JP2008018543A - Hard coat film, antireflection film and antireflection near-infrared shielding film using the same - Google Patents

Abstract

A hard coat film capable of improving the adhesion of a hard coat layer to a transparent substrate film while suppressing the occurrence of interference fringes, and an antireflection film and an antireflection near-infrared shielding film using the same. provide.
A hard coat film 10 is formed by laminating a hard coat layer 13 on a transparent substrate film 11 with an adhesive layer 12 interposed therebetween. The difference in refractive index between the transparent substrate film 11 and the hard coat layer 13 is within 0.02, and the film thickness of the adhesive layer 12 is 5 to 30 nm. The antireflection film 14 is configured by laminating an antireflection layer 15 on the hard coat layer 13 of the hard coat film 10. The antireflection near-infrared shielding film 16 is configured by laminating a near-infrared shielding layer 17 on the transparent base film 11 on the side opposite to the side on which the antireflection layer 15 of the antireflection film 14 is provided. Yes.
[Selection] Figure 1

Description

  The present invention relates to a hard coat film provided on a display screen of an electronic image display device such as a plasma display (PDP) or a liquid crystal display (LCD), an antireflection film and an antireflection near infrared shielding film using the same. Is. More specifically, a hard coat film capable of improving the adhesion of the hard coat layer to the transparent substrate film while suppressing the occurrence of interference fringes, an antireflection film and an antireflection near-infrared shielding film using the same It is about.

  In recent years, electronic image display devices (electronic displays) are widely used for televisions and monitors. Among them, plasma displays are attracting a lot of attention as being optimal for large-screen flat panel displays, and their surfaces have anti-reflective films and anti-reflective properties for improving visibility and shielding near infrared rays emitted from plasma display panels. A near-infrared shielding film is provided. In order to improve the physical strength of these functional optical films, a transparent (clear) hard coat layer using an ionizing radiation curable resin such as an ultraviolet curable resin or an electron beam curable resin is provided on a transparent base film. It is common.

  Since the refractive index of a polyethylene terephthalate (PET) film mainly used as a transparent substrate film is 1.65, and the refractive index of a normally used hard coat layer is 1.50 to 1.55. In addition, a refractive index difference of 0.10 to 0.15 occurs between the PET film and the hard coat layer. Since reflection of light occurs at the interface between layers having different refractive indices, rainbow-colored unevenness (interference fringes) is observed when the film is viewed under a fluorescent lamp or the like due to interference of reflected light generated at the interface between the two.

Therefore, in order to suppress the interference fringes, the refractive index difference between the refractive index of the transparent substrate film and the refractive index of the hard coat layer is set within 0.03, and the relationship between the reflectance and wavelength in the visible light region is shown. A hard coat film having a reflection spectrum that does not have a maximum value and a minimum value has been proposed (see, for example, Patent Document 1).
Japanese Patent Laying-Open No. 2005-215283 (Page 2, Page 3 and Page 8)

  However, in the hard coat film described in Patent Document 1, the hard coat layer is directly provided on the transparent substrate film. That is, a hard coat layer coating solution containing an ultraviolet curable resin is applied onto a transparent substrate film, and cured by irradiating with ultraviolet rays to form a hard coat layer. Therefore, the hard coat layer is bonded to the transparent substrate film by curing the ultraviolet curable resin, but the ultraviolet curable resin is for forming the hard coat layer, and the hard coat layer is formed on the transparent substrate film. Adhesion was clearly insufficient. Therefore, further improvement is required for the adhesion of the hard coat layer to the transparent substrate film while suppressing the generation of interference fringes.

  Therefore, an object of the present invention is to provide a hard coat film capable of improving the adhesion of the hard coat layer to the transparent substrate film while suppressing the occurrence of interference fringes, an antireflection film and a reflection using the same. It is providing the preventive near-infrared shielding film.

  In order to achieve the above object, the hard coat film of the first invention in the present invention is constituted by laminating a hard coat layer on an adhesive layer on a transparent base film, and the hard base film and the hard base film are hardened. The difference in refractive index from the coat layer is 0.02 or less, and the film thickness of the adhesive layer is 5 to 30 nm.

