.47.
(A) low refractive index hollow silica particles and (B) silica particles are contained in a blending ratio of 10 to 90% by weight: 90 to 10% by weight.
(C) A silane coupling compound or a hydrolyzate thereof and (D) a metal chelate compound are contained in a blending ratio of 70 to 98% by weight: 30 to 2% by weight.
(A) The low refractive index hollow silica particles are preferably 20 parts by weight or less based on the total amount of the low refractive index layer.

[(A) Low refractive index hollow silica particles]
The low refractive index hollow silica particles are hollow silica particles having a space inside from the viewpoint of exhibiting an antireflection effect. The average particle size is preferably 10 to 150 nm.
Since the low refractive index hollow silica particles are hollow particles, the density of the low refractive index hollow silica particles is lower than that of other silica particles, for example, usually 1.5 g / cm ³ or less.
Such low-refractive-index hollow silica particles are known by themselves, and are produced, for example, by synthesizing silica in the presence of a surfactant as a template, and finally performing firing to decompose and remove the surfactant. And is commercially available. In such a commercially available product, since the hollow silica particles use a solvent dispersion such as water or alcohol, the antireflection layer (IV) is formed in the antireflection layer (IV) forming solution prepared for forming the antireflection layer (IV). Inevitably, these solvents are mixed. However, in the drying and curing processes after coating, these solvents are volatilized and removed together with the solvent separately added to prepare the coating solution.

[(B) Silica particles]
Silica particles are particles that contribute to the improvement of scratch resistance and moisture resistance, and are composed of single particles or aggregated particles.
The average particle size of the silica particles is preferably 5 to 110 nm. The refractive index of the silica particles is preferably 1.44 to 1.50.
Unlike (A) low refractive index hollow silica particles, the silica particles are non-hollow particles having a dense inside and no space inside, and the density is usually 1.9 g / cm ³ or more. The silica particles are known by themselves, and commercially available products can be used as they are. The silica particles are also usually provided in a state of being dispersed in a solvent, and the solvent behaves in the same manner as in the case of the low refractive index hollow silica particles.

[(C) Silane coupling compound or its hydrolyzate]
The silane coupling compound or its hydrolyzate hydrolyzes itself to form a dense siliceous film.
As the silane coupling compound, known ones can be used without limitation. For example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, γ-glycid. Xypropitrimethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane Examples thereof include silane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanuppropyltriethoxysilane and the like.

Depending on the type of the silane coupling compound, it is preferable to use a decomposition product that has been hydrolyzed in advance with a dilute acid or the like for the purpose of improving the solubility in water or a solvent. The method of pre-hydrolyzing is not particularly limited, and a method of hydrolyzing a part thereof using an acid catalyst such as acetic acid, or a silane cup in a coating solution for forming an antireflection layer (IV) together with other components. A method is adopted in which a ring compound and the above acid or the like coexist and are partially hydrolyzed.

[(D) Metal chelate compound]
The metal chelate compound is contained for the purpose of increasing the density and strength of the layer, as well as the hardness. The metal chelate compound is a compound in which a chelating agent typified by a bidentate ligand is coordinated to a metal such as titanium, zirconium, or aluminum.

Specifically, triethoxy mono (acetylacetonate) titanium, tri-n-propoxymono (acetylacetonate) titanium, diethoxybis (acetylacetonate) titanium, monoethoxytris (acetylacetonate) titanium, Tetrakiss (acetylacetonate) titanium, triethoxy mono (ethylacetate acetate) titanium, diethoxy bis (ethylacetacetate) titanium, monoethoxy tris (ethylacetacetate) titanium, mono (acetylacetonate) tris ( Titanium chelating compounds such as ethylacetate acetate) titanium, bis (acetylacetonate) bis (ethylacetacetate) titanium, tris (acetylacetonate) mono (ethylacetacetate) titanium;
Triethoxy mono (acetylacetonate) zirconium, tri-n-propoxymono (acetylacetonate) zirconium, diethoxybis (acetylacetonate) zirconium, monoethoxytris (acetylacetonate) zirconium, tetrakis (acetylacetonate) ) Zirconium, triethoxy mono (ethylacetate acetate) zirconium, diethoxy bis (ethylacetacetate) zirconium, monoethoxy tris (ethylacetacetate) zirconium, tetrakis (ethylacetacetate) zirconium, mono (acetylacetate) Zirconium chelate compounds such as nat) tris (ethylacetacetate) zirconium, bis (acetylacetonate) bis (ethylacetacetate) zirconium, tris (acetylacetonate) mono (ethylacetacetate) zirconium;
Diethoxy mono (acetylacetonate) aluminum, monoethoxybis (acetylacetonate) aluminum, di-i-propoxymono (acetylacetonate) aluminum, mono-i-propoxybis (ethylacetoneacetate) aluminum, Examples thereof include aluminum chelate compounds such as monoethoxybis (ethylacetateacetate) aluminum and diethoxymono (ethylacetateacetate) aluminum.

