JP2003145689A - Laminated film, image display protective film, and image display device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film excellent in antistatic properties, high transparency or the like and especially suitably used as an antireflection film by forming a high refractive index layer highly controlled in composition and structure in an antireflection film wherein a thin film having a low refractive index and a thin film having a high refractive index are alternately laminated. SOLUTION: In the laminated film wherein a hard coat layer (b) containing a polyfunctional (meth)acrylate compound, a conductive layer (c) containing tin-containing indium oxide particles and a resin layer (d) containing a fluorine- containing copolymer are laminated on at least the single surface of a substrate film (a), the conductive layer (c) comprises a binder component (A) containing the polyfunctional (meth)acrylate compound, tin-containing indium oxide particles (B) with a mean primary particle size of 0.5 μm or less and a photopolymerization initiator, and a weight mixing ratio [(A)/(B)] of the binder component (A) and the indium oxide particles (B) is 10/90-30/70.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film, which is particularly excellent in transparency and antistatic property, for an antireflection film provided on the surface of a display screen or a polarizing plate thereof.

[0002]

2. Description of the Related Art Conventionally, in a display device for a display such as a television or a personal computer monitor, external light such as sunlight or a fluorescent lamp is reflected on the surface to reflect the outside scenery, so that the visibility of the displayed image is deteriorated. There was a problem. In order to solve this problem, a method has been performed in which thin films having a low refractive index and a high refractive index are alternately laminated to prevent light reflection. Furthermore, in this structure, a method of imparting antistatic property by forming a transparent metal thin film as a high refractive index layer is known.

[0003]

However, in a method for preventing light reflection by alternately laminating thin films having a low refractive index and a high refractive index, a conventional method for forming a transparent metal thin film is as follows. A metal oxide such as tin-containing indium oxide (ITO) by a vapor phase method such as vacuum deposition, sputtering, or ion plating, a sol-gel method, or a thermal decomposition method (for example, Fairness 0
6-085001 and Japanese Patent Publication No. 07-046570) are known.

The vacuum vapor deposition method, sputtering method and ion plating method are the most widely used film forming methods in the past, and when films are formed using these methods, they have low surface resistance and high transparency. It is possible to obtain a high refractive index thin film of However, when the film is formed by the above method, there are drawbacks that the optimum condition range for the film formation is narrow and the equipment cost of the film forming apparatus is high. In addition, the method of forming a film by the sol-gel method and the thermal decomposition method has a problem that the material of the base material is restricted because it needs to be baked at a high temperature of 400 ° C. or higher.

[0005]

The present invention employs the following means in order to solve such problems.

Conductive particles such as ITO having a specific particle size and a specific amount are dispersed in a specific binder solution having excellent transparency such as acrylic resin, and a coating material having a highly controlled agglomeration structure is applied to a substrate. An antireflection laminated film having low surface resistance and high transparency is formed by a coating method of forming a high refractive index thin film by drying at a temperature of about 200 ° C. or lower and photocuring.

That is, in the laminated film of the present invention, a hard coat layer (b) containing a polyfunctional (meth) acrylate compound and a conductive layer containing tin-containing indium oxide particles (a) on at least one surface of the base film (a). c) is a laminated film obtained by laminating a resin layer (d) containing a fluorine-containing copolymer, and the conductive layer (c) contains a binder component (A) containing a polyfunctional (meth) acrylate compound. ), A tin-containing indium oxide particles (B) having an average primary particle diameter of 0.5 μm or less, and a photopolymerization initiator, and a weight mixing ratio [(A) of the binder component (A) and the indium oxide particles (B)]. / (B)] is 10/90 to 30/70, and the image display protective film of the present invention is characterized by comprising the above laminated film. The image display device of the present invention is characterized in that the image protective film is attached to the image surface and / or the surface of the front plate thereof via an adhesive layer or an adhesive layer. Thus, the above object is achieved.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The laminated film of the present invention contains a hard coat layer (b) containing a polyfunctional (meth) acrylate compound and tin-containing indium oxide particles on at least one surface of a base film (a). It is formed by laminating a conductive layer (c) and a resin layer (d) containing a fluorine-containing copolymer.

The substrate film (a) in the present invention preferably has a high light transmittance and a low haze value for use as a display material. For example, 400 to 800n
The light transmittance at m is preferably 40% or more, more preferably 60% or more, and the haze value is preferably 5 or more.
% Or less, more preferably 3% or less. Satisfying these conditions is preferable because it provides excellent clarity when used as a display member. Further, in view of exerting such an effect, the upper limit value of the light transmittance is about 99.5%,
Further, the lower limit of the haze value is a practical range up to about 0.1%.

The resin material forming the base film (a) is not particularly limited and can be appropriately selected and used from the resin materials used for the known plastic base film (a). As a resin material for such a base film (a), for example, a polyester-based material,
Polyethylene type, polypropylene type, diacetate type,
Examples thereof include triacetate-based, polystyrene-based, polycarbonate-based, polymethylpentene-based, polysulfone-based, polyether ethyl ketone-based, polyimide-based, fluorine-based, nylon-based and acrylate-based resins.

Among these resins, polyester resins such as polyethylene terephthalate, acetate resins such as triacetyl cellulose, and acrylate resins such as polymethylmethacrylate are excellent in transparency and have no optical anisotropy. It is preferably used from the viewpoints of optical properties and strength, and also has excellent uniformity. In particular, the base film (a) made of a polyester resin is particularly preferable from the viewpoint of optical characteristics and mechanical characteristics.

As the polyester resin, polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, polyethylene-
α, β-bis (2-chlorophenoxy) ethane-4,
4'-dicarboxylate and the like. Moreover, 20 mol% or less of other dicarboxylic acid components and diol components may be copolymerized with these polyesters.
Among them, polyethylene terephthalate is particularly preferable when comprehensively judging the quality and economy.

Even if only one of these constituent resin components is used,
Two or more kinds may be used in combination and either may be used.

The thickness of the base film (a) used in the present invention is not particularly limited, but from the viewpoint of mechanical strength and thermal conductivity, it is usually 5 to 800 μm, preferably 10 to 250 μm. is there. Alternatively, two or more films may be laminated by a known method.

The base film (a) may be subjected to various surface treatments (for example, before forming the hard coat layer (b)).
Corona discharge treatment, glow discharge treatment, flame treatment, etching treatment, roughening treatment, etc.) may be applied. Alternatively, the hard coat layer (b) may be provided after performing a surface coating for promoting adhesion (for example, a polyurethane type, polyester type, polyester acrylate type, polyurethane acrylate type, polyepoxy acrylate type, titanate type compound, etc.). Good. In particular, undercoating a composition comprising a copolymer obtained by grafting an acrylic compound to a hydrophilic group-containing polyester resin and a cross-linking agent has improved adhesiveness and improved durability such as heat resistance and water resistance. Since it is excellent, it is preferable as the base film (a).