The hard coat film of the second invention is characterized in that, in the first invention, the transparent substrate film is a polyester film.
The hard coat film of the third invention is characterized in that, in the first or second invention, metal oxide fine particles are contained in the hard coat layer.

  The antireflection film of the fourth invention is characterized in that an antireflection layer is further laminated on the hard coat layer in the hard coat film of the invention according to any one of the first to third aspects. It is.

  The antireflective near-infrared shielding film of 5th invention laminate | stacks a near-infrared shielding layer on the transparent base film opposite to the side in which the antireflection layer in the antireflective film of 4th invention is provided. It is characterized by being comprised.

According to the present invention, the following effects can be exhibited.
In the hard coat film of the first invention, since the difference in refractive index between the transparent base film and the hard coat layer is set within 0.02, interference fringes generated based on the refractive index difference can be suppressed. it can. Furthermore, since the film thickness of the adhesive layer is set to a thin thickness of 5 to 30 nm, it is possible to improve the adhesion between the transparent base film and the hard coat layer by avoiding the generation of interference fringes by the adhesive layer. it can. Therefore, the adhesion of the hard coat layer to the transparent substrate film can be improved while suppressing the generation of interference fringes.

  In the hard coat film of the second invention, since the transparent base film is a polyester film, in addition to the effects of the first invention, it is easy to mold to a predetermined thickness and is easily available. The manufacturing cost can be reduced.

  In the hard coat film of the third invention, since the metal oxide fine particles are contained in the hard coat layer, in addition to the effects of the first or second invention, the transparent substrate film, the hard coat layer, The refractive index difference can be easily set within 0.02.

  In the antireflection film of the fourth invention, since an antireflection layer is further laminated on the hard coat layer, in addition to the effects of any one of the first to third inventions, the antireflection performance is exhibited. And can be suitably used for an electronic image display device.

  In the antireflection near-infrared shielding film of the fifth invention, the near-infrared shielding layer is laminated on the transparent substrate film on the side opposite to the side on which the antireflection layer is provided. In addition to the effects of the invention, the performance of shielding near infrared rays can be expressed, and it can be suitably used for an electronic image display device.

In the following, embodiments that are considered to be the best of the present invention will be described in detail.
As shown in FIG. 1A, the hard coat film 10 of the present embodiment is configured by laminating a hard coat layer 13 on a transparent base film 11 with an adhesive layer 12 interposed therebetween, and the transparent base film 11 The difference in refractive index between the hard coat layer 13 and the hard coat layer 13 is within 0.02, and the film thickness of the adhesive layer 12 is set to 5 to 30 nm. By suppressing the difference in refractive index between the transparent substrate film 11 and the hard coat layer 13 within 0.02, interference fringes generated based on the difference in refractive index can be suppressed. Moreover, the adhesiveness of the transparent base film 11 and the hard-coat layer 13 can be improved, suppressing generation | occurrence | production of an interference fringe by setting the film thickness of the contact bonding layer 12 to 5-30 nm very thin.

  As shown in FIG. 1B, the antireflection film 14 using the hard coat film 10 is configured by providing an antireflection layer 15 on a hard coat layer 13. As shown in FIG. 1C, the antireflection near-infrared shielding film 16 using the hard coat film 10 is provided with an antireflection layer 15 on the hard coat layer 13 and an antireflection layer 15. The near-infrared shielding layer 17 is provided on the transparent substrate film 11 on the opposite side to the surface on which the light is applied.

  First, the transparent substrate film 11 will be described. The transparent substrate film 11 is not particularly limited as long as it has transparency. However, in order to suppress reflection, the refractive index (n) is 1.55 to 1.70. Those within the range are preferred. Examples of such transparent resin base materials include polyesters such as polyethylene terephthalate (PET, n = 1.65), polycarbonate (PC, n = 1.59), polyarylate (PAR, n = 1.60), and polyether sulfone. (PES, n = 1.65) and the like are preferable. Among these, a polyester film, particularly a polyethylene terephthalate film is preferable in terms of ease of molding, availability, and cost.