[Combining components (A) to (D)]
The low refractive index layer (IV-L) contains (A) low refractive index hollow silica particles and (B) silica particles in a compounding ratio of 5 to 95% by weight: 95 to 5% by weight, and (C) silane. It is preferable that the hydrolyzate of the coupling compound and the metal chelate compound (D) are contained in a blending ratio of 60 to 99% by weight: 40 to 1% by weight.
When the compounding ratio of the (A) low refractive index hollow silica particles and the (B) silica particles is 5% by weight or more, the scratch resistance and the moisture resistance are improved.

When the compounding ratio of the hydrolyzate of the (C) silane coupling compound and the (D) metal chelate compound is 40% by weight or less, the film becomes brittle or the chelate compound. Is less likely to precipitate.
Further, the ratio of the total amount of (A) low refractive index hollow silica particles and (B) silica particles to the total amount of (C) silane coupling compound or its hydrolyzate and (D) metal chelate compound is 10 to 50% by weight: 90 to 50% by weight, and (A) low refractive index hollow silica particles are preferably 30 parts by weight or less based on the total amount of the low refractive index layer.

The ratio of the total amount of (A) low refractive index hollow silica particles and (B) silica particles to the total amount of (C) silane coupling compound or its hydrolyzate and (D) metal chelate compound is 10: When 90% by weight (lower limit value) is satisfied, the antireflection effect is good, and when 50:50% by weight (upper limit value) is not exceeded, scratch resistance and moisture resistance are good. Further, when the low refractive index silica particles (A) do not exceed 30 parts by weight with respect to the total amount of the low refractive index layer, the moisture resistance becomes good.
The above compounding ratio is a compounding ratio of (A) low refractive index hollow silica particles and (B) silica particles from 10 to 90% by weight: 90 to 10 from the viewpoint of balancing the antireflection effect, scratch resistance, and moisture resistance. The blending ratio of (C) the silane coupling compound or its hydrolyzate to (D) the metal chelate compound was 70 to 98% by weight: 30 to 2% by weight, and (A) low refractive index silica particles were formed. It is preferably 20 parts by weight or less based on the total amount of the low refractive index layer.

[Formation of low refractive index layer (IV-L)]
In the low refractive index layer (IV-L), each of the essential components (A) to (D) is dissolved in a specific amount, and any component is dissolved in the following solvent for the purpose of viscosity adjustment and easy coating, and is low. A coating solution for the refractive index layer (IV-L) is prepared, and this solution is applied to the hard coat layer (III), dried, and then heated and cured to form. The thickness of the layer is set in the range of 50 to 200 nm from the viewpoint of antireflection performance.

Solvents used in the coating solution for low refractive index layer (IV-L) are alcohol compounds such as methyl alcohol, ethyl alcohol and propyl alcohol; aromatic compounds such as toluene and xylene; ethyl acetate, butyl acetate, isobutyl acetate and the like. Ester compounds: Acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diacetone alcohol and other ketone compounds are suitable. In addition, solvents such as methylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and cellosolve compounds such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether can also be used.
Each of the above components constituting the coating solution for the low refractive index layer (IV-L) is usually mixed and stirred arbitrarily near room temperature to obtain a solution. When a commercially available particle dispersion is used, a solvent as a dispersion medium is inevitably mixed in the solution. The solvent in the coating solution for the low refractive index layer (IV-L) and the solvent to be separately blended are removed in the drying and curing steps.