The hard coat layer (b) in the present invention comprises
It is essential that it is formed on the base film (a) and contains a (meth) acrylate compound. The (meth) acrylate compound is radically polymerized by irradiation with actinic rays to improve the solvent resistance and hardness of the formed film. Specifically, methyl (meth) acrylate, n-butyl (meth)
Monofunctional acrylate compounds such as acrylate, polyester (meth) acrylate, lauryl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and the like can be mentioned. Further, a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in the molecule improves solvent resistance and the like, and is therefore particularly preferable in the present invention. Specific examples of the polyfunctional (meth) acrylate include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta. Examples thereof include (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and trimethylolpropane tri (meth) acrylate. These monomers may be used alone or in combination of two or more.

The thickness of the hard coat layer (b) is appropriately selected depending on the application, but is usually 1 μm to 50 μm, preferably 2 μm to 30 μm. When the thickness of the hard coat layer (b) is within this range, an appropriate surface hardness is obtained, scratches are less likely to occur, and the cured film is less likely to become brittle.
It is preferable that the hard coat layer (b) is less likely to be cracked when the surface-hardened film is bent.

It is essential that the conductive layer (c) in the present invention is formed on the hard coat layer (b) and contains tin-containing indium oxide (ITO) particles (B) and a binder component (A).

In the present invention, the ITO particles may be commercially available products or may be produced by a known method. For example, as a manufacturing method, there is a method in which an acidic solution in which tin and indium chlorides are dissolved is neutralized with an alkali to coprecipitate a tin / indium hydroxide, and the coprecipitate is baked. In addition, in the ITO particles, the content of Sn with respect to (In + Sn) is 1 to 15 mol%, preferably 3 to 10%.
Those having a range of are preferable because they have high conductivity.

Regarding the ITO particles constituting the conductivity,
Average primary particle diameter (sphere equivalent diameter measured by BET method)
Is 0.5 μm or less. When the average particle diameter exceeds this range, the transparency of the coating film (conductive layer (c)) formed is reduced. Preferably, 0.
001-0.3 μm, more preferably 0.005-0.
A particle size of 2 μm is used. The average particle size is
Within this range, the inorganic particles are less likely to aggregate, so that the haze value of the formed film (conductive layer (c)) can be suppressed from increasing.
In either case, the desired transparency is easily obtained, which is preferable.

As the binder component (A) constituting the conductive layer (c), a (meth) acrylate compound is used.
A (meth) acrylate compound is preferable because it is radically polymerized by irradiation with an actinic ray to improve solvent resistance and hardness of a formed film, and further, a (meth) acryloyl group has two or more polyfunctional (meth) acryloyl groups in the molecule. ) Acrylate compounds are particularly preferred in the present invention because they improve solvent resistance and the like. For example, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate,
Trifunctional (meth) acrylates such as ethylene-modified trimethylolpropane tri (meth) acrylate, tris- (2-hydroxyethyl) -isocyanuric acid ester tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( Examples thereof include tetra- or higher functional (meth) acrylates such as (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

The binder component (A) constituting the conductive layer (c) is a (meth) acrylate compound having a carboxyl group or an acidic functional group such as a phosphoric acid group or a sulfonic acid group in order to improve the dispersibility of ITO. Can be used. Specifically, as the acid functional group-containing monomer, acrylic acid,
Unsaturated carboxylic acids such as methacrylic acid, crotonic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, mono (2- (meth) acryloyloxyethyl) acid phosphate, diphenyl-2- (meth) acryloyl Examples thereof include phosphoric acid (meth) acrylic acid esters such as oxyethyl phosphate and 2-sulfoester (meth) acrylates. In addition, a (meth) acrylate compound having a polar bond such as an amide bond, a urethane bond, or an ether bond can be used. Furthermore, a resin having a urethane bond, such as a urethane (meth) acrylate oligomer, is particularly preferable because it has a high polarity and improves the dispersibility of the conductive inorganic particles.

When forming the hard coat layer (b) and the conductive layer (c) in the present invention, an initiator may be used to accelerate the curing of the applied binder component. As the initiator, the applied binder component is one that initiates or accelerates polymerization and / or crosslinking reaction by radical reaction, anion reaction, cation reaction, etc., and various conventionally known photopolymerization initiators can be used. is there. Specifically, sulfides such as sodium methyl dithiocarbamate sulfide, diphenyl monosulfide, dibenzothiazoyl monosulfide and disulfide; thioxanthone, 2-ethylthioxanthone, 2-
Thioxanthone derivatives such as chlorothioxanthone and 2,4-diethylthioxanthone; azo compounds such as hydrazone and azobisisobutyronitrile; diazo compounds such as benzenediazonium salts; benzoin, benzoin methyl ether, benzoin ethyl ether, benzophenone, dimethylaminobenzophenone , Michler's ketone,
Benzyl anthraquinone, t-butyl anthraquinone,
Aromatic carbonyl compounds such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-aminoanthraquinone and 2-chloroanthraquinone; methyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate,
Dialkylaminobenzoic acid esters such as butyl D-dimethylaminobenzoate and isopropyl p-diethylaminobenzoate; peroxides such as benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, cumene hydroperoxide; 9 Acridine derivatives such as -phenylacridine, 9-p-methoxyphenylacridine, 9-acetylaminoacridine and benzacridine; 9,10-dimethylbenzphenazine, 9-
Methylbenzphenazine, phenazine derivatives such as 10-methoxybenzphenazine; quinoxaline derivatives such as 6,4 ′, 4 ″ -trimethoxy-2,3-diphenylquinoxaline; 2,4,5-triphenylimidazoyl dimer, 2 -Nitrofluorene, 2,4,6-triphenylpyrylium boron tetrafluoride salt, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 3,3'-
Carbonyl biscoumarin, thiomichler ketone, 2,
4,6-Trimethylbenzoyldiphenylphosphine oxide, oligo (2-hydroxy-2-methyl-1-
(4- (1-methylvinyl) phenyl) propanone, 2
-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone and the like can be mentioned.

Further, in order to prevent a decrease in sensitivity due to oxygen inhibition, an amine compound may coexist with the photopolymerization initiator. Such an amine compound is not particularly limited as long as it is a non-volatile compound such as an aliphatic amine compound or an aromatic amine compound. For example, triethanolamine, methyldiethanolamine and the like are suitable.