  Moreover, the thickness of the transparent base film 11 is preferably 25 to 400 μm, and more preferably 50 to 200 μm. In addition, the transparent substrate film 11 may contain various additives. Examples of such additives include ultraviolet absorbers, antistatic agents, stabilizers, plasticizers, lubricants, flame retardants, and the like. As the ultraviolet absorber, a known ultraviolet absorber is used, and for example, a salicylic acid compound, a benzophenone compound, a benzotriazole compound, a cyclic imino ester compound, and the like are preferable. Among these, a benzophenone compound, a benzotriazole compound, Cyclic imino ester compounds are particularly preferred.

  The content of the ultraviolet absorber is preferably such that the light transmittance of ultraviolet rays having a wavelength of 380 nm or less is 5% or less, more preferably 3% or less, and 1% or less. It is particularly preferable to add such that When the light transmittance of a wavelength of 380 nm or less exceeds 5%, a sufficient ultraviolet shielding effect cannot be expected for the near infrared absorbing dye in the near infrared shielding layer 17, which is not preferable.

Next, the hard coat layer 13 provided on one surface of the transparent substrate film 11 will be described.
The hard coat layer 13 is used for the hard coat layer 13 as long as the difference in refractive index between the refractive index and the refractive index of the transparent substrate film 11 is within 0.02, and the surface hardness and scratch resistance can be improved. Any known resin can be used, and it is particularly preferable that the resin is formed from a material containing an ionizing radiation curable resin and metal oxide fine particles. Here, the metal oxide fine particles mean metal oxides having an average particle diameter of preferably 150 nm or less, more preferably 10 to 150 nm. If this average particle diameter exceeds 150 nm, the fine particles become too large, resulting in a loss of transparency of the hard coat layer 13.

  By reducing the reflected light by making the refractive index of the hard coat layer 13 close to the refractive index of the transparent base film 11, interference fringes generated by interference of the reflected light can be reduced. On the other hand, when the difference in refractive index between the transparent substrate film 11 and the hard coat layer 13 exceeds 0.02, the reflected light at the interface between the transparent substrate film 11 and the hard coat layer 13 becomes stronger. The interference fringes become strong and inappropriate.

  The ionizing radiation curable resin is a resin that undergoes a curing reaction when irradiated with active energy rays such as ultraviolet rays and electron beams, and the type thereof is not particularly limited. Specifically, for example, monofunctional (meth) acrylate [in the present specification, (meth) acrylate means a generic name including both acrylate and methacrylate. ], Starting materials such as polyfunctional (meth) acrylates and reactive silicon compounds such as tetraethoxysilane. Among these, from the viewpoint of achieving both productivity and hardness, a composition containing an ultraviolet curable polyfunctional acrylate as a main component is preferable. The composition containing such an ultraviolet curable polyfunctional acrylate is not particularly limited. For example, a mixture of two or more known ultraviolet curable polyfunctional acrylates is commercially available as an ultraviolet curable hard coat material. Are listed.

  The ultraviolet curable polyfunctional acrylate is not particularly limited. For example, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane triacrylate, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, 1, Acrylic derivatives of polyfunctional alcohols such as 6-bis (3-acryloyloxy-2-hydroxypropyloxy) hexane, polyethylene glycol diacrylate and polyurethane acrylate are preferred.

  When the metal oxide fine particles added to the ionizing radiation curable resin are dispersed in the ionizing radiation curable resin to form a coating film, the difference in refractive index between the transparent substrate film 11 and the hard coat layer 13 is zero. Those that can be adjusted to be 0.02 or less are selected. Examples of the metal oxide include ITO (indium-tin composite oxide, refractive index 2.0), ATO (antimony-tin composite oxide, refractive index 2.1), tin oxide (refractive index 2.0), From antimony oxide (refractive index 2.1), zinc oxide (refractive index 2.1), zirconium oxide (refractive index 2.1), titanium oxide (refractive index 2.4) and aluminum oxide (refractive index 1.6). At least one selected from the group consisting of Of these, tin oxide and antimony oxide are particularly preferable in terms of particle dispersibility, average particle diameter, availability, and production cost. The addition amount of the metal oxide fine particles to the ionizing radiation curable resin is about 1 to 400 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

  In addition, other components can be further added to the ionizing radiation curable resin as long as the effects of the present invention are not impaired. Examples of such other components include additives such as a polymer, a polymerization initiator, a polymerization inhibitor, an antioxidant, a dispersant, a surfactant, a light stabilizer, and a leveling agent. Further, any amount of solvent can be added as long as it is dried after film formation in the wet coating method.

  Subsequently, the method for forming the hard coat layer 13 is not particularly limited, and a general wet coat method such as a roll coat method, a coil bar method, or a die coat method is employed. The formed layer can be subjected to a curing reaction by heating or irradiation with active energy rays such as ultraviolet rays and electron beams, as necessary.

Next, the adhesive layer 12 provided on the transparent substrate film 11 will be described.
The adhesive layer 12 has a function of improving the adhesion between the transparent base film 11 and the hard coat layer 13 without adversely affecting optically. The film thickness of the adhesive layer 12 is 5 to 30 nm, preferably 10 to 20 nm, and has a known refractive index as an adhesive as long as the adhesion between the transparent substrate film 11 and the hard coat layer 13 can be improved. The resin layer can be applied. When the film thickness of the adhesive layer 12 is less than 5 nm, the adhesion between the transparent substrate film 11 and the hard coat layer 13 cannot be maintained, while when the film thickness of the adhesive layer 12 exceeds 30 nm, for example, The transparent base film 11 provided with the adhesive layer 12 has many interference fringes because the adhesive layer 12 has an optical adverse effect.

  As a method for forming the adhesive layer 12, a method of applying a coating liquid containing a water-dispersible or water-soluble polyester resin as an adhesive on the transparent substrate film 11 and then drying it is preferable. In particular, when a polyester film is used as the transparent base film 11, it is preferable to use a polyester resin, particularly a copolymerized polyester resin, as an adhesive for forming the adhesive layer 12. The copolyester resin means a polyester resin obtained by a polycondensation reaction between a plurality of dicarboxylic acids and a plurality of polyols or a transesterification reaction between a plurality of esters and a plurality of polyols. Such a copolyester resin is formed by a polycondensation reaction of a dicarboxylic acid and a polyol.

  Dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, dimer acid Etc. In addition to the dicarboxylic acid, a sulfonic acid metal base-containing dicarboxylic acid may be added to impart water dispersibility.

  Examples of polyols include ethylene glycol, propylene glycol, tetramethylene glycol, 1,4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, 1,4-butanediol, dipropylene glycol, 1,6-hexanediol, and xylene glycol. Although it is mentioned, it is not limited to these.

  A filler, wax, or the like may be added to the coating solution containing the copolymerized polyester resin for the purpose of imparting blocking resistance and slipperiness. Examples of the filler include silica, titanium oxide, calcium carbonate, calcium silicate, barium sulfate, calcium phosphate, aluminum oxide, magnesium oxide, zinc oxide, and tin oxide. Among these, it is preferable to select one that does not settle in the coating solution. These fillers usually have an average particle size of 20 to 60 nm. When the average particle size is less than 20 nm, sufficient blocking resistance and slipping properties may not be obtained, and when it exceeds 60 nm, the filler tends to fall off.

  As the wax, water-dispersible or water-soluble waxes such as carnauba wax, candelilla wax, rice wax, wood wax, palm wax, montan wax, ozokerite, ceresin wax, paraffin wax, polyethylene glycol, and polypropylene glycol are preferable.

  In order to further improve the scratch resistance, it is preferable to add a crosslinking agent to the adhesive layer 12. As the crosslinking agent, oxazolines, epoxy compounds, melamine compounds, isocyanate compounds, coupling agents and the like can be used, and among them, oxazolines are preferable. As the oxazolines, a polymer containing an oxazoline group is preferable. This is obtained by copolymerization with an addition polymerizable oxazoline group-containing monomer alone or with another monomer. Examples of the addition polymerizable oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, and 2-isopropenyl-2-oxazoline. Among these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.

  Other monomers are not limited as long as they are copolymerizable with addition-polymerizable oxazoline group-containing monomers, and are acrylic acid esters, unsaturated carboxylic acids, unsaturated nitriles, unsaturated amides. , Vinyl esters, vinyl ethers, α-olefins, halogen-containing α, β-unsaturated monomers, α, β-unsaturated aromatic monomers, and the like.

  In order to provide the adhesive layer 12 on the transparent base film 11, the coating liquid is applied to one or both sides of the transparent base film 11. The application can be carried out at an arbitrary stage, but is preferably carried out during the production process of the transparent substrate film 11. As a coating method, any known coating method can be used. For example, a gravure coating method, a roll brush method, a spray coating method, an air knife method, a coil bar method, a dip coating method and the like can be mentioned.

Next, the antireflection layer 15 will be described.
The antireflection layer 15 can have a single layer structure or a multilayer structure. In the case of a single layer configuration, one layer having a refractive index lower than that of the hard coat layer 13 (low refractive index layer) is formed on the hard coat layer 13. In the case of a multilayer structure, layers having different refractive indexes are laminated on the hard coat layer 13 in a multilayer form. By adopting a multilayer structure, the reflectance can be lowered more effectively. Specifically, the antireflection layer 15 includes a two-layer configuration including a high refractive index layer and a low refractive index layer in order from the hard coat layer 13 side, a medium refractive index layer, a high refractive index layer, and a low refractive index layer. Or a four-layer configuration including a high refractive index layer, a low refractive index layer, a high refractive index layer, and a low refractive index layer. From the viewpoint of the antireflection effect, a structure of three or more layers is preferable, and from the viewpoint of productivity and production cost, a single-layer structure or a two-layer structure is preferable.

  The method for forming the antireflection layer 15 is not particularly limited, and for example, a dry coating method, a wet coating method, or the like is employed. Among these methods, the wet coating method is particularly preferable in terms of productivity and production cost. The wet coating method may be a known method, and for example, a roll coating method, a spin coating method, a coil bar method, a dip coating method, etc. are representative methods. Among these, a method capable of continuously forming the antireflection layer 15 such as a roll coating method is preferable from the viewpoint of productivity and production cost. In order to express the function of the antireflection layer 15, the refractive index of the low refractive index layer is that the layer to be formed has a lower refractive index than the layer immediately below, and the refractive index is 1.20. It is preferable to be in the range of ~ 1.55. When the refractive index exceeds 1.55, it is difficult to obtain a sufficient antireflection effect by the wet coating method, whereas when it is less than 1.20, it tends to be difficult to form a sufficiently hard layer.

  Furthermore, in the case of a two-layer structure, the refractive index of the high refractive index layer needs to be higher than that of the low refractive index layer formed immediately above, so that the refractive index is 1.65 to 1.90. It is preferable to be within the range. If the refractive index is less than 1.65, it is difficult to obtain a sufficient antireflection effect, and it tends to be difficult to form a layer exceeding 1.90 by the wet coating method. Further, in the case of a multilayer structure provided with a middle refractive index layer, any layer having a refractive index lower than that of the high refractive index layer to be laminated and higher in refractive index than that of the low refractive index layer may be used. Not.

The thickness of the antireflection layer 15 varies depending on the type and shape of the transparent substrate film 11 and the structure of the antireflection layer 15, but a thickness equal to or less than the wavelength of visible light per layer is preferable. For example, when the effect of reducing reflection with respect to visible light is expressed, the optical film thickness n _H · d of the high refractive index layer is 500 ≦ 4 n _H · d (nm) ≦ 750, and the optical film of the low refractive index layer The thickness n _L · d is designed to satisfy 400 ≦ 4n _L · d (nm) ≦ 650. Here, n _H and n _L are the refractive indexes of the high refractive index layer and the low refractive index layer, respectively, and d is the thickness of the layer.

  The material constituting the high refractive index layer is not particularly limited, and an inorganic material or an organic material can be used. Specific examples of the inorganic material include zinc oxide, titanium oxide, cerium oxide (refractive index 2.30), tin oxide, aluminum oxide, silane oxide (refractive index 1.90), zirconium oxide, and indium tin oxide (refractive index 2). .00) and the like. As the organic material, specifically, a high refractive index organic monomer or polymer containing a thiol group or phenyl group having a refractive index of 1.60 to 1.80 can be used.

  The high refractive index layer containing fine particles of the inorganic material can use an organic monomer or a polymer as a binder during wet coating. The average particle diameter of the fine particles of the inorganic material preferably does not greatly exceed the thickness of the layer, and is particularly preferably 0.1 μm or less. When the average particle size of the fine particles is increased, scattering is caused and the optical function of the high refractive index layer is deteriorated. Further, the surface of the fine particles can be modified with various coupling agents as required. Examples of such a coupling agent include organically substituted silicon compounds, organic acid salts containing metal alkoxides such as aluminum, titanium, zirconium, and antimony.

  As a material constituting the low refractive index layer, for example, inorganic fine particles such as hollow silicon oxide, colloidal silicon oxide, lanthanum fluoride, and magnesium fluoride, organic polymer fine particles, or a simple substance or a mixture of a fluorine-containing organic compound is used. be able to. In addition, a simple substance, a mixture, or a polymer of an organic compound not containing fluorine (hereinafter abbreviated as a non-fluorine organic compound) can be used as the binder resin.

  The average particle diameter of the inorganic fine particles preferably does not greatly exceed the thickness of the low refractive index layer, and is particularly preferably 0.1 μm or less. When the average particle size is increased, the optical performance of the low refractive index layer is deteriorated, such as light scattering. Furthermore, the surface of the fine particles can be modified with various coupling agents as required. An example of such a coupling agent is an organically substituted silicon compound. In particular, a film having high hardness can be formed by modifying the surface with a reactive group such as a (meth) acryloyl group.

  The fluorine-containing organic compound is not particularly limited. For example, fluorine-containing monofunctional (meth) acrylate, fluorine-containing polyfunctional (meth) acrylate, fluorine-containing itaconic acid ester, fluorine-containing maleic acid ester, fluorine-containing silicon compound And the like, and polymers thereof. Among these, fluorine-containing (meth) acrylate is preferable from the viewpoint of reactivity, and fluorine-containing polyfunctional (meth) acrylate is particularly preferable from the viewpoint of hardness and refractive index. By curing these fluorine-containing organic compounds, a layer having a low refractive index and a high hardness can be formed.

  Examples of the fluorine-containing monofunctional (meth) acrylate include 1- (meth) acryloyloxy-1-perfluoroalkylmethane, 1- (meth) acryloyloxy-2-perfluoroalkylethane, and the like. Examples of the perfluoroalkyl group include those having a linear, branched or cyclic structure having 1 to 8 carbon atoms.

  As the fluorine-containing polyfunctional (meth) acrylate, fluorine-containing bifunctional (meth) acrylate, fluorine-containing trifunctional (meth) acrylate and fluorine-containing tetrafunctional (meth) acrylate are preferable. Examples of the fluorine-containing bifunctional (meth) acrylate include 1,2-di (meth) acryloyloxy-3-perfluoroalkylbutane, 2-hydroxy-1H, 1H, 2H, 3H, 3H-perfluoroalkyl-2 ′. 2,2′-bis {(meth) acryloyloxymethyl} propionate, α, ω-di (meth) acryloyloxymethyl perfluoroalkane and the like are preferable. The perfluoroalkyl group preferably has a linear, branched or cyclic structure having 1 to 11 carbon atoms, and the perfluoroalkane group is preferably a linear one. These fluorine-containing bifunctional (meth) acrylates can be used alone or as a mixture when used.

  Examples of the fluorine-containing trifunctional (meth) acrylate include 2- (meth) acryloyloxy-1H, 1H, 2H, 3H, 3H-perfluoroalkyl-2 ′, 2′-bis {(meth) acryloyloxymethyl} Examples include propionate. The perfluoroalkyl group is preferably a linear, branched or cyclic group having 1 to 11 carbon atoms.

  Examples of the fluorine-containