KR100966546B1 - Laminated film, filter for display, and display - Google Patents

Abstract

In the antireflection film in which the low refractive index and high refractive index thin films are laminated, the surface hardness of the low refractive index layer is improved to improve the scratch resistance of the surface, and is preferably used as an antireflection film having low reflection and excellent transparency. Provided are a display filter and a display using a film and the laminated film thereof.

On at least one surface of the base film (a), a hard coat layer (b) containing a (meth) acrylate compound, a conductive layer (c) containing conductive particles, and a resin layer (d) containing a fluorine compound are laminated. In the laminated film comprising fine irregularities on the surface of the resin layer (d), the arithmetic mean roughness (Ra) value of the irregularities is 0.003 µm or more and 0.025 µm or less, and the reflectance on the surface of the laminated film is 2%. Laminated | multilayer film which is less than, the display filter and display using this laminated | multilayer film.

Description

Laminated film, display filter and display {LAMINATED FILM, FILTER FOR DISPLAY, AND DISPLAY}

BACKGROUND OF THE INVENTION Field of the Invention The present invention is, for example, for an antireflection film disposed on a display display surface such as a cathode ray tube (CRT), a liquid crystal display device (LCD), a plasma display (PDP), and the like. It relates to a filter for.

In display displays such as TVs and PC monitors, since external light such as sunlight or fluorescent light is reflected and reflected on the surface, there is a problem that the display image is hardly visible. In order to solve this problem, irregularities are formed on the surface, as suggested by Japanese Patent Application Laid-Open No. 12-329905 or Japanese Patent Application Laid-open No. A method of preventing the reflection of light by laminating in a manner has been performed.

However, in the method of diffusely reflecting external light, a new problem arises because the image on the display looks crushed. Further, in the method of forming a low refractive index fluorine-containing compound on the surface layer, as proposed in Japanese Patent Application Laid-Open No. Hei 4-355401, Japanese Patent Application Laid-Open No. Hei 11-92750 or Japanese Patent Application Laid-Open No. Hei 11-174971, Since the surface hardness of the compound was low and not abrasion resistance, there was a problem that the image appeared crushed when the display was assembled or the surface was cleaned.

SUMMARY OF THE INVENTION An object of the present invention is to provide a laminated film which is preferably used as an antireflection film having a low reflection and excellent transparency by improving the surface scratch resistance by increasing the surface hardness of the low refractive index layer, have.

The laminated | multilayer film of this invention has the following structures mainly, in order to solve such a subject. That is, the hard coat layer (b) containing a (meth) acrylate compound, the conductive layer (c) containing electroconductive particle, and the resin layer (d) containing a fluorine compound in at least one surface of a base film (a) In the laminated film formed by laminating, fine irregularities are formed on the surface of the resin layer (d), and the arithmetic mean roughness (Ra) value of the irregularities is 0.003 µm or more, 0.025 µm or less, and the resin layer (d) side. Laminated film, characterized in that the reflectance of the laminated film surface is less than 2%.

In addition, the film for displays of this invention has the following structures mainly. That is, it is a display film which forms an adhesion layer or an adhesive bond layer on the base film side of the opposite surface of the resin layer (d) of the said laminated | multilayer film, and adhere | attaches a protective film on the adhesion layer or adhesive bond layer surface.

In addition, the display filter of this invention has the following structures mainly. That is, it is a display filter which adhere | attaches the said laminated | multilayer film on the surface of a display surface through an adhesion layer or an adhesive bond layer.

Moreover, the front protection plate for plasma display panels of this invention has the following structures mainly. That is, the said laminated | multilayer film is a front protective plate for plasma displays formed by adhering to the surface of the front plate for plasma display panels through an adhesion layer or an adhesive bond layer.

1 is an example of the cross-sectional view of the film schematically showing the laminated structure of the laminated film of the present invention.

2 is an example of the form diagram of a PDP front plate using the laminated film of the present invention.

(Explanation of the sign)

1: laminated film 2: substrate film

3: hard coat layer 4: conductive layer

5: Resin layer 6: conductive particles

7: Silica fine particles 8: Front protector for plasma display

9: glass with electromagnetic shielding function 10: adhesive layer

The laminated | multilayer film of this invention contains the hard-coat layer (b) containing a (meth) acrylate compound, the conductive layer (c) containing electroconductive particle, and a fluorine compound on at least one surface of a base film (a). The resin layer (d) is laminated.

In the laminated | multilayer film of this invention, (1) the arithmetic mean roughness (Ra) value of the unevenness | corrugation of the resin layer (d) surface is 0.003 micrometer or more and 0.025 micrometer or less, and the reflectance of the laminated film surface of the said resin layer (d) side Less than 2%, (2) Haze of laminated film is less than 3%, (3) Substrate film (a) is ester, olefin, acetate, styrene, carbonate, sulfone, ether ethyl ketone, imide, fluorine, Consisting of polymers comprising one unit selected from nylons, acrylates and cycloaliphatic olefins, (4) Polymers in which the base film (a) comprises one unit selected from esters, acetates, and acrylates Consisting of (5) the conductive layer (c) having a layer thickness of 0.01 μm to 1.0 μm, and (6) the conductive layer (c) having a conductive particle content of 70 wt% to 90 wt% And (7) The resin layer (d) is composed of a composition containing silica fine particles having a particle diameter of 0.001 µm to 0.2 µm, and (8) silly That the fine particles consist of a composition having a particle size distribution of two or more ingredients, (9) the resin layer (d) a silane represented by (formula), R (1) R _a (2) _b SiX _{4- (a + b)} What consists of the composition containing a coupling agent or its hydrolyzate, or its reactant. (Wherein R (1) and R (2) are each an alkyl group, an alkenyl group, an allyl group, or a hydrocarbon group having a halogen group, an epoxy group, an amino group, a mercapto group, a methacryloxy group, a cyano group, and the like. Is a hydrolyzable substituent selected from an alkoxyl group, an alkoxyalkoxy group, a halogen group to an acyloxy group, a and b are each 0, 1 or 2, and a + b is 1, 2 or 3.) (10) The fluorine compound of the resin layer (d) comprising a composition containing an alkoxysilyl group, (11) a display film using the laminated film, (12) a display using the display film, (13) the laminated film The display filter used, (14) the front protective plate for the plasma display panel using the laminated film, and (15) the plasma display using the front protective plate for the plasma display panel are preferred embodiments, and It can further exhibit the effect.

It will be described in more detail below.