The method of applying the solution onto the hard coat layer (III) is not particularly limited, and methods such as a dip coat method, a roll coat method, a die coat method, a flow coat method, and a spray method are adopted, but the appearance quality and the film are used. The dip coating method is preferable from the viewpoint of thickness control. When the antireflection layer (IV) is composed of two layers, a medium refractive index layer (IV-M) and a low refractive index layer (IV-L), which will be described later, first, the hard coat layer (III) is placed first. A medium refractive index layer (IV-M) is formed, and then a low refractive index layer (IV-L) is formed on the layer. Further, when the antireflection layer (IV) is composed of three layers of a medium refractive index layer (IV-M), a high refractive index layer (IV-H), and a low refractive index layer (IV-L) described later. First, a medium refractive index layer (IV-M) is formed on the hard coat layer (III), then a high refractive index layer (IV-H) is formed on the layer, and then a low refractive index layer (IV-H) is further formed on the layer. IV-L) is formed.

[Medium refractive index layer (IV-M)]
The antireflection layer (IV) has a medium refractive index layer (IV-M) laminated on the base material (I) side of the low refractive index layer (IV-L) in order to further enhance its antireflection effect. Is preferable.
The refractive index of the medium refractive index layer (IV-M) is preferably 1.50 or more and less than 1.75. The thickness of the medium refractive index layer (IV-M) is preferably 50 to 200 nm.

The medium refractive index layer (IV-M) has a refractive index of 1.50 or more and less than 1.75, a thickness of 50 to 200 nm, and a thickness of 50 to 200 nm.
(C) Silane coupling compound or its hydrolyzate,
Contains (D) a metal chelate compound and (E) metal oxide particles having an average particle size of 10 to 100 nm and a refractive index of 1.70 or more and 2.80 or less (hereinafter, also referred to as metal oxide particles). It is a layer of metal
(C) 20 to 80 parts by weight of the silane coupling compound or its hydrolyzate, (D) 0.1 to 2 parts by weight of the metal chelate compound, and (E) 20 to 80 parts by weight of the metal oxide particles. Is preferable.
The (C) silane coupling compound or its hydrolyzate, and (D) the metal chelate compound are the same as the components of the low refractive index layer (IV-L).

[(E) Metal oxide particles]
The metal oxide particles are contained for the purpose of satisfying that the refractive index of the medium refractive index layer (IV-M) is 1.50 or more and less than 1.75, and has an average particle size of 10 to 100 nm and a refractive index. Is a metal oxide particle having a value of 1.70 or more and 2.80 or less.
Examples of the metal oxide particles include zirconium oxide particles (refractive index = 2.40), composite zirconium metal oxide particles in which zirconium oxide and other oxides such as silicon oxide are composited at the molecular level to adjust the refractive index. Titanium oxide particles (refractive index = 2.71), composite titanium metal oxide particles whose refractive index is adjusted by combining titanium oxide with other oxides such as silicon oxide and zirconium oxide at the molecular level are used. .. These metal oxide particles are appropriately combined to prepare a layer having a desired refractive index. Such particles are known in their own right and are commercially available.

[Formation of medium refractive index layer (IV-M)]
As for the medium refractive index layer (IV-M), various components (C), (D) and (E) are used in specific amounts, and any component is used at the time of forming the low refractive index layer (IV-L). It is formed by dissolving it in a solvent to prepare a solution for a medium refractive index layer (IV-M), applying this solution to the hard coat layer (III), drying it, and then heating and curing it. The thickness of the layer is set in the range of 50 to 200 nm from the viewpoint of antireflection performance.
The mixing order and conditions of each of the above components constituting the solution for the medium refractive index layer (IV-M), and the coating method on the hard coat layer (III) are not particularly limited, and the low refractive index layer (IV-M) ( The method at the time of IV-L) formation can be adopted.
However, when the antireflection layer (IV) is composed of two layers, a low refractive index layer (IV-L) and a medium refractive index layer (IV-M), the medium refractive index layer (I) is on the base material (I) side. In the absence of IV-M), it is difficult for the antireflection effect to appear. Therefore, a medium refractive index layer (IV-M) is first formed on the hard coat layer (III), and then low on the medium refractive index layer (IV-M) according to the method described above. A refractive index layer (IV-L) is formed to form two layers.

[High Refractive Index Layer (IV-H)]
The antireflection layer (IV) further has a high refractive index layer (IV-M) between the low refractive index layer (IV-L) and the medium refractive index layer (IV-M) in order to exhibit an extremely high antireflection effect. It is preferable that H) is laminated.
The refractive index of the high refractive index layer (IV-H) is preferably 1.60 or more and less than 2.00. The thickness of the high refractive index layer (IV-H) is preferably 50 to 200 nm.
The high refractive index layer (IV-H) has a refractive index of 1.60 or more and less than 2.00, a thickness of 50 to 200 nm, and a thickness of 50 to 200 nm.
(C) A layer containing 10 to 50 parts by weight of a silane coupling compound or a hydrolyzate thereof, and (E) 50 to 90 parts by weight of metal oxide particles.
It is preferable that the refractive index of the high refractive index layer (IV-H) is larger than the refractive index of the medium refractive index layer (IV-M).
The (C) silane coupling compound or its hydrolyzate, and (E) metal oxide particles are the same as the components of the medium refractive index layer (IV-M).

[Formation of high refractive index layer (IV-H)]
In the high refractive index layer (IV-H), each component (C) and (E) is dissolved in a specific amount, and an arbitrary component is dissolved in various solvents used when forming the low refractive index layer (IV-L). A coating solution for a high refractive index layer (IV-H) is obtained, and this solution is applied to the medium refractive index layer (IV-M), dried, and then heated and cured to form. The thickness of the layer is set in the range of 50 to 200 nm from the viewpoint of antireflection performance.

The mixing order and conditions of each of the above components constituting the coating solution for the high refractive index layer (IV-H), and the coating method on the hard coat layer (III) are not particularly limited, and the low refractive index layer. The method at the time of (IV-L) formation can be adopted.
However, when the antireflection layer (IV) is composed of three layers, a low refractive index layer (IV-L), a high refractive index layer (IV-H), and a medium refractive index layer (IV-M), the low refractive index A high index of refraction layer (IV-H) needs to be present between the layer (IV-L) and the medium index of refraction layer (IV-M). Therefore, a medium refractive index layer (IV-M) is first formed on the hard coat layer (III) according to the method described above, and then a high refractive index layer (IV-M) is formed on the medium refractive index layer (IV-M). A low refractive index layer (IV-L) is formed on the rate layer (IV-H) and the layer to form three layers.

The antireflection layer (IV) includes a medium refractive index layer (IV-M), a high refractive index layer (IV-H), and the low refractive index layer (IV-L) from the hard coat layer (III) side.
The medium refractive index layer (IV-M) is a layer having a refractive index of 1.50 or more and less than 1.75 and a thickness of 50 to 200 nm.
The high refractive index layer (IV-H) is a layer having a refractive index of 1.60 or more and less than 2.00 and a thickness of 50 to 200 nm.
The low refractive index layer (IV-L) is a layer having a refractive index of less than 1.48 and a thickness of 50 to 200 nm.
Is preferable.

<Anti-fouling layer (V)>
An antifouling layer (V) may be laminated on the outermost surface depending on the application. When the antifouling layer is provided, it becomes easy to remove stains (human fingerprints, etc.) adhering to the antireflection film. The antifouling layer is preferably a layer constituting the outermost surface of the functional layer in order to fully exert its function.
The antifouling layer (V) can be formed by coating with a fluororesin-based antifouling agent. Examples of the fluororesin-based compound include an organosilicon compound having one or more groups selected from the group consisting of a polyfluoropolyether group, a polyfluoroalkylene group, and a polyfluoroalkyl group. The polyfluoropolyester group is a divalent group having a structure in which polyfluoroalkylene groups and etheric oxygen atoms are alternately bonded.
Specifically, as an antifouling agent, AGC's "SURECO (registered trademark) AF" series, Shin-Etsu Chemical's "SHIN-ETSU SUBELYN (registered trademark)" series, and Daikin Industries'"Optur" series. , Fluorotechnology's "Fluorosurf (registered trademark)" series, Harves'"DURASURF" series, and Neos's "Futergent" series are readily available on the market.
The thickness of the antifouling layer (V) is preferably 2 to 20 nm, more preferably 2 to 15 nm, and even more preferably 2 to 10 nm.