In the present invention, the mixing ratio of the constituent components of the conductive layer (c) is such that the weight ratio [(A) / (B)] of the binder component (A) and the ITO particles (B) is from 10/90 to 3.
Must be 0/70, preferably 15/8
5 to 25/75. When the amount of ITO particles (B) is less than the above range, the resulting film has poor transparency even if it has sufficient transparency. On the contrary, when the amount is too large, various physical properties of the resulting film,
It is not preferable because the chemical strength becomes worse. The amount of the photopolymerization initiator is 100 parts by weight of the binder component (A),
Usually, it is added preferably in the range of 0.1 to 20 parts by weight, more preferably 1.0 to 15.0 parts by weight. Within such a preferable range, photopolymerization proceeds properly, and it is not necessary to perform light irradiation for a long time in order to satisfy hardness and scratch resistance, and it is hard to be uncured, and a coating film added in a large amount It becomes difficult for functional deterioration such as conductivity, abrasion resistance, and weather resistance to occur.

The conductive layer (c) of the present invention comprises the above-described binder component (A), ITO particles (B) and photopolymerization initiator as essential components, and if necessary, for example, polymerization. Inhibitors, curing catalysts, antioxidants, dispersants,
You may contain various additives, such as a leveling agent and a silane coupling agent.

In the present invention, a conductive polymer such as polypyrrole and polyaniline, and an organometallic compound such as a metal alcoholate and a chelate compound are further added to the constituent components of the conductive layer (c) for the purpose of imparting conductivity. be able to. Further, for the purpose of improving the surface hardness, the constituent components of the conductive layer (c) are dispersed in the form of colloidal inorganic particles such as alkyl silicates and hydrolysates thereof, colloidal silica, dry silica, wet silica, titanium oxide and the like. The silica fine particles and the like may be further contained.

In order to impart a desired level of antistatic property to the conductive layer (c) of the present invention, the surface resistance value of the conductive layer (c) is preferably 1011 Ω / □ or less,
More preferably, it is 107Ω / □ or more and 1010Ω / □ or less.

The conductive layer (c) in the present invention has a sharpness,
From the viewpoint of transparency, the layer has a total light transmittance of preferably 40% or more, more preferably 50% or more.

The thickness of the conductive layer (c) of the present invention is 0.01 to.
The thickness is preferably 1.0 μm, more preferably 0.
03-0.2 μm, more preferably 0.06-0.12
μm.

The resin layer (d) in the present invention is formed on the conductive layer (c), and it is essential that the resin layer (d) contains a fluorine-containing copolymer, and the fluorine-containing copolymer mainly contains a vinyl ether structure in its main chain. It is composed of a system copolymer. The fluorine-containing copolymer preferably has a fluorine content of 30% by weight or more and a fluorine-containing olefin chain having a polystyrene-reduced number average molecular weight of 5000 or more.

This fluorine-containing copolymer is obtained by polymerizing a curable composition containing a fluorine-containing compound and a vinyl ether-containing compound, and is preferably a fluorine-containing olefin compound or this fluorine-containing olefin compound. It can be obtained by polymerizing a curable composition comprising a vinyl ether-containing compound copolymerizable with, an azo group-containing polysiloxane compound, and a reactive emulsifier, which is optionally blended.

The above-mentioned fluorine-containing olefin compound constituting the fluorine-containing copolymer is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Is, for example, (1)
Tetrafluoroethylene, hexafluoropropylene, 3,
Fluoroolefins such as 3,3-trifluoropropylene; (2) Alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers;
(3) Perfluoro (alkyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether) and the like; (4) perfluoro (propoxypropyl vinyl ether) And other perfluoro (alkoxyalkyl vinyl ethers); and the like. These compounds can be used alone or in combination of two or more kinds. Of the above, hexafluoropropylene, perfluoroalkyl perfluorovinyl ether or perfluoroalkoxyalkyl perfluorovinyl ether is particularly preferable, and it is more preferable to use them in combination.

Specific examples of the vinyl ether-containing compound constituting the fluorine-containing copolymer and copolymerizable with the above-mentioned fluorine-containing olefin compound include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether and n-. Butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n
Examples thereof include alkyl vinyl ethers such as hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether, or cycloalkyl vinyl ethers.

In addition to the above-mentioned monomer components constituting the fluorine-containing copolymer, if necessary, another monomer compound copolymerizable with the fluorine-containing olefin compound may be copolymerized. it can. For example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl stearate, and other carboxylic acid vinyl esters; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl. (Meth) acrylate, isobutyl (meth) acrylate,
(Meth) acrylic acid esters such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) acrylate; (4) (meth) acrylic acid, croton Examples thereof include carboxyl group-containing monomer compounds such as acids, maleic acid, fumaric acid, and itaconic acid.

The vinyl ether-containing compound and the other monomer compounds constituting the fluorine-containing copolymer preferably have a functional group capable of reacting with the crosslinkable compound. The functional group is preferably a hydroxyl group or an epoxy group, and may have both of them.

Examples of the vinyl ether-containing compound having a hydroxyl group include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether and 2
-Hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-
Examples thereof include hydroxyl group-containing vinyl ethers such as hydroxyhexyl vinyl ether. Examples of the vinyl ether-containing compound containing an epoxy group include vinyl glycidyl ether.

Examples of the other monomer compound having a hydroxyl group include hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether and glycerol monoallyl ether; allyl alcohol; hydroxyethyl. (Meth) acrylic acid ester; and others. Also,
Examples of the other monomer compound having an epoxy group include allyl glycidyl ether, glycidyl (meth) acrylate, glycidyl crotonic acid, methyl glycidyl maleate, and the like.

These monomer compounds forming the fluorine-containing copolymer may be used alone or in combination of two or more.

Of these monomer compounds, alkyl vinyl ethers are used from the viewpoint of increasing the yield when a curable composition containing a fluorine-containing compound is polymerized and cured.
Cycloalkyl vinyl ethers or carboxylic acid vinyl esters are preferably used. On the other hand, from the viewpoint of increasing the content of fluorine to be copolymerized, for example, a low molecular weight unit weight of methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, etc. It is preferable to use the body. Furthermore, the hardness of the thin film after curing the curable composition is increased,
In order to lower the refractive index, it is effective to use a branched monomer such as isopropyl vinyl ether, tert-butyl vinyl ether and vinyl pivalate.

The azo group-containing polysiloxane compound constituting the fluorine-containing copolymer is a compound having a polysiloxane segment and an azo group. As this azo group-containing polysiloxane compound, azo group-containing polydimethylsiloxane can be used.