In order to use the base film a in this invention as a member for display apparatuses (henceforth a display member hereafter), it is preferable that a light transmittance is high and its haze value is low. For example, the light transmittance at a wavelength of 400 to 800 nm is preferably 40% or more, more preferably 60% or more, and the haze value is preferably 5% or less, and more preferably 3% or less. When one or both of these conditions are not satisfied, there is a tendency for lack of sharpness of the image when used as a display member. In addition, the upper limit of light transmittance is about 99.5%, and the lower limit of haze value is about 0.1% in the point which exhibits such an effect, and is the range which can be produced.

The resin material constituting the base film (a) is not particularly limited, and may be appropriately selected from resin materials used for known plastic base films. As such a resin material for the base film (a), for example, ester, ethylene, propylene, di acetate, triacetate, styrene, carbonate, methylpentene, sulfone, ether ethyl ketone, imide, fluorine, nylon, acrylate, The polymer or copolymerized polymer which makes one selected from an alicyclic olefin type etc. as a structural unit is mentioned.

Among these resins, polymers or copolymerized polymers having one selected from esters such as polyethylene terephthalate, acetates such as triacetyl cellulose, and acrylates such as polymethyl methacrylate, have transparency strength and It is excellent in the uniformity of thickness and is used preferably. In particular, the base film (a) which consists of a polymer which makes an ester system a structural unit from the point of transparency, a haze value, and a mechanical characteristic is especially preferable.

Examples of such polyester resins include polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, polyethylene-α, β-bis (2-chlorophenoxy) ethane-4,4'-dicarboxyl The rate etc. are mentioned. In addition, these polyesters may be copolymerized as long as the other dicarboxylic acid component or diol component is 20 mol% or less. Among them, polyethylene terephthalate is particularly preferred in view of comprehensive evaluation of quality, economy and the like.

1 type of these structural resin components may be used, or they may be used together 2 or more types.

The thickness of the base film (a) used in the present invention is not particularly limited, but is usually 5 to 800 µm, preferably 10 to 250 µm, in terms of transparency, haze value and mechanical properties. Moreover, what joined two or more films by a well-known method may be sufficient.

In addition, the base film (a) is subjected to various surface treatments (e.g., corona discharge treatment, glow discharge treatment, flame treatment, etching treatment, roughening treatment, etc.) before the hard coat layer (b) is formed. It may be implemented. In addition, in order to promote adhesion, the surface of the base film (a) is coated as a primer layer (for example, polyurethane, polyester, polyester acrylate, polyurethane acrylate, polyepoxy acrylate, titanate) After coating of a compound or the like), a hard coat layer (b) may be formed. In particular, a primer coating of a composition comprising a copolymer obtained by grafting an acrylic compound to a hydrophilic group-containing polyester resin and a crosslinking agent is preferable as the base film (a) because of improved adhesiveness and excellent durability such as heat resistance and water resistance. .

It is essential that the hard coat layer (b) in this invention is formed on the base film (a), and contains a (meth) acrylate compound. A (meth) acrylate compound radically polymerizes by actinic light irradiation, and improves the solvent resistance and hardness of the film | membrane formed. Specifically, methyl (meth) acrylate, n-butyl (meth) acrylate, polyester (meth) acrylate, lauryl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) Monofunctional acrylate compounds, such as a) acrylate, are mentioned. Moreover, since the solvent resistance etc. improve the polyfunctional (meth) acrylate compound in which two (meth) acryloyl groups are in a molecule | numerator, it is especially preferable in this 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 (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimetholpropane tri (meth) acrylate, and the like. You may use these monomers 1 type or in mixture of 2 or more types.

In the constituent resin component for forming the hard coat layer (b) in the present invention, for the purpose of improving the hardness of the hard coat layer (b), alkyl silicates and its hydrolyzate, colloidal silica, dry Inorganic particles, such as silica, wet silica, and titanium oxide, silica fine particles dispersed in the colloidal form, etc. may be contained.                 

Although the thickness of the hard-coat layer (b) is suitably selected according to a use, it is 1 micrometer-50 micrometers normally, Preferably they are 2 micrometers-30 micrometers. If the thickness of the hard coat layer (b) is less than 2 µm, the surface hardness is insufficient, and scratches tend to occur, which is not preferable. Moreover, when it exceeds 50 micrometers, since transparency falls, a haze value becomes high easily, a cured film becomes weak, and when a film is bent and folded, a crack occurs easily in the hard-coat layer (b), and it is unpreferable.

It is essential that the conductive layer (c) in the present invention is formed on the hard coat layer (b) and contain the conductive particles (B) and the binder component (A).

The electroconductive particle in this invention refers to a metal particle or metal oxide fine particle. Among them, metal oxide fine particles are preferable because of their high transparency. Particularly preferred metal oxide fine particles include tin-containing antimony oxide particles (ATO), zinc-containing antimony oxide particles, tin-containing indium oxide particles (ITO), zinc oxide / aluminum oxide particles, antimony oxide particles, and more preferably tin-containing oxides. Indium oxide particles (ITO) and tin-containing antimony oxide particles (ATO).

The particles constituting the conductivity are preferably particles having an average primary particle size (sphere equivalent diameter measured by the BET method) of 0.5 µm or less, but more preferably 0.001 to 0.3 µm, even more preferably. The particle diameter of 0.005-0.2 micrometer is used. When the said average particle diameter exceeds this range, transparency of the film | membrane (conductive layer (c)) produced | generated will fall, and if it is less than this range, the said particle will aggregate easily, and the haze value of the produced | generated film (electrically conductive layer (c)) will be It increases and it becomes difficult to obtain a desired haze value in either case.                 

As the binder component (A) constituting the conductive layer (c), a (meth) acrylate compound is used. Since the (meth) acrylate compound improves the solvent resistance and hardness of the film | membrane radically polymerized by actinic light irradiation, and also the polyfunctional (meth) which has two or more (meth) acryloyl groups in a molecule | numerator Since an acrylate compound improves solvent resistance etc., it is especially preferable in this invention. For example, pentaerythritol tri (meth) acrylate, trimetholpropane tri (meth) acrylate, glycerol tri (meth) acrylate, ethylene-modified trimetholpropane tri (meth) acrylate, tris- (2 Trifunctional (meth) acrylates such as -hydroxyethyl) -isocyanuric acid ester tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythrol hexa (Meth) acrylates more than tetrafunctional, such as (meth) acrylate, etc. are mentioned.

In order to improve the dispersibility of particle | grains, the binder component (A) which comprises a conductive layer (c) can use the (meth) acrylate compound which has acidic functional groups, such as a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Specifically, as the acidic functional group-containing monomer, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, mono (2- ( Phosphoric acid (meth) acrylic acid ester, such as a meta) acryloyloxyethyl) acid phosphate and a diphenyl-2- (meth) acryloyloxyethyl phosphate, a 2-sulfoester (meth) acrylate, etc. are mentioned. In addition, the (meth) acrylate compound which has a bond with polarity, such as an amide bond, a urethane bond, an ether bond, can be used. Moreover, it is especially preferable if it is resin which has urethane bonds, such as a urethane (meth) acrylate oligomer, since polarity is high and particle dispersibility improves.