<Characteristics of antireflection film>
[Surface visual average reflectance]
The visual average reflectance of the surface of the antireflection film of the present invention is preferably 0.2 to 1.8%. The visual average reflectance is preferably 0.2 to 1.5%, more preferably 0.2 to 1.2%.

[Total light transmittance]
The total light transmittance of the antireflection film of the present invention is preferably 93 to 96%.
The total light transmittance is preferably 94 to 96%, more preferably 95 to 96%.

[Visual average transmittance absorption loss]
The visual average transmittance absorption loss of the antireflection film of the present invention is preferably in the range of 0.2 to 1%. The visual average transmittance absorption loss is preferably 0.2 to 0.9%, more preferably 0.2 to 0.6%.

[Haze]
The haze of the antireflection film of the present invention is preferably in the range of 0.2 to 0.5%. The haze is preferably 0.2 to 0.4%, more preferably 0.2 to 0.3%.

[Surface resistance rate]
The surface resistance value of the antireflection film of the present invention is preferably in the range of 1.0 × 10 ⁷ Ω / □ to 1.0 × 10 ¹² Ω / □. The surface resistance value is preferably 10 ⁷ to 10 ¹¹ , more preferably 10 ⁷ to 10 ⁹ .

Hereinafter, the present invention will be specifically described with reference to examples of the present invention, but the present invention is not limited to these examples. Also, not all combinations of features described in the examples are essential to the solution of the present invention.
The measurement methods used in the following examples and comparative examples are as follows.

(1) Surface Visual Average Reflectance Using a "V-650" tester manufactured by JASCO Corporation, the reflectance was measured at a scanning speed of 1000 nm / min and the reflectance at every 10 nm in the wavelength range of 380 to 780 nm. Subtract half of the measured value of double-sided reflectance to obtain the surface reflectance.
The reflectance was multiplied by the weighting factor described in JIS Z 8722 and integrated, and divided by the integrated value of the weighting factor to obtain the visual average reflectance.
The smaller the value, the better the antireflection ability.

(2) Total light transmittance Using a "V-650" tester manufactured by JASCO Corporation and an integrating sphere, a scanning speed of 1000 nm / min and a reflectance of every 10 nm in the wavelength range of 380 to 780 nm were measured, and the reflectance was measured. The total light transmittance was obtained by multiplying by the weight coefficient described in JIS Z 8722 and integrating, and dividing by the integrated value of the weight coefficient.

(3) Visual Average Transmittance Absorption Loss The difference from the total light transmittance of the laminated body without the antistatic layer was calculated.

(4) Using a haze spectrophotometer (manufactured by JASCO Corporation, "V-650"), the total light transmittance and diffuse transmittance in the wavelength range of 550 nm were measured under the condition of a scanning speed of 1000 nm / min, and the following formula was used. The haze value was calculated. The larger the haze value, the better the antireflection property. Haze value (%) = (diffusion transmittance / total light transmittance) x 100

(5) Surface resistivity An electrode was connected to the super insulation meter (manufactured by Hioki Electric Co., Ltd., "SM-8220" and "SME-8310"), and the measurement was performed in accordance with JIS K 6911.

(6) Refractive Index A coating liquid for a low refractive index layer was applied onto a glass substrate to a thickness of 100 nm and cured to form a low refractive index layer. The reflectance of the low refractive index layer was measured using a spectrophotometer (manufactured by JASCO Corporation, "V-550"), and the refractive index was calculated.
The medium refractive index layer and the high refractive index layer were also measured in the same manner.

<Example 1>
An antistatic layer (II), a hard coat layer (III), an antireflection layer (IV) and an antifouling layer (V) are placed on a polymethylmethacrylate (PMMA) substrate (I) having a thickness of 1 mm in this order. It was formed by the method of. The antistatic layer (II) was formed by using the solution 3 having a conductive particle content of 40% by weight.

[Antistatic layer (II)]
(Antistatic solution)
The components shown in Tables 1 and 2 below were mixed to prepare antistatic layer solutions 1 to 6.

A laminate in which the base material (I) is dipped in the obtained solution and then heat-treated at 60 ° C. for 8 minutes to form an antistatic layer (II) having a thickness of 50 nm on the base material (I). (II) was obtained.

[Hard coat layer (III)]
(Solution for forming hard coat layer)
A hard coat solution was prepared by mixing the following components shown in Table 3 below.

After dipping the laminate (II) into the hard coat solution, the laminate (II) was dried at 60 ° C. for 5 minutes and UV-cured to form a 2 μm-thick hard coat layer (III) on the laminate (II). Body (III) was obtained.

[Anti-reflective layer (IV)]
Using the solution for forming a low refractive index layer, the solution for forming a medium refractive index layer, and the solution for forming a high refractive index layer having the compositions shown in Tables 4 to 6 below, an antireflection film consisting of three layers is prepared by the following method. Formed.
The laminate (III) was dipped in a solution for forming a medium refractive index layer and then heat-treated at 90 ° C. for 30 minutes to form a medium refractive index layer (IV-M) having a thickness of 85 nm. -M) was obtained.
Next, after dipping the laminate (IV-M) into the solution for forming a high refractive index layer, the laminate was heat-treated at 90 ° C. for 30 minutes to form a high refractive index layer (IV-H) having a thickness of 80 nm. The body (IV-MH) was obtained.
Subsequently, the laminate (IV-MH) was dipped in a solution for forming a low refractive index layer, and then heat-treated at 100 ° C. for 120 minutes to form a low refractive index layer (IV-L) having a thickness of 100 nm. A laminate (IV) was obtained.

[Anti-fouling layer (V)]
"SHIN-ETSU SUBELYN (registered trademark)" KY-100 series manufactured by Shin-Etsu Chemical Co., Ltd. is applied to the laminate (IV) by dipping and then dried at 90 ° C. for 6 hours to form an antifouling layer (V). , Anti-reflection film was obtained.

<Example 2>
An antireflection film was produced by the same method as in Example 1 except that the antistatic layer (II) was formed by using the solution 4 having a conductive particle content of 60% by weight.
<Example 3>
An antireflection film was produced by the same method as in Example 1 except that the antistatic layer (II) was formed by using the solution 5 having a conductive particle content of 90% by weight.

<Comparative example 1>
An antireflection film was produced by the same method as in Example 1 except that the antistatic layer (II) was formed by using the solution 2 having a conductive particle content of 30% by weight.
<Comparative example 2>
An antireflection film was produced by the same method as in Example 1 except that the antistatic layer (II) was formed by using the solution 6 having a conductive particle content of 95% by weight.
The characteristics of the antireflection films obtained in Examples 1 to 2 and Comparative Examples 1 and 2 are shown in Table 9 below. As is clear from the results of Comparative Example 1, if the content of the conductive particles in the antistatic layer (II) is small, a good surface resistivity cannot be obtained. Further, if the content of the conductive particles in the antistatic layer (II) is too large as in Comparative Example 2, the visual average transmittance absorption loss becomes large.

<Example 4>
The antistatic layer (II) was formed by using the solution 1 having a conductive particle content of 80% by weight, and the antistatic layer (II) was made 30 nm in thickness by the same method as in Example 1. The film was manufactured.
<Example 5>
The antistatic layer (II) was formed by using the solution 1 having a conductive particle content of 80% by weight, and the antistatic layer (II) was made 60 nm in thickness by the same method as in Example 1. The film was manufactured.

<Example 6>
The antistatic layer (II) was formed by using the solution 1 having a conductive particle content of 80% by weight, and the antistatic layer (II) was made 90 nm in thickness by the same method as in Example 1. The film was manufactured.
<Example 7>
The antistatic layer (II) was formed by using the solution 1 having a conductive particle content of 80% by weight, and the antistatic layer (II) was made 120 nm in thickness by the same method as in Example 1 to prevent reflection. The film was manufactured.

<Comparative example 3>
The antistatic layer (II) was formed by using the solution 1 having a conductive particle content of 80% by weight, and the antistatic layer (II) was made 20 nm in thickness by the same method as in Example 1. The film was manufactured.
<Comparative example 4>
The antistatic layer (II) was formed by using the solution 1 having a conductive particle content of 80% by weight, and the antistatic layer (II) was made to have a thickness of 150 nm in the same manner as in Example 1. The film was manufactured.
The characteristics of the antireflection films obtained in Examples 4 to 7 and Comparative Examples 3 to 4 are shown in Table 9 below. As is clear from Comparative Example 3, when the antistatic layer (II) is thin, the surface resistivity is high and good antistatic properties cannot be obtained. Further, if the antistatic layer (II) is too thick, the visual average transmittance absorption loss becomes large.

<Example 8>
Antistatic layer (II) was formed using solution 1 having a conductive particle content of 80% by weight, and antireflection was performed in the same manner as in Example 1 except that the thickness of the hard coat layer (III) was 1 μm. The film was manufactured.
<Example 9>
The antistatic layer (II) was formed using the solution 1 having a conductive particle content of 80% by weight, and the thickness of the hard coat layer (III) was set to 2 μm, but the same method as in Example 1 was used to prevent reflection. The film was manufactured.
<Example 10>
The antistatic layer (II) was formed using the solution 1 having a conductive particle content of 80% by weight, and the thickness of the hard coat layer (III) was set to 3 μm, but the same method as in Example 1 was used to prevent reflection. The film was manufactured.

<Comparative example 5>
The antistatic layer (II) was formed by using the solution 1 having a conductive particle content of 80% by weight, and the thickness of the hard coat layer (III) was set to 0.5 μm in the same manner as in Example 1. Manufactured anti-reflection film.
<Comparative Example 6>
The antistatic layer (II) was formed by using the solution 1 having a conductive particle content of 80% by weight, and the thickness of the hard coat layer (III) was 4 μm, but the same method as in Example 1 was used to prevent reflection. The film was manufactured.

<Example 11>
An antireflection film was produced in the same manner as in Example 1 except that the thickness of the hard coat layer (III) was set to 1 μm.
<Example 12>
The antistatic layer (II) was formed by using the solution 5 having a conductive particle content of 90% by weight.
An antireflection film was produced in the same manner as in Example 1 except that the thickness of the antistatic layer (II) was 120 nm and the thickness of the hard coat layer (III) was 3 μm.
The characteristics of the antireflection films obtained in Examples 8 to 12 and Comparative Examples 5 to 6 are shown in Table 9 below.

<Example 13>
An antistatic layer (II), a hard coat layer (III), an antireflection layer (IV) and an antifouling layer (V) are added to a 1 mm thick polymethylmethacrylate (PMMA) substrate (I) in this order. An antireflection film was manufactured by the above method.
[Antistatic layer (II)]
The antistatic layer (II) was formed by using the solution 1 having a conductive particle content of 80% by weight.
The antistatic layer (II) was formed by the same method as in Example 1 except that the thickness of the antistatic layer (II) was 40 nm.
[Hard coat layer (III)]
The hard coat layer (III) was formed in the same manner as in Example 1 except that the thickness was 1.5 μm.
[Anti-reflective layer (IV)]
The antireflection layer (IV) was formed by the same method as in Example 1 except that only the low refractive index layer (IV-L) was used.

<Comparative Example 7>
(Antistatic layer (II) and hard coat layer (III))
The antistatic layer (II) was not formed, and the conductive particles (ATO sol, particle size: 8 nm, refractive index: 1.6, solid content: 1.5 weight) used in the examples were contained in the hard coat layer (III). %, Dispersion solvent: alcohol) to form a hard coat layer (III) so that the proportion of conductive particles was 6.8% by weight.
[Anti-reflective layer (IV)]
The antireflection layer (IV) was formed by the same method as in Example 1 except that only the low refractive index layer (IV-L) was used.
[Anti-fouling layer (V)]
The antifouling layer (V) was formed in the same manner as in Example 1.

The characteristics of the antireflection film obtained in Example 13 and Comparative Example 7 are shown in Table 10 below.
When conductive particles are contained in the hard coat layer (III) having a large film thickness (5 μm) as in Comparative Example 7, the content of the conductive particles used increases, and the total light transmittance and the visual average are increased. Optical characteristics such as transmittance absorption loss and haze deteriorate.
The amount of conductive particles per unit area of Example 13 was 80% by weight × 40 nm, whereas the amount of conductive particles per unit area of Comparative Example 7 was 6.8% by weight × 5000 nm (5 μm). Yes, the amount of conductive particles per unit area of Comparative Example 7 is 10 times or more that of Example 13.

The antireflection film of the present invention can be used for the front panel of an optical display device such as a CRT display, a liquid crystal display (LCD), or a plasma display (PDP).

1 Base material (I)
2 Antistatic layer (II)
3 Hard coat layer (III)
4 Antireflection layer (IV)
4 (M) Medium refractive index layer (IV-M)
4 (H) High refractive index layer (IV-H)
4 (L) Low refractive index layer (IV-L)
5 Antifouling layer (V)

Claims (10)

An antireflection film comprising a base material (I), an antistatic layer (II), a hard coat layer (III) and an antireflection layer (IV) in this order.
(1) The antistatic layer (II) is a layer having a thickness of 10 to 200 nm containing 40 to 90% by weight of conductive particles.
(2) The hard coat layer (III) is a layer having a thickness of 1 to 3 μm containing a resin component (A) obtained by curing a urethane acrylate (A1) having a trifunctionality or less and a urethane acrylate (A2) having a trifunctionality or higher. And
(3) The antireflection layer (IV) includes a low refractive index layer (IV-L).
The antireflection film. The antireflection film according to claim 1, wherein the base material (I) is formed of at least one resin selected from the group consisting of an acrylic resin, a polycarbonate resin, a polyethylene terephthalate resin, and a triacetyl cellulose resin. The antireflection film according to claim 1, wherein the antistatic layer (II) contains a resin component (a) obtained by curing a tetrafunctional or higher functional urethane acrylate (a2). The antistatic layer (II) is at least one conductive particle selected from the group consisting of indium oxide-tin oxide (ITO), antimony-doped tin oxide (ATO), phosphorus-doped tin oxide (PTO), and fluorine-doped tin oxide (FTO). The antireflection film according to claim 1, which contains. The hard coat layer (III) is composed of 100 parts by weight of the resin component (A).
The following general formula (1) of 1 to 30 parts by weight;
R _{n −} Si (OR ₁ ) _4-n (1)
In the formula, R is an alkyl or alkenyl group, R ₁ is an alkyl group, an alkoxyalkyl group, an acyloxy group or a halogen atom, and n is a number of 1 or 2.
The compound represented by (B) or its hydrolyzate (B),
10 to 80 parts by weight of silica particles (C) having a particle size of 5 to 500 nm and a refractive index in the range of 1.44 to 1.5.
Formed from 0.1 to 30 parts by weight of the metal chelating compound (D),
The antireflection film according to claim 1. The antireflection layer (IV) includes a medium refractive index layer (IV-M), a high refractive index layer (IV-H), and the low refractive index layer (IV-L) from the hard coat layer (III) side.
The medium refractive index layer (IV-M) is a layer having a refractive index of 1.50 or more and less than 1.75 and a thickness of 50 to 200 nm.
The high refractive index layer (IV-H) is a layer having a refractive index of 1.60 or more and less than 2.00 and a thickness of 50 to 200 nm.
The low refractive index layer (IV-L) is a layer having a refractive index of less than 1.48 and a thickness of 50 to 200 nm.
The antireflection film according to claim 1. The antireflection film according to any one of claims 1 to 6, wherein the surface visual average reflectance is in the range of 0.2 to 1.8%. The antireflection film according to any one of claims 1 to 6, wherein the total light transmittance is in the range of 93 to 96%. The antireflection film according to any one of claims 1 to 6, wherein the visual average transmittance absorption loss is in the range of 0.2 to 1%. The antireflection film according to any one of claims 1 to 6, wherein the surface resistivity is in the range of 1.0 × 10 ⁷ Ω / □ to 1.0 × 10 ¹² Ω / □.