The curable composition used for forming the fluorine-containing copolymer preferably contains a reactive emulsifier as one component. By using this reactive emulsifier component, the fluorine-containing copolymer contained in the coating liquid can be coated with good coatability and leveling properties. As the reactive emulsifier, it is particularly preferable to use a nonionic reactive emulsifier.

In the fluorine-containing copolymer constituting the resin layer (d), the structural unit derived from the fluorine-containing olefin compound component is preferably 20 to 70 mol%, more preferably 25 to 65 mol%, and further preferably. It is 30 to 60 mol%. If the ratio of the structural units derived from the fluorine-containing olefin compound component is within such a preferable range,
Since the fluorine content in the obtained fluorinated copolymer is not too small, the obtained resin layer (d) has an appropriate refractive index, and the uniformity of the coating solution is not deteriorated. It is preferable because a uniform coating film can be easily formed, and transparency and adhesion to a substrate can be sufficiently obtained.

In the fluorine-containing copolymer, the structural unit derived from the vinyl ether structure-containing compound component is 10 to 7
0 mol% is preferable, 15-65 mol% is more preferable, and 30-60 mol% is further preferable. When the ratio of the structural unit derived from the vinyl ether structure-containing compound component is within such a preferable range, the uniformity of the coating solution is good and the formation of a uniform coating film is facilitated, and the optical characteristics of transparency and low reflectance Is preferable, which is preferable.

When a curable resin composition obtained by using a monomer having a reactive functional group such as a hydroxyl group or an epoxy group as the vinyl ether structure-containing compound component is used as a coating agent, It is preferable because the strength of the cured film can be improved. The proportion of the monomer containing a hydroxyl group or an epoxy group in all the monomers is preferably 20 mol% or less, more preferably 1 to 20 mol%, further preferably 3 to 15 mol%. When this ratio is 20 mol% or less, the obtained resin layer (d) has favorable optical characteristics, and the cured film is unlikely to become brittle, which is preferable.

In the fluorine-containing copolymer, the ratio of the structural units derived from the polysiloxane compound component is such that the general formula --Si (R1) (R2) O-- (wherein R1 and R2 are the same or different). Often,
A hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group is shown. ) The polysiloxane segment represented by
1 to 20 mol%, more preferably 0.1 to 15 mol%,
The ratio is more preferably 0.1 to 10 mol%. When the proportion of the polysiloxane segment represented by the above general formula is within such a preferable range, the resin layer (d) obtained has excellent transparency and cissing and the like are less likely to occur during coating.

In the fluorine-containing copolymer, the proportion of the constituent units derived from the reactive emulsifier component is usually preferably 10 mol% or less, more preferably 0.1 to 5 mol%.
Is. When this ratio is 10 mol% or less, the obtained resin layer (d) does not have tackiness and is easy to handle,
Further, the moisture resistance of the coating agent is good, which is preferable.

The resin layer (d) in the present invention preferably further contains a crosslinkable compound, which is effective for imparting desired curability and improving curing characteristics.

Examples of the crosslinkable compound include various amino compounds, pentaerythritol, polyphenol,
Various hydroxyl group-containing compounds such as glycol and the like can be mentioned. The amino compound used as the crosslinkable compound has two or more in total of one or both of an amino group capable of reacting with a hydroxyl group or an epoxy group present in a fluorine compound, for example, a hydroxyalkylamino group and an alkoxyalkylamino group. The compound to be contained, and specific examples thereof include a melamine compound, a urea compound, a benzoguanamine compound, a glycoluril compound and the like. The melamine-based compound is generally known as a compound having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples thereof include melamine, alkylated melamine, methylolmelamine, and alkoxylated methylmelamine. Yes, but 1
Those having a total of two or more of either one or both of a methylol group and an alkoxylated methyl group in the molecule are preferable. Specifically, a methylolated melamine obtained by reacting melamine and formaldehyde under a basic condition, an alkoxylated methylmelamine, or a derivative thereof is preferable, and particularly, a curable resin composition having good storage stability can be obtained. The alkoxylated methyl melamine is preferable in that it can be obtained and good reactivity can be obtained. There is no particular limitation on the methylolated melamine and the alkoxylated methylmelamine used as the crosslinkable compound, and they can be obtained, for example, by the method described in the literature “Plastic Materials Course [8] Urea Melamine Resin” (Nikkan Kogyo Shimbun). It is also possible to use various resinous materials. In addition to urea, examples of the urea compound include polymethylolated urea and its derivatives such as alkoxylated methylurea, methylolated urone having an uron ring, and alkoxylated methyluron. Also, with respect to compounds such as urea derivatives, various resinous substances described in the above-mentioned documents can be used.

The amount of the crosslinkable compound used is preferably 70 parts by weight or less, more preferably 3 to 50 parts by weight, further preferably 5 to 30 parts by weight, based on 100 parts by weight of the fluorine-containing copolymer. It is a department. When the amount of the crosslinkable compound used is within such a preferable range, the durability of the thin film formed by coating and curing can be sufficiently obtained, and gelation can be avoided in the reaction with the fluorine-containing copolymer. ,
Moreover, the cured film has a low refractive index and the cured product does not become brittle, which is preferable.

The resin layer (d) in the present invention is formed by applying a curable composition containing a fluorine-containing copolymer and a crosslinkable compound on the conductive layer (c), followed by drying and curing. Preferably. The heating temperature for causing the curing reaction between the fluorine-containing copolymer and the crosslinkable compound in the drying step after coating is preferably in the range of 30 to 150 ° C, more preferably in the range of 50 to 120 ° C. is there. If the heating temperature is within the preferable range, the reaction proceeds properly, and a crosslinking reaction due to the reaction between the methylol group and the alkoxylated methyl groups in the crosslinkable compound does not occur in addition to the intended reaction, It is preferable because no gel is formed.

The curable composition for forming the resin layer (d) in the present invention further comprises an alkyl silicate, its hydrolyzate and colloidal silica for the purpose of improving the surface hardness of the resin layer (d). Inorganic particles such as dry silica, wet silica, and titanium oxide, and colloidally dispersed silica fine particles are preferably contained, and more preferably, colloidally dispersed silica fine particles are contained.

The silica fine particles having an average primary particle diameter (sphere equivalent diameter: BET method) of 0.001 to 0.2 μm can generally be preferably used, but more preferably 0.
Particles having a particle diameter of 005 to 0.1 μm, more preferably 0.006 to 0.07 μm are used. When the average particle diameter is within this range, the transparency of the resulting coating film (resin layer (d)) is good, and the surface hardness is easily improved, which is preferable. The shape of the silica fine particles is preferably spherical or beaded, but is not limited to this.

The content of the silica fine particles is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 1 part by weight of the total amount of the organic resin components such as the fluorine-containing copolymer. -10 times by weight, more preferably,
It is 0.1 to 2 parts by weight.

In order for the surface of the resin layer (d) of the laminated film of the present invention to have low reflectivity, the product of the refractive index and the thickness of the resin layer (d) corresponds to the wavelength of the target light ray (usually visible light ray). It is preferably set to 1/4. Therefore, in the resin layer (d), four times the product of the thickness d of the resin layer (d) and the refractive index n of the resin layer (d) is preferably in the range of 380 to 780 nm. That is, the relationship between the refractive index n and the thickness d of the resin layer (d) is preferably within the range that satisfies the following formula (1).

Nd = λ / 4 Equation (1) (where λ is the wavelength range of visible light, usually 380 nm
The range is ≦ λ ≦ 780 nm. Further, in order for the surface of the resin layer (d) of the laminated film of the present invention to have low reflectivity, the refractive index of the resin layer (d) is smaller than that of the conductive layer (c), that is, the resin Layer (d)
The refractive index ratio of the resin layer (d) / conductive layer (c) is preferably less than 1.0, and more preferably 0.6 to 0.95. Further, the resin layer (d)
The refractive index of is preferably 1.47 or less, and more preferably 1.35 to 1.45. When the refractive index of the resin layer (d) is within this range, the coatability of the coating liquid when forming the resin layer (d) is sufficient, and the low reflectivity is sufficient, which is preferable. This refractive index is measured based on Japanese Industrial Standard JIS K7105 using an Abbe refractometer.

In order to impart low reflectivity to the laminated film of the present invention, the preferable thickness range of the resin layer (d) is 0.
01-1.0 μm, more preferably 0.07-
It is 0.12 μm.

The laminated film of the present invention contains a hard coat layer (b) containing the polyfunctional (meth) acrylate compound of the base film (a), a conductive layer (c) containing tin-containing indium oxide particles, and An adhesive layer or an adhesive layer can be provided on the surface opposite to the surface having the resin layer (d) containing the fluorocopolymer. 2 as the adhesive layer or the adhesive layer
There is no particular limitation as long as it adheres two objects by their adhesive action. As the pressure-sensitive adhesive or the adhesive forming the pressure-sensitive adhesive layer or the adhesive layer, a rubber type, a vinyl polymerization type, a condensation polymerization type, a thermosetting resin type or a silicone type can be used. Among them, as a rubber-based adhesive or adhesive, a butadiene-styrene copolymer system (SB
R), butadiene-acrylonitrile copolymer system (NB
R), chloroprene polymer system, isobutylene-isoprene copolymer system (butyl rubber) and the like. Examples of the vinyl polymerization type pressure-sensitive adhesive or adhesive include acrylic resin type, styrene resin type, vinyl acetate-ethylene copolymer system, vinyl chloride-vinyl acetate copolymer system and the like. Examples of the condensation polymerization type pressure-sensitive adhesive or adhesive include polyester resin type. Examples of thermosetting resin-based adhesives or adhesives include epoxy resin-based, urethane resin-based or formalin resin-based adhesives. These resins may be used alone or in combination of two or more.

Further, the pressure-sensitive adhesive or the adhesive may be used in either a solvent type or a solventless type. The pressure-sensitive adhesive layer or the adhesive is formed by using the above-mentioned pressure-sensitive adhesive or adhesive and using a commonly used technique such as coating. Further, the adhesive or the adhesive may contain a colorant. This is easily achieved by using a pressure-sensitive adhesive or adhesive mixed with a colorant such as a pigment or a dye. When it contains a colorant, the light transmittance of the laminated film at 550 nm is preferably in the range of 40 to 80%.

Next, the method for producing the laminated film of the present invention will be described.

The laminated film of the present invention comprises a hard coat layer (b) containing a polyfunctional (meth) acrylate compound and a conductive layer (c) containing tin-containing indium oxide particles on at least one side of a base film (a). ) And a resin layer (d) containing a fluorine-containing copolymer can be laminated.

In the present invention, for the conductive layer (c) and the resin layer (d), a coating liquid in which the respective constituents are dispersed, preferably in a solvent, is prepared, and the coating liquid is coated on the base film (a). After that, it can be formed by drying and curing.

The solvent used in the formation of the conductive layer (c) of the present invention is a solvent to be added in order to improve the coating or printing workability of the composition of the present invention and the dispersibility of ITO particles. Therefore, any conventionally known organic solvent can be used as long as it can dissolve the binder component (A). In particular, in the present invention, an organic solvent having a boiling point of 60 to 180 ° C. is preferable from the viewpoint of the stability of viscosity and the drying property of the composition, and the organic solvent having an oxygen atom has a good affinity with the ITO particles. Therefore, it is preferable.
Specific examples of such organic solvent include methanol, ethanol, isopropyl alcohol, cyclohexanone, ethylene glycol monomethyl ether, and the like.
Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, butyl acetate, isopropyl acetone, methyl ethyl ketone, diacetyl acetone,
Suitable examples include acetylacetone. These may be used alone or in combination of two or more.

The organic solvent may be added in any amount so that the composition has a viscosity in a workable state depending on the coating means and the printing means. Usually, the solid content concentration of the composition is It is appropriate that the amount is 60% by weight or less, preferably 50% by weight or less. Any method can be adopted for preparation of the composition for forming a photocurable conductive film of the present invention. Usually, ITO particles (B) are added to a solution prepared by dissolving the binder component (A) in an organic solvent. A suitable method is to add and disperse with a paint shaker, a ball mill, a sand mill, a triple roll, an attritor, a homomixer, or other dispersing machine, and then add the photopolymerization initiator (C) to uniformly dissolve it. is there.

When the resin layer (d) is formed,
A curable composition mainly composed of a fluorine-containing copolymer having a vinyl ether structure and silica fine particles is prepared by adding methyl isobutyl ketone, methyl ethyl ketone, acetylacetone, tert-butanol, 2-propanol, 1-
It is preferable to adopt a method of forming a resin layer (d) by applying a liquid dispersed in at least one solvent selected from methoxy-2-propanol and propylene glycol monomethyl ether, followed by drying and curing.

The amount of the solvent in this case can be appropriately changed depending on the required viscosity of the composition, the desired thickness of the cured film, the drying temperature condition and the like. Usually, the amount of the fluorine-containing copolymer containing a vinyl ether structure and the constituents such as silica fine particles in the coating liquid is preferably 0.
The solvent is used in an amount of 05 to 100 times by weight, more preferably 0.1 to 50 times by weight, and even more preferably 1 to 40 times by weight.

The layer structure of the laminated film of the present invention comprises a base film (a), a hard coat layer (b) containing a polyfunctional (meth) acrylate compound, and a conductive film containing tin-containing indium oxide particles on at least one side. It is preferable to provide the layer (c) and the resin layer (d) containing the fluorine-containing copolymer. As a specific example of the other layer structure, the conductive layer (c) may be provided on both the front and back sides of the base film (a),
In this case, it is preferable to provide the resin layer (d) on at least one of the conductive layers (c). When a plurality of conductive layers (c) are provided on one side of the base film (a), a plurality of conductive layers (c) are provided on the same side of the base film (a) so that the outermost surface is the resin layer (d). It is preferable to provide the resin layer (d). Alternatively, an undercoat layer and a transparent conductive layer (c) may be provided on the surface of the base film (a) opposite to the hard coat layer (b). Alternatively, a moisture-proof layer or a protective layer may be provided on the surface of the resin layer (d). The thickness of the moisture-proof layer and the protective layer is preferably 20 nm or less so as not to affect the antireflection function.

The laminated film of the present invention comprises a liquid crystal display (LCD), a plasma display panel (PDP),
It can be applied to the surface of an image display device such as an electroluminescence display (ELD), a cathode ray tube display device (CRT), and a portable digital assistant (PDA). In addition, it can be applied to surfaces of curved mirrors, rearview mirrors, goggles, window glass, posters, advertising towers, and various other commercial displays. In order to exert an antireflection function when applied to these surfaces, it can be preferably used as an image display protective film by laminating the laminated film of the present invention so that the resin layer (d) side is the outermost surface. In particular, the image display member includes a liquid crystal display (LCD), a cathode ray tube (CRT) such as a television and a computer, a plasma display (PD).
P), glass, etc. are raised, and this image display surface and /
Alternatively, it can be used as an image display device by mounting it on its front plate.

The means for bringing the laminated film prepared as described above into close contact with the image display surface and / or the surface of the front plate thereof is not particularly limited. For example, an adhesive layer is applied to the display member or the laminated film and dried to laminate. The resin layer (d) of the film is attached to the outermost layer by a pressure roller or the like, and the display member and the laminated film are adhered to each other via the adhesive material layer, so that an image display device equipped with the image display protective film is attached. Obtainable.

Next, the evaluation method and measurement method in the present invention will be described.

[Evaluation of Steel Wool Hardness] Using # 0000 steel wool, the number of scratches was observed after 10 reciprocations under a load of 250 gf / cm 2. The hardness was classified into the following 5 levels according to the level of scratches (level 5: no scratches, level 4: 1-5 scratches, level 3: 5-10)
Main scratch, Level 2: 10 or more scratches, Level 1: Full surface scratch).

[Evaluation of Adhesion (Adhesion)] As a method for evaluating the adhesive force between the conductive layer made of inorganic fine particles and the antifouling layer, the surface of the antifouling layer is cut in a grid pattern and a silicone-based or An epoxy-based or acrylic-based adhesive tape was attached, peeled off in the direction of 180 degrees, and the number of squares which were not peeled out of 100 squares was counted.

[Evaluation of surface resistance value (antistatic property)] The surface resistance value was measured using HIRESTA manufactured by Mitsubishi Yuka.

[Measurement of average reflectance] Hitachi spectrophotometer U
The measurement was performed using -3410. The back side of the sample film was evenly scratched with 320 to 400 waterproof sandpaper, and a black paint was applied to the sample film to completely eliminate reflection from the back side. The incident light angle was 6 to 10 °, and the inspection wavelength range was 380 nm ≦ λ ≦ 780 nm.

[Refractive Index Measurement] Based on JIS K 7105, the measurement was performed using an Abbe refractometer.

[0076]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. In addition, "part" and "%" in the sentence
Unless otherwise specified, the weight is based on the weight.

FIG. 1 is a schematic sectional view of a laminated film. In the laminated film, a hard coat layer 2, a conductive layer 3 and a resin layer 4 are laminated on a base film 1.

Example 1 A laminated film having the structure shown in FIG. 1 was produced by the following method.

(Formation of Hard Coat Layer 2) 51 parts of dipentaerythritol hexaacrylate, 7 parts of polyester acrylate, 3 parts of hydroxypropyl acrylate
Parts, and 5 parts of the initiator “IRGACURE 184” (manufactured by Ciba Specialty Chemicals Co., Ltd.) with toluene 27
Parts, 27 parts of methyl ethyl ketone, 18 parts of isopropyl alcohol, and 18 parts of butyl acetate were dissolved in a mixed solvent to prepare a hard coat coating solution. This hard coat coating solution was applied onto the surface of a polyester film (Lumirror, manufactured by Toray Industries, Inc.) having a thickness of 188 μm using a reverse coater, dried at 80 ° C., and then irradiated with ultraviolet rays of 1.0 J / cm 2. The coating layer was cured to provide the hard coat layer 2 having a thickness of about 5.0 μm.

(Preparation of Conductive Layer 3) Paint containing tin-containing indium oxide particles (ITO) (solid content 35.7%, polyfunctional urethane (meth) acrylate / ITO particles (average primary particle size 30 nm) = 15/85 ) (Manufactured by Dainippon Paint Co., Ltd.,
2.5 parts of EI-3 (ST) and 0.03 part of pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer were dissolved in 25 parts of n-butyl alcohol and 2.5 parts of diacetone alcohol.
The coating solution obtained by stirring the mixture is coated on the surface of the hard coat layer 2 using a gravure coater, dried at 80 ° C., and then irradiated with ultraviolet rays of 1.0 J / cm 2 to cure the coating layer. Then, a conductive layer 3 having a thickness of about 0.1 μm and a refractive index n = 1.682 was formed. (Formation of Resin Layer 4) Paint (solid content 3%) containing a fluorine-containing copolymer (fluoroolefin / vinyl ether copolymer having a polydimethylsiloxane unit) (JS
R-7, JN-7215, and colloidal silica dispersion (average primary particle size 50 nm, solid content 15%,
Isopropyl alcohol dispersion) 0.15 parts to 0.6
Part of 1-methoxy-2-propanol was dissolved and stirred to prepare a coating solution. This coating solution is applied onto the conductive layer 3 using a gravure coater, dried at 150 ° C., and cured to have a thickness of about 0.1 μm and a refractive index n = 1.4.
Two resin layers 4 were formed to produce a laminated film having the laminated structure shown in FIG.

The reflectance, surface resistance and steel wool hardness of the surface of the obtained laminated film on the resin layer side were measured. The results are shown in Table 1.

Example 2 With respect to the laminated film having the structure shown in FIG. 1, the base film 1 and the hard coat layer 2 were formed in the same manner as in Example 1. Then, a paint containing tin-containing indium oxide particles (ITO) (solid content: 35.7).
%, Polyfunctional urethane (meth) acrylate / ITO particles (average primary particle size 30 nm) = 15/85) (Dainippon Paint Co., Ltd.)
(Manufactured by EI-3 (ST)) 2.5 parts, 25 parts n
-Butyl alcohol, dissolved in 2.5 parts diacetone alcohol. The coating solution obtained by stirring the mixture was applied onto the surface of the hard coat layer 2 using a gravure coater, and 8
After drying at 0 ° C., the coating layer is cured by irradiating with ultraviolet rays of 1.0 J / cm 2 to have a thickness of about 0.1 μm and a refractive index n = 1.6.
The conductive layer 3 of No. 8 was formed. Then, in the same manner as in Example 1, a resin layer 4 was formed on the conductive layer 3 using a gravure coater. The evaluation results are shown in Table 1.

Example 3 With respect to the laminated film having the structure shown in FIG. 1, the base film 1 and the hard coat layer 2 were formed in the same manner as in Example 1. Then, a paint containing tin-containing indium oxide particles (ITO) (solid content: 35.7).
%, Polyfunctional urethane (meth) acrylate / ITO particles (average primary particle size 30 nm) = 15/85) (Dainippon Paint Co., Ltd.)
Co., Ltd., EI-3 (ST)) 2.5 parts, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer 0.04 parts, 25 parts n-
Butyl alcohol, dissolved in 2.5 parts diacetone alcohol. The coating solution obtained by stirring the mixture is applied onto the surface of the hard coat layer 2 using a gravure coater,
After drying at ℃, the coating layer is cured by irradiating with ultraviolet rays 1.0 J / cm2, thickness is about 0.1 μm, refractive index n = 1.68.
The conductive layer 3 was formed. Then, in the same manner as in Example 1, a resin layer 4 was formed on the conductive layer 3 using a gravure coater. The evaluation results are shown in Table 1.

Example 4 With respect to the laminated film having the structure shown in FIG. 1, the base film 1, the hard coat layer 2 and the conductive layer 3 were formed in the same manner as in Example 1. Then,
A coating material containing a fluorine-containing copolymer (fluoroolefin / vinyl ether copolymer having a polydimethylsiloxane unit) (solid content: 3%) (JSR Corporation, JN
-7215) 3 parts, and 0.08 parts of colloidal silica dispersion liquid (average primary particle size 13 nm, solid content 15%, isopropyl alcohol dispersion liquid) are dissolved in 0.6 parts of 1-methoxy-2-propanol. The coating liquid was adjusted by stirring. This coating liquid is applied onto the conductive layer 3 using a gravure coater, dried at 150 ° C., and cured,
The resin layer 4 having a thickness of about 0.1 μm and a refractive index n = 1.42 was formed to prepare a laminated film having the laminated structure shown in FIG. The evaluation results are shown in Table 1.

Example 5 A laminated film having the structure shown in FIG. 1 was produced by the following method.

Pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer 5
1 part, 7 parts of polyester acrylate, 3 parts of hydroxypropyl acrylate, and the initiator "Irgacure 1"
A hard coat coating solution was prepared by dissolving 5 parts of 84 "(manufactured by Ciba Specialty Chemicals Co., Ltd.) in a mixed solvent of 27 parts of toluene, 27 parts of methyl ethyl ketone, 18 parts of isopropyl alcohol and 18 parts of butyl acetate. The coating liquid was applied on the surface of a 188 μm-thick polyester film (Lumirror, manufactured by Toray Industries, Inc.) using a reverse coater, dried at 80 ° C., and then exposed to ultraviolet light 1.
The coating layer is cured by irradiating with 0 J / cm2, and the thickness is about 5.
The hard coat layer 2 having a thickness of 0 μm was provided. Then Example 1
The conductive layer 3 and the resin layer 4 were formed on the hard coat layer 2 by the same method as described above. The evaluation results are shown in Table 1.

Comparative Example 1 With respect to the laminated film having the structure shown in FIG. 1, the base film 1 and the hard coat layer 2 were formed in the same manner as in Example 1. Next, 15.7 parts of zinc antimonate sol (average primary particle size 30 nm, solid content 51%, methanol dispersion), 2 parts of pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, 2-methyl 1 [4-methylthiophenyl] A coating solution was prepared by dissolving 0.5 part of 2-morpholipropan-1-one in 314 parts of 1-methoxy-2-propanol and stirring. This coating solution is applied onto the surface of the hard coat layer 2 by using a gravure coater, dried at 80 ° C., and then irradiated with ultraviolet rays to cure the applied layer to have a thickness of about 0.1 μm and a refractive index. A conductive layer 3 with n = 1.67 was formed. Then, a resin layer 4 was formed on the conductive layer 3 using a gravure coater in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 2 With respect to the laminated film having the structure shown in FIG. 1, the base film 1 and the hard coat layer 2 were formed in the same manner as in Example 1. Next, 23 parts of ITO sol (average primary particle size 30 nm, solid content 30%, methyl ethyl ketone dispersion), 2-methyl 1 [4-methylthiophenyl] -2-morpholinpropan-1-one 0.5
Parts were dissolved in 310 parts of 1-methoxy-2-propanol and stirred to prepare a coating solution. The coating solution is applied onto the surface of the hard coat layer 2 by using a gravure coater, dried at 80 ° C., and then irradiated with ultraviolet rays to solidify the applied layer to have a thickness of about 0.1 μm and a refractive index. A conductive layer 3 having n = 2.0 was formed. Then, a resin layer 4 was formed on the conductive layer 3 using a gravure coater in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 3 With respect to the laminated film having the structure shown in FIG. 1, the base film 1 and the hard coat layer 2 were formed in the same manner as in Example 1. Then, a paint containing tin-containing indium oxide particles (ITO) (solid content: 35.7).
%, Polyfunctional urethane (meth) acrylate / ITO particles (average primary particle size 30 nm) = 15/85) (Dainippon Paint Co., Ltd.)
Co., Ltd., EI-3 (ST)) is applied on the surface of the hard coat layer 2 using a gravure coater, dried at 80 ° C., and then irradiated with ultraviolet rays of 1.0 J / cm 2 to apply the coating. The layer was cured to form a conductive layer 3 having a thickness of about 1.0 μm and a refractive index n = 1.68. Then, the conductive layer 3 is formed in the same manner as in Example 1.
A resin layer 4 was formed on the above using a gravure coater. The evaluation results are shown in Table 1.

Comparative Example 4 With respect to the laminated film having the structure shown in FIG. 1, the base film 1, the hard coat layer 2 and the conductive layer 3 were formed in the same manner as in Example 1. Then,
A coating material containing a fluorine-containing copolymer (fluoroolefin / vinyl ether copolymer having a polydimethylsiloxane unit) (solid content: 3%) (JSR Corporation, JN
-7215) and 0.08 part of colloidal silica dispersion liquid (average primary particle size 50 nm, solid content 15%, isopropyl alcohol dispersion liquid) were stirred to prepare a coating liquid. This coating solution is applied onto the conductive layer 3 using a gravure coater, dried at 150 ° C. and cured to form a resin layer 4 having a thickness of about 1.0 μm and a refractive index n = 1.42. A laminated film having the laminated constitution shown in FIG. 1 was prepared. The evaluation results are shown in Table 1.

Comparative Example 5 A laminated film having the structure shown in FIG. 1 was produced by the following method.

61 parts of hydroxypropyl acrylate,
Also, 5 parts of the initiator "Irgacure 184" (manufactured by Ciba Specialty Chemicals Co., Ltd.), 27 parts of toluene, 27 parts of methyl ethyl ketone, and 18 parts of isopropyl alcohol.
Parts and 18 parts of butyl acetate were dissolved in a mixed solvent to prepare a hard coat coating solution. This hard coat coating solution,
188 μm thick polyester film (Toray Industries, Inc.)
Manufactured by Lumirror), coated with a reverse coater, dried at 80 ° C., irradiated with 1.0 J / cm 2 of ultraviolet rays to cure the coating layer, and hard coat layer having a thickness of about 5.0 μm. 2 was provided. Then, the conductive layer 3 and the resin layer 4 were formed on the hard coat layer 2 in the same manner as in Example 1. The evaluation results are shown in Table 1.

In Examples 1 to 5, good results were obtained in all evaluation items. On the other hand, in Comparative Example 1, since the conductive particles were not ITO, the adhesion was relatively low, and the refractive index of the conductive layer was low, so that the antireflection property was insufficient. In Comparative Example 2, the acrylic resin was not mixed in the conductive layer, so there was no steel wool hardness and the hardness was insufficient. In Comparative Example 3, since the conductive layer was thick, the average reflectance was high and the antireflection property was insufficient. In Comparative Example 4, since the resin layer was thick, the average reflectance was high and the antireflection property was insufficient. Comparative Example 5 is the hard coat layer 5
Since no polyfunctional (meth) acrylate compound was used in the above, there was no steel wool hardness and the hardness was insufficient.

Example 6 An image display device having the structure shown in FIG. 2 was produced by the following method.

In order to bond the laminated film obtained in Example 1 to glass, AGR-100 as an adhesive was used.
(Manufactured by Nippon Kayaku Co., Ltd.) with a thickness of 20 μm on the front surface of a display screen of a 17-inch TV cathode ray tube (CRT), liquid crystal display (LCD) and plasma display (PDP)
Then, the laminated film obtained in Example 1 was laminated and then cured with an ultraviolet irradiation amount of 1.0 J / cm 2 to be mounted to obtain an image display device. The steel wool hardness was not scratched, the adhesion was not peeled off, and the reflectance was 0.9%, which was good in all evaluation items as a display member.

[0096]

[Table 1]

[0097]

Industrial Applicability The composite film of the present invention has a low reflectance on the surface, excellent scratch resistance, and characteristics suitable as an antireflection film. Further, this laminated film has high antistatic properties and is excellent in flexibility of the laminated film, so that it is suitable as an antireflection film applied to the surface of a flat-screen television having a large screen.

[Brief description of drawings]

FIG. 1 is a film sectional view schematically showing a laminated structure of a laminated film of the present invention.

FIG. 2 is a film cross-sectional view schematically showing a laminated structure of an image display device using the laminated film of the present invention.

[Explanation of symbols]

1 ... Base film 2 ... Hard coat layer 3 ... Conductive layer 4 ... Resin layer 5 ... Adhesive layer 6 ... Display front plate

Continued front page    F term (reference) 2K009 AA02 AA15 BB14 BB24 CC03                       CC09 CC24 CC26 EE03                 4F100 AA20D AA33 AA33C AA33E                       AJ04A AK01D AK01E AK17D                       AK17E AK21D AK25A AK25B                       AK25C AK25E AK41A AL01D                       AL01E AL05C AL05D AL05E                       AS00C AS00E AT00A BA04                       BA05 BA06 BA07 BA10D                       BA10E DE01C DE01E EH46                       EH462 EJ08 EJ082 EJ54                       EJ542 EJ86 EJ862 GB41                       JG01C JG01E JG04C JG04E                       JK12B JK12E JL13E JN06                       JN10 YY00C YY00D YY00E

Claims (8)

[Claims] 1. A hard coat layer (b) containing a (meth) acrylate compound, a conductive layer (c) containing tin-containing indium oxide particles, and a fluorine-containing copolymer on at least one side of the base film (a). Resin layer containing coalescence (d)
A conductive film (c) in a laminated film formed by laminating
Contains a binder component (A) containing a (meth) acrylate compound, tin-containing indium oxide particles (B) having an average primary particle diameter of 0.5 μm or less, and a photopolymerization initiator, and a binder component (A) The weight mixing ratio [(A) / (B)] of the indium oxide particles (B) is 10/90 to 30/7.
A laminated film, which is 0. 2. The resin layer (d) has a thickness of 0.01 μm to 1.0 μm, and the conductive layer (c) has a thickness of 0.01 μm.
To 1.0 μm, and the refractive index ratio between the resin layer (d) and the conductive layer (c) is: resin layer (d) / conductive layer (c) is 1.
It is less than 0, The laminated film of Claim 1 characterized by the above-mentioned. 3. The laminated film according to claim 1, wherein the conductive layer (c) has a surface resistance value of 1 × 10 11 Ω / □ or less. 4. The laminated film according to claim 1, wherein the conductive layer (c) contains a (meth) acrylate compound having at least one urethane bond. 5. The resin layer (d) comprises a fluorine-containing copolymer having a vinyl ether structure in the main chain, and a particle size of 0.00.
The laminated film according to any one of claims 1 to 4, which is composed of a composition containing silica fine particles of 1 µm to 0.2 µm. 6. The laminated film according to claim 1, wherein the base film (a) is made of polyester, acetate, or acrylate resin. 7. An image display protective film comprising the laminated film according to claim 1. 8. An image display device comprising the laminated film according to claim 1 attached to an image display surface and / or the surface of a front plate thereof via an adhesive layer or an adhesive layer. .