When forming a hard coat layer (b) and a conductive layer (c) in this invention, you may use an initiator in order to advance hardening of the apply | coated binder component. As said initiator, the apply | coated binder component starts or promotes superposition | polymerization and / or crosslinking reaction by radical reaction, anion reaction, cation reaction, etc., and various conventionally well-known photoinitiators can be used. Specifically, sulfides such as sodium methyldithiocarbamate sulfide, diphenyl monosulfide, dibenzothiazoyl monosulfide and disulfide; Thioxanthone derivatives such as thioxanthone, 2-ethyl thioxanthone, 2-chlorothioxanthone and 2,4-diethyl thioxanthone; 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, 2-methylanthraquinone, 2-ethylanthraquinone, 2-amino Aromatic carbonyl compounds such as anthraquinone and 2-chloroanthraquinone; dialkylamino benzoic acid esters such as methyl p-dimethylamino benzoate, ethyl p-dimethylamino benzoate, butyl D-dimethylamino benzoate and isopropyl p-diethylamino benzoate; Peroxides such as benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide and cumene hydroperoxide; Acridine derivatives such as 9-phenylacridine, 9-p-methoxyphenylacridine, 9-acetylaminoacridine and benzacridin; Phenazine derivatives such as 9,10-dimethylbenzphenazine, 9-methylbenzphenazine, and 10-methoxybenzphenazine; Quinoxaline derivatives such as 6,4 ', 4 "-trimethoxy-2,3-diphenylquinoxaline; 2,4,5-triphenylimidazoyl dimer, 2-nitrofluorene, 2,4, 6-triphenylpyrilium tetrafluoroborate, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 3,3'-carbonylbiscoumarin, thiomihilerketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone etc. are mentioned.

In the present invention, when the hard coat layer (b) and the conductive layer (c) are formed, an amine compound may coexist in the photopolymerization initiator in order to prevent a decrease in sensitivity due to oxygen inhibition of the initiator. As such an amine compound, if it is nonvolatile, such as an aliphatic amine compound and an aromatic amine compound, it will not specifically limit, for example. For example, triethanolamine, methyl diethanolamine, etc. are suitable.

In the present invention, the blending ratio of the components of the conductive layer (c) is that the weight ratio [(A) / (B)] of the binder component (A) and the particle (B) is 10/90 to 30/70. It is necessary, Preferably it is 15 / 85-25 / 75. When particle | grains (B) are less than the said range, even if transparency is sufficient, electroconductivity will worsen, and if too many, on the contrary, since the various physical and chemical strength of the film obtained will worsen, it is unpreferable. The amount of the photopolymerization initiator is usually added in an amount of 0.1 to 20 parts by weight, preferably 1.0 to 15.0 parts by weight based on 100 parts by weight of the binder component (A). If it is less than 0.1 part by weight, photopolymerization is delayed, and in order to satisfy hardness and abrasion resistance, a long time light irradiation tends to be required, and sometimes it is easy to be uncured. On the other hand, when it exceeds 20 weight part, functions, such as electroconductivity, abrasion resistance, and weather resistance of a coating film, fall easily.

The constituent components of the conductive layer (c) of the present invention include the binder component (A), the particles (B), and the photopolymerization initiator described above as essential constituents, and, if necessary, for example, a polymerization inhibitor or a curing catalyst. You may contain various additives, such as antioxidant, a dispersing agent, a leveling agent, and a silane coupling agent.

In the present invention, the constituent components of the conductive layer (c) may further contain organic metal compounds such as conductive polymers such as polypyrrole and polyaniline, metal alcoholates and chelate compounds for the purpose of imparting conductivity. In addition, to the components of the conductive layer (c), for the purpose of improving the surface hardness, alkyl silicates and hydrolyzates thereof, colloidal silica, dry silica, wet silica, titanium oxide, and other inorganic particles, and colloidal phases are used. The dispersed silica fine particles may be further contained.

In order to impart a desired level of antistatic property by the conductive layer (c) of the present invention, the surface resistance of the conductive layer (c) is preferably 1 × 10 ¹¹ Ω / □ or less, more preferably 1 × 10 ¹⁰ Ω / □ or less

The conductive layer (c) in the present invention is preferably a layer having a total light transmittance of 40% or more, more preferably 60% or more, in terms of clarity and transparency.

It is essential that the resin layer (d) in this invention is formed on the conductive layer (c), and contains a fluorine compound. The fluorine compound used in the present invention is preferably a fluorine compound crosslinked by heat or ionizing radiation. As a fluorine compound bridge | crosslinked, you may use the fluorine-containing copolymer which has an unsaturated group, the fluoropolymer which has a crosslinkable group, or the fluorine-containing monomer and the monomer for providing a crosslinkable group as a structural unit.

In particular, the main chain is preferably composed of a fluorine-containing copolymer having a vinyl ether structure. The fluorine-containing copolymer preferably has a fluorine-containing olefin chain having a fluorine content of 30% by weight or more and a number average molecular weight in terms of polystyrene of 500 or more, preferably 5000 or more.

The fluorine-containing copolymer is obtained by polymerizing a curable composition containing a fluorine-containing compound and a vinyl ether-containing compound, preferably a fluorine-containing olefin compound, a vinyl ether-containing compound copolymerizable with the fluorine-containing olefin compound, and It can obtain by polymerizing-reacting the curable composition which consists of reactive emulsifiers mix | blended as needed.

It is preferable to contain a reactive emulsifier as one component in the curable composition used in order to form a fluorine-containing copolymer. By using this reactive emulsifier component, the fluorine-containing copolymer contained in the coating liquid can be applied with good applicability and leveling property. As this 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 20 to 70 mol%, preferably 25 to 65 mol%, more preferably 30 to 60 mol%. to be. If the ratio of the structural unit derived from the fluorine-containing olefin compound component is less than 20 mol%, the fluorine content in the fluorine-containing copolymer obtained is likely to be excessive, so that the resin layer (d) obtained does not have a sufficiently low refractive index. On the other hand, when the proportion of the structural unit derived from the fluorine-containing olefin compound component exceeds 70 mol%, the uniformity of the coating liquid is deteriorated, making it difficult to form a homogeneous coating film, and the transparency and adhesion to the substrate It is lowered, which is not preferable.

In the fluorine-containing copolymer, the structural unit derived from the vinyl ether structure-containing compound component is 10 to 70 mol%, preferably 15 to 65 mol%, more preferably 30 to 60 mol%. If the proportion of the structural units derived from the vinyl ether structure-containing compound component is less than 10 mol%, the uniformity of the coating liquid is deteriorated, making it difficult to form a homogeneous coating film, and the resin layer (d) obtained when it exceeds 70 mol%. The transparency and low reflectance of the optical properties tend to be deteriorated, which is not preferable.

Moreover, since the intensity | strength of the cured film at the time of using the curable resin composition obtained as a coating agent can be improved by using the monomer containing reactive functional groups, such as a hydroxyl group or an epoxy group, as this vinyl ether structure containing compound component. The ratio in the shear monomer of the monomer containing a hydroxyl group or an epoxy group is 0-20 mol%, Preferably it is 1-20 mol%, More preferably, it is 3-15 mol%. When this ratio exceeds 20 mol%, the obtained resin layer (d) tends to deteriorate optical characteristics, and tends to be a fragile cured film.

In the fluorine-containing copolymer containing a reactive emulsifier, the proportion of the structural units derived from the reactive emulsifier component is usually 0 to 10 mol%, preferably 0.1 to 5 mol%. When this ratio exceeds 10 mol%, since the resin layer (d) obtained becomes adhesive, handling becomes difficult, and since the moisture resistance of a coating agent falls, it is unpreferable.

It is preferable to mix | blend a crosslinking | crosslinked compound with the resin layer (d) in this invention other than a fluorine-containing copolymer, and since it gives predetermined curability and improves a hardening characteristic, it is effective.

As said crosslinkable compound, various amino compounds, various hydroxyl-containing compounds, such as pentaerythritol, polyphenol, glycol, alkyl silicates, and its hydrolyzate, etc. are mentioned, for example. The amino compound used as the crosslinkable compound is a compound containing two or more of a total of any one or both of an amino group, for example, a hydroxyalkylamino group and an alkoxyalkylamino group, capable of reacting with a hydroxyl group or an epoxy group present in the fluorine compound, Specifically, a melamine type compound, a urea type compound, a benzoguanamine type compound, a glycoluril type compound, etc. are mentioned, for example. Melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples thereof include melamine, alkylated melamine, metyrolmelamine, alkoxylated methylmelamine, and the like. It is preferable to have two or more of either a tyrol group and the alkoxylated methyl group in total. Specifically, metharolized melamine, alkoxylated methylmelamine, or derivatives thereof obtained by reacting melamine and formaldehyde under basic conditions are preferable, in particular, good storage stability is obtained in the curable resin composition, and good reactivity is obtained. Preferred is alkoxylated methylmelamine. There is no restriction | limiting in particular in the metharolized melamine and the alkoxylated methyl melamine used as a crosslinking | crosslinked compound, For example, various kinds obtained by the method described in the literature "Plastic material course [8] Yuri melamine resin" (Nigan Kogyo Shimbun) The use of resinous materials is also possible. As the urea compound, in addition to urea, alkoxylated methyl urea which is a derivative of polymethyrrole urea, methirolated uron having a uron ring, alkoxylated methyluron and the like can be mentioned. Moreover, also about compounds, such as a urea derivative, can use the various resin-like thing described in the said document.

The usage-amount of this crosslinking | crosslinked compound is 70 weight part or less with respect to 100 weight part of fluorine-containing copolymers, Preferably it is 3-50 weight part, More preferably, it is 5-30 weight part. If the amount of the crosslinkable compound is less than 3 parts by weight, the durability of the thin film formed by coating and curing may become insufficient. If it exceeds 70 parts by weight, it is difficult to avoid gelation in the reaction with the fluorine-containing copolymer. In addition, a cured film does not become a thing of low refractive index, and a hardened | cured material may become weak.

In order to provide abrasion resistance, the resin layer (d) preferably contains a fluororesin having silica fine particles, and / or a silane coupling agent, and / or an alkoxysilyl group.

It is preferable that a silica fine particle component contains dry silica, wet silica, the silica fine particle disperse | distributed to the colloidal form, etc., and it is preferable to contain the silica fine particle disperse | distributed to a colloidal form.

As for the particle size of the said silica fine particle, what has an average primary particle diameter (diameter per spherical diameter: BET method) can generally use 0.001-0.2 micrometer, Preferably, the particle diameter of 0.005-0.15 micrometer is used. If the said average particle diameter is such a preferable range, the transparency of a production film (resin layer (d)) will not fall, and it will not become difficult to improve surface hardness. In addition, the shape of the said silica microparticle is spherical and the columnar phase is used preferably.                 

As the silica particles, two or more particles having different average particle diameters may be used.

The said silica fine particles can also be surface-treated and used. Surface treatment methods include physical surface treatments such as plasma discharge treatment and corona discharge treatment, and chemical surface treatment using a coupling agent, but chemical treatment is preferably used. As the coupling agent used for the chemical treatment, a silane coupling agent is particularly preferably used.

The component derived from the silica fine particles is preferably 5 to 50%, 5 to 40%, and particularly 5 to 30% by solid content. If the component derived from silica microparticles | fine-particles is such a preferable range, the surface hardness of the resin layer (d) obtained is sufficient, and it can also be made excellent in optical characteristics, such as transparency and a low reflectance.

The silane coupling agent component is a compound represented by general formula R (1) _a R (2) _b SiX _{4- (a + b)} or a hydrolysis product thereof. Here, R (1) _a R (2) _b is a hydrocarbon group each having an alkyl group, an alkenyl group, an allyl group, or a halogen group, an epoxy group, an amino group, a mercapto group, a methacryloxy group, a cyano group, or the like. X is a hydrolyzable substituent selected from an alkoxyl group, an alkoxyalkoxy group, a halogen group to an acyloxy group. a, b is 0, 1 or 2, respectively, and a + b is 1, 2 or 3.

It is preferable to make the component derived from a silane coupling agent into 5 to 70%, 15 to 65%, especially 20 to 60% by solid content. If the component derived from a silane coupling agent is such a preferable range, the surface hardness of the resin layer (d) obtained is sufficient, and it can also be made excellent in optical characteristics, such as transparency and a low reflectance.                 

The fluororesin having an alkoxysilyl group is a compound represented by the general formula R (3) _c R (4) _d SiX _{4- (c + d)} or a hydrolyzate product thereof. Here, R (3) _c R (4) _d is a hydrocarbon group each having a fluorine-substituted alkyl group, alkenyl group, allyl group, methacryloxy group, to (meth) acryloyl group. X is a hydrolyzable substituent selected from an alkoxyl group, an alkoxyalkoxy group, a halogen group or an acyloxy group. c and d are each 0, 1, 2 or 3 and a + b is 1, 2 or 3, respectively.

It is preferable to make the component derived from the fluororesin which has an alkoxy silyl group into 20 to 90%, 25 to 80%, especially 30 to 70% by solid content ratio. If the component derived from the fluororesin which has an alkoxysilyl group is such a preferable range, the optical characteristic of transparency and low reflectance of the resin layer (d) obtained is favorable, and surface hardness of a resin layer (d) can also be made good.

When forming the resin layer (d) in this invention, in order to advance hardening of a coating liquid, you may use a curing catalyst. As a curing catalyst, it is preferable to accelerate the condensation reaction of a silane coupling agent, and an acid compound is mentioned as such. Of these, Lewis acid compounds are preferred. Examples of the Lewis acid compound include metal alkoxides and metal chelates such as acetacetoxy aluminum. Although the quantity of this hardening catalyst can be determined suitably, it is 0.1-10 weight part normally with respect to 100 weight part of silane coupling agents, for example.

In this invention, when forming a resin layer (d), you may contain various additives, such as a polymerization inhibitor, antioxidant, a dispersing agent, a leveling agent, as needed.                 

In order for the laminated | multilayer film of this invention to become high transparency, haze is made into less than 3%, Preferably it is less than 2.7%. If the haze is 3% or more, transparency tends to be insufficient.

In order for the surface of the resin layer (d) in this invention to become favorable abrasion resistance, it is necessary to have a fine unevenness | corrugation on the surface of the resin layer (d). The relationship between surface roughness and abrasion resistance due to the irregularities is considered to be due to the following mechanism. In other words, in the fine concave-convex surface, when the concave-convex surface is slid with steel wool or the like, the steel wool portion is slid in contact only with the convex portion, and the contact area with the surface of the resin layer d is suppressed to the minimum necessary. As a result, in particular, the scratch resistance is improved.

As for the range of the arithmetic mean roughness Ra value of the said unevenness | corrugation of the surface of the said resin layer (d), 0.003 micrometer or more and 0.025 micrometer or less are essential. More preferably, it is 0.004 micrometer or more and 0.022 micrometer or less, More preferably, it is 0.004 micrometer or more and 0.020 micrometer or less. When the average arithmetic roughness (Ra) value of the said unevenness | corrugation exceeds this range, the haze of the resin layer (d) will become high and transparency will fall. Moreover, when the arithmetic mean roughness Ra value of the said unevenness | corrugation is less than this range, it will become difficult to improve abrasion resistance.

In order to form fine iron on the surface of the resin layer (d) of the present invention, inorganic particles such as colloidal silica, dry silica, wet silica, titanium oxide, glass beads, aluminum oxide, silicon carbide, silicon nitride, and colloidal phases are used. It is preferable to contain dispersed silica fine particles and the like, and more preferably contain fine silica particles dispersed in a colloidal form. Especially preferably, the silica fine particles can be formed by having a particle size distribution of two or more components. For example, fine unevenness | corrugation can be formed by mixing the particle | grains whose average particle diameters of a silica fine particle are 0.001-0.02 micrometer, and the particle | grains whose average particle diameter are 0.02-0.2 micrometer.

In order for the surface of the laminated film on the resin layer (d) side of the present invention to become low reflective, the reflectance of the surface is less than 2%, preferably less than 1.7%. When the reflectance exceeds this range, it is easy to cause the external light to shine, and the surface of the laminated film does not become low reflective.

In order for the surface of the laminated film on the resin layer (d) side of the present invention to become low reflective, the product of the refractive index and the thickness of the conductive layer (c) and the resin layer (d) is 1 / of the wavelength of the target light (normally visible light). It is preferable to make it four. Therefore, in the conductive layer (c) and the resin layer (d), it is preferable that four times the product of the thickness d of each layer and the refractive index n is in the range of 380 to 780 nm. That is, it is preferable that the relationship between the refractive index n and the thickness d in the said conductive layer (c) and the resin layer (d) is thickness within the range which satisfy | fills following formula (1).

n · d = λ / 4... Formula (1)

(Here, λ is the wavelength range of visible light and is usually in the range of 380 nm ≦ λ ≦ 780 nm.)

In order to provide low reflectivity to the laminated | multilayer film of this invention, it is preferable that the thickness of the conductive layer (c) is 0.01-1.0 micrometer, More preferably, it is 0.06-0.12 micrometer. Moreover, the preferable thickness range of resin layer (d) is 0.01-1.0 micrometer, More preferably, it is 0.07-0.12 micrometer. When the thickness of the conductive layer (c) and the resin layer (d) is out of this range, the above formula (1) cannot be satisfied, and the surface of the laminated film on the resin layer (d) side does not become low reflective.

Further, in order for the surface of the laminated film on the resin layer (d) side of the present invention to become low reflective, the refractive index of the resin layer (d) is smaller than that of the conductive layer (c), that is, the resin layer (d) / It is preferable that the conductive layer (c) is less than 1.0, More preferably, it is 0.6-0.95. Moreover, it is preferable that the refractive index of the resin layer (d) is 1.47 or less, More preferably, it is 1.35-1.45. It is difficult in the present situation to form a resin having a refractive index of less than 1.35, and the refractive index is higher when the refractive index is higher than 1.47.

Next, the manufacturing method of the laminated | multilayer film of this invention is demonstrated.

The laminated | multilayer film of this invention contains the hard-coat layer (b) containing a (meth) acrylate compound, the conductive layer (c) containing electroconductive particle, and a fluorine compound on at least one surface of a base film (a). It can manufacture by laminating | stacking a resin layer (d).

In the present invention, the conductive layer (c) and the resin layer (d), after adjusting the coating liquid in which each component is preferably dispersed in a solvent, applying the coating liquid onto the base film (a), It can form by drying and hardening.

As a solvent used in formation of the conductive layer (c) of this invention, it mix | blends in order to improve the application | coating or printing workability of the composition of this invention, and to improve the dispersibility of particle | grains, and melt | dissolves a binder component (A). If it does so, conventionally well-known various organic solvents can be used. In particular, in the present invention, an organic solvent having a boiling point of 60 to 180 ° C. is preferable from the viewpoint of stability of the viscosity and dryness of the composition, and among these, an organic solvent having an oxygen atom has good affinity with metal particles. desirable. Specific examples of such organic solvents include methanol, ethanol, isopropyl alcohol, n-butanol, tert-butanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, and propylene glycol monomethyl ether. , Cyclohexanone, butyl acetate, isopropyl acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetyl acetone, acetyl acetone, etc. are preferable. These may be used individually and may be used in mixture of 2 or more types.

The amount of the organic solvent may be any compounding amount so as to form a composition having a viscosity in a state of good workability depending on the coating means or printing means, but the solid content concentration of the composition is usually 60% by weight or less, preferably 50% by weight. It is appropriate to be less than or equal to%. Usually, the particles (B) are added to a solution in which the binder component (A) is dissolved in an organic solvent and dispersed by a paint shaker or a disperser such as a ball mill, a sand mill, three rolls, an attritor, a homomixer, and the like. The method of adding and dissolving uniformly a photoinitiator (C) is suitable.

In the case of forming the resin layer (d), a curable composition mainly composed of a fluorine compound may be methanol, ethanol, isopropyl alcohol, n-butanol, tert-butanol, ethylene glycol monomethyl ether, or 1-methoxy-2. Applying a liquid dispersed in at least one solvent selected from propanol, propylene glycol monomethyl ether, cyclohexanone, butyl acetate, isopropyl acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetyl acetone, acetyl acetone Then, it is preferable to take the method of drying and hardening and forming a resin layer (d).

The quantity of the solvent in this case can also be suitably changed according to the viscosity of the composition required, the thickness of the cured film made into the objective, drying temperature conditions, etc.                 

The laminated structure of the laminated | multilayer film of this invention is a hard-coat layer (b) containing a (meth) acrylate compound, the conductive layer (c) containing electroconductive particle, and a fluorine compound in at least one surface of a base film (a). It is preferable to form the resin layer (d) containing the above. As a specific example of other laminated constitution, although the conductive layer (c) may be formed in both the front and back of the base film (a), in this case, a resin layer (at least) of the conductive layer (c) of both the conductive layers (c) It is preferable to form d). In addition, in the case where the plurality of conductive layers c are formed on one surface side of the base film a, the plurality of resin layers may be formed on the same side of the base film a so that the outermost surface is the resin layer d. It is preferable to form d). Alternatively, the primer layer and the transparent conductive layer (c) may be formed 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 formed 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 in order not to affect the antireflection function.

The film for display of this invention forms an adhesion layer or an adhesive layer in the side of the base film (a) of the opposite surface of the resin layer (d) of the said laminated | multilayer film, and adhere | attaches a protective film on the adhesion layer or adhesive layer surface.

It will not specifically limit, if it adhere | attaches two things by the adhesion or adhesion action as an adhesion layer or an adhesion layer. As an adhesive or adhesive which forms an adhesive layer or an adhesive layer, a rubber type, a vinyl polymerization type, a condensation polymerization type, a thermosetting resin type, a silicone type, etc. can be used. Among them, butadiene-styrene copolymerization system (SBR), butadiene-acrylonitrile copolymerization system (NBR), chloroprene polymer system, isobutylene-isoprene copolymerization system (butyl rubber), etc. are mentioned as a rubber-based adhesive agent or adhesive agent. Can be. As an adhesive or adhesive agent of a vinyl polymerization system, an acrylic resin type, a styrene resin type, a vinyl acetate-ethylene copolymerization system, a vinyl chloride-vinyl acetate copolymerization system, etc. are mentioned. As an adhesive or adhesive agent of a condensation polymerization system, polyester resin system is mentioned. Examples of the thermosetting resin pressure sensitive adhesive include epoxy resins, urethane resins, formalin resins, and the like. These resins may be used alone or in combination of two or more thereof.

In addition, an adhesive or an adhesive can use either a solvent type or a non-solvent type. Formation of an adhesion layer or an adhesive layer is performed using the technique currently performed, such as application | coating, using the above adhesive or adhesive agent. Moreover, you may contain a coloring agent in an adhesion layer or an adhesion layer. This is easily achieved by mixing and using a coloring agent containing pigment | dyes, such as a pigment and dye, to an adhesive or an adhesive agent. When it contains a coloring agent, it is preferable that the light transmittance in 550 nm is 40 to 80% of range as a laminated film. In addition, especially when used for a plasma display, since the transmitted light is neutral gray or blue gray, and the color purity and contrast of the emission color of a display are calculated | required, it is achieved by using the adhesive layer or adhesive layer containing a pigment | dye. Can be.

The resin material which comprises a protective film is not specifically limited, It can select from the resin material used for a well-known plastic base film suitably, and can use. As the resin material for the protective film, for example, ester, ethylene, propylene, diacetate, triacetate, styrene, carbonate, methyl pentene, sulfone, ether ethyl ketone, nylon, acrylate, cycloaliphatic olefin, etc. And a copolymer or a polymer having a dog as a structural unit.

Among these resin materials, polymers or copolymerized polymers having one selected from ethylene such as polyethylene and polypropylene, esters such as propylene and polyethylene terephthalate as structural units are preferably used. In particular, the base film which consists of a polymer which makes an ester type a structural unit from the point of transparency and a mechanical characteristic is especially preferable.

The display filter of the present invention is a liquid crystal display (LCD), a plasma display panel (PDP), an electro luminescence display (ELD) or a cathode ray tube display device (CRT) via an adhesive layer or an adhesive layer of the display film. ) And a display surface of a display surface such as a portable digital assistant (PDA) and / or a surface of the front plate thereof.

Liquid crystal display (LCD), plasma display panel (PDP), electro luminescence display (ELD), cathode ray tube display (CRT), portable digital assistant (PDA) via an adhesive layer or adhesive layer of the display film of the present invention The display can be obtained by adhering to the display surface of the display surface such as).

The means for closely contacting the laminated film produced as described above with the surface of the display display surface and / or its front plate is not particularly limited. For example, an adhesive layer or an adhesive layer is applied to the display display member or the base film (a). It is dried, and it adhere | attaches with a press roller etc. so that the resin layer (d) of laminated | multilayer film may become a surface layer, and the display display member and base film (a) are adhere | attached through an adhesive layer or an adhesive layer, and the display film consists of laminated | multilayer film You can get a filter or display.

Although the embodiment of the plasma display panel front protection plate (PDP front plate) which can use the laminated | multilayer film of this invention is demonstrated based on drawing, it is not limited to this. 2 is a schematic cross-sectional view of the PDP front plate of the present invention. The laminated film 1 is laminated on both surfaces of a transparent substrate 9 such as glass, acrylic, polycarbonate, etc. via an adhesive layer or an adhesive layer 10 on the surface side of the base film 2.

In addition, a layer such as an electromagnetic shielding layer, a near infrared shielding layer, and an ultraviolet shielding layer can be formed between the transparent substrate 9 and the adhesive layer 10 of the plasma display panel front protection plate.

Next, the evaluation method and the measuring method in this invention are demonstrated.

[Steel Wool Hardness Evaluation]

Using the steel wool of # 0000, the number of wounds when reciprocating 10 times under a load of 250 gf / cm 2 was observed. According to the level of the wound, the hardness was classified into the following five levels (level 5: no wound, level 4: 1 to 5 wounds, level 3: 5 to 10 wounds, level 2: 10 or more wounds, level 1: total) Cotton wound).

Haze measurement

The measurement was performed using the direct reading haze computer of the Sugashi Kenki product.

[Evaluation of Surface Resistance (Antistatic)]

The surface resistance value was measured using the HIRESTA made from Mitsubishi Yuka.

Reflectance Measurement

The measurement was performed using the spectrophotometer U-3410 by Hitachi Keisoku. The sample film is made of 320-400 water-resistant sandpaper that is wound evenly on the back surface and coated with black paint to completely eliminate the reflection from the back surface, and the incident light angle of 6 to 10 with respect to the surface of the resin layer (d) side. Measurement was carried out at °. In addition, the reflectance here shows the minimum value in wavelength range 380nm <=== 780nm.

[Measure surface roughness]

The film surface shape was observed with the atomic force microscope of Digital Instruments, and surface roughness was computed.

Example

Next, an Example and a comparative example are given and this invention is demonstrated further more concretely. In addition, "part" and "%" in content are a basis of weight unless there is particular notice.

1 is a schematic sectional view of a laminated film, in which a hard coat layer 3, a conductive layer 4, and a resin layer 5 are laminated on a base film 2.

Example 1

The laminated film of the structure shown in FIG. 1 was produced with the following method.

(Formation of the hard coat layer 3)

On the surface of the base film 2 made of a polyester film (Toray Co., Ltd., Lumirror) having a thickness of 188 μm of a coating material (50% solids) (manufactured by JSR Corporation, KZ7224) containing a polyfunctional acrylic resin After apply | coating using a roll coater and drying at 80 degreeC, ultraviolet-ray 1.0J / cm <2> was irradiated, the coating layer was hardened | cured, and the hard-coat layer 3 of thickness about 10.0micrometer was formed.

(Formation of the conductive layer 4)                 

Paint containing tin-containing indium oxide particles (ITO) (solid content 35.7%, polyfunctional urethane (meth) acrylate / ITO particles (average primary particle size 30nm) = 18/82) (product of Dainippon Paint Co., Ltd., EI -3) 3 parts were dissolved in 10 parts of n-butyl alcohol and 7 parts of isopropyl alcohol. The coating liquid obtained by stirring the mixture was applied onto the surface of the hard coat layer 3 using a gravure coater, dried at 80 ° C., and then irradiated with ultraviolet light at 1.0 J / cm 2 to cure the coating layer to a thickness of about 0.1 μm, The conductive layer 4 of refractive index n = 1.682 was formed.

(Formation of Resin Layer 5)

40 parts of paint (solid content 3%) (JSR Co., Ltd. product, JN-7215) containing a fluorine-containing copolymer (fluoroolefin / vinyl ether copolymer), colloidal silica dispersion (average primary particle size 13 nm, solid content 30) %, Methyl isobutyl ketone dispersion) 1 part and colloidal silica dispersion liquid (average primary particle diameter 100 nm, solid content 30%, methyl isobutyl ketone dispersion liquid) were stirred by stirring. This coating liquid was applied onto the conductive layer 4 using a gravure coater, dried and cured at 150 ° C to form a resin layer 5 having a thickness of about 0.1 占 퐉 and a refractive index (n) = 1.42. The laminated | multilayer film which has a lamination structure shown to was produced.

The reflectance, surface resistance value, and steel wool hardness in the surface of the resin layer 5 of the obtained laminated | multilayer film 1 were measured. The results are shown in Table 1.                 

Example 2

About the laminated | multilayer film of the structure shown in FIG. 1, the base film 2, the hard-coat layer 3, and the conductive layer 4 were formed by the method similar to Example 1. FIG. Subsequently, 40 parts of paint (solid content 3%) containing a fluorine-containing copolymer (fluoroolefin / vinyl ether copolymer) (JSR Co., Ltd. product, JN-7215), a colloidal silica dispersion (average primary particle diameter of 13 nm) The coating liquid was adjusted by stirring 1 part of solid content, 30% of solid content, methyl isobutyl ketone dispersion), and 0.1 part of colloidal silica dispersion liquid (average primary particle diameter of 50 nm, 30% of solid content, methyl isobutyl ketone dispersion). This coating liquid was applied onto the conductive layer 4 using a gravure coater, dried at 150 ° C., and cured to form a resin layer 5 having a thickness of about 0.1 μm and a refractive index n of 1.42. The evaluation results are shown in Table 1 together.

Example 3

13 parts colloidal silica dispersion (average primary particle size 13nm, solid content 30%, isopropyl alcohol dispersion), 3 parts colloidal silica dispersion (average primary particle size 50nm, solid content 30%, methyl isobutyl ketone dispersion), silane coupling agent (Tetraethoxysilane, 100% solids) 11 parts, 27.28 parts of fluororesin (KBM7803 made by Shin-Etsu Chemical Co., Ltd.) having an alkoxysilyl group, 6.82 parts of methanol, 2.25 parts of 0.01 N hydrochloric acid, 0.2 parts of acetacetoxy aluminum, isopropyl alcohol 230 Coating liquid was adjusted by adding and stirring a part. After leaving this coating liquid at room temperature for 24 hours, it was applied to the conductive layer 4 using a gravure coater, dried and cured at 150 ° C, and the resin layer 5 having a thickness of about 0.1 µm and a refractive index (n) = 1.42. Was formed to produce a laminated film having the laminated structure shown in FIG.

Example 4

About the laminated | multilayer film of the structure as shown in FIG. 1, the base film 2 and the hard-coat layer 3 were formed by the method similar to Example 1. FIG. Subsequently, 3 parts of paint (10% of solid content, polyfunctional urethane (meth) acrylate / ATO particle | grains) (JSR Corporation make, TU-4005) containing tin containing antimony oxide particle (ATO) are 7 parts of methyl iso It dissolved in butyl ketone. The coating liquid obtained by stirring the mixture was applied onto the surface of the hard coat layer 2 using a gravure coater, dried at 80 ° C., and then irradiated with ultraviolet light at 1.0 J / cm 2 to cure the coating layer to a thickness of about 0.1 μm, The conductive layer 4 of refractive index n = 1.65 was formed. Then, the resin layer 5 was formed on the conductive layer 4 using the gravure coater by the method similar to Example 3. The evaluation results are shown in Table 1.

Comparative Example 1

About the laminated | multilayer film of the structure shown in FIG. 1, the base film 2, the hard-coat layer 3, and the conductive layer 4 were formed by the method similar to Example 1. FIG. Subsequently, 40 parts of paint (solid content 3%) containing a fluorine-containing copolymer (fluoroolefin / vinyl ether copolymer) (JSR Co., Ltd. product, JN-7215), silica particle (average primary particle diameter 1.4 micrometers) 0.3 part was added and the coating liquid was adjusted by stirring. This coating liquid was apply | coated on the conductive layer 4 using the gravure coater, and it dried and hardened | cured at 150 degreeC, and formed the resin layer 5 of about 0.1 micrometer in thickness, and refractive index (n) = 1.42. The evaluation results are shown in Table 1 together.

Comparative Example 2

About the laminated | multilayer film of the structure shown in FIG. 1, the base film 2, the hard-coat layer 3, and the conductive layer 4 were formed by the method similar to Example 1. FIG. Subsequently, 40 parts of paint (solid content 3%) (JSR Co., Ltd. product, JN-7215) containing a fluorine-containing copolymer (fluoroolefin / vinyl ether copolymer) were used for the conductive layer 4 on the gravure coater. And apply | coated, and it dried and hardened | cured at 150 degreeC, and formed the resin layer 5 of thickness about 0.1 micrometer and refractive index (n) = 1.42. The evaluation results are shown in Table 1 together.

Comparative Example 3                 

About the laminated | multilayer film of the structure shown in FIG. 1, the base film 2 and the hard-coat layer 3 were formed by the method similar to Example 1. FIG. Subsequently, 23 parts of ITO sol (average primary particle diameter 30nm, 30% of solid content, methyl ethyl ketone dispersion), 23 parts of 2-methyl 1 [4-methylthio phenyl] -2- morpholipropan- 1-one, 310 parts of 1 -The coating liquid was adjusted by melt | dissolving in methoxy-2-propanol and stirring. This coating liquid was applied onto the surface of the hard coat layer 3 using a gravure coater, dried at 80 ° C., and then irradiated with ultraviolet rays to solidify the coating layer, thereby having a thickness of about 0.1 μm and a refractive index (n) of 2.0. The conductive layer 4 was formed. Subsequently, the resin layer 5 was formed on the conductive layer 4 using the gravure coater in the same manner as in Example 1. The evaluation results are shown in Table 1 together.

Example 5

In order to bond the laminated | multilayer film obtained in Example 1 to glass, it bonded to glass using AGR-100 (made by Nihon Kayaku Co., Ltd.) as an adhesive on the surface which does not form the resin layer (d), and was 1,000, It hardened | cured by the ultraviolet-ray irradiation amount of mj / cm <2>. The test results are shown in Table 1 together.

Examples 1-4 and 5 were favorable results in all the evaluation items. On the other hand, in Comparative Example 1, since the particle diameter of the resin layer silica particles was too large, the average surface roughness was high, resulting in insufficient transparency and antireflection. In Comparative Example 2, since no silica particles were added to the resin layer, irregularities could not be formed on the surface, and steel wool hardness was insufficient. In Comparative Example 3, when the acrylic resin was not blended with the conductive layer, the conductive layer became hardened and the steel wool hardness was insufficient.                 

Example 6

In order to bond the laminated | multilayer film obtained in Example 1 to both surfaces of glass, respectively, on the surface of the base film (a), it used for the glass using the adhesive containing the pigment | dye which has absorption maximum at wavelength 595nm, and the pigment | dye which corrects the chromaticity of white light. It bonded together and obtained the front protection plate for plasma display panels.

Example 7

As a result of setting the front protective plate for the plasma display panel of Example 6 on the entire surface of the plasma display panel, a plasma display displaying a good image with little reflection was obtained.

The laminated | multilayer film of this invention is low in reflectance of a surface, is excellent in abrasion resistance, and has the characteristic characteristic as an antireflection film. In addition, since the laminated film has high antistatic property and excellent flexibility of the laminated film, it is preferable as an antireflective film applied to the display surface.

Claims (17)

On at least one surface of the base film (a), a hard coat layer (b) containing a (meth) acrylate compound, a conductive layer (c) containing conductive particles, a fluorine compound and silica fine particles having a particle diameter of 0.001 µm to 0.2 µm. In the laminated film formed by laminating a resin layer (d) containing a, the surface of the resin layer (d) has fine irregularities, and the arithmetic mean roughness (Ra) value of the irregularities is 0.003 µm or more and 0.025 µm or less Laminated film, characterized in that the reflectance of the surface of the laminated film on the resin layer (d) is less than 2%. The laminated film according to claim 1, wherein the laminated film has a haze of less than 3%. The method of claim 1, wherein the base film (a) is selected from ester, olefin, acetate, styrene, carbonate, sulfone, ether ethyl ketone, imide, fluorine, nylon, acrylate, alicyclic olefin Laminated film, characterized in that the polymer. The laminated film according to claim 3, wherein the base film (a) is a polymer comprising one selected from esters, acetates, and acrylates. The laminated film according to claim 1, wherein the layer thickness of the conductive layer (c) is 0.01 µm to 1.0 µm. The laminated film according to claim 1, wherein the conductive particles of the conductive layer (c) are metal oxide fine particles. The laminated film according to claim 1, wherein the content of the conductive particles in the conductive layer (c) is 70% by weight to 90% by weight. The laminated film according to claim 1, wherein the resin layer (d) is made of a fluorine-containing copolymer having a vinyl ether structure in the main chain. delete The laminated film according to claim 1, wherein the silica fine particles have a particle size distribution of two or more components. The laminated film according to claim 1, wherein the resin layer (d) contains a silane coupling agent represented by the following general formula or a hydrolyzate thereof or a reactant thereof. (Formula) R (1) _a R (2) _b SiX _{4- (a + b)} Here, R (1) and R (2) are each an alkyl group, an alkenyl group, an allyl group, or a hydrocarbon group having a halogen group, an epoxy group, an amino group, a mercapto group, a methacryloxy group, and a cyano group. X is a hydrolyzable substituent selected from an alkoxyl group, an alkoxyalkoxy group, a halogen group to an acyloxy group. a and b are 0, 1 or 2, respectively, and a + b is 1, 2 or 3, respectively. The laminated film according to claim 1, wherein the fluorine compound of the resin layer (d) contains an alkoxysilyl group. The laminated film of Claim 1 was used, The display film characterized by the above-mentioned. The display film of Claim 13 was used. The display characterized by the above-mentioned. The laminated film of Claim 1 was used, The display filter characterized by the above-mentioned. A front protective plate for plasma display panel, comprising using the display filter according to claim 15. A plasma display comprising the front protective plate for a plasma display panel according to claim 16.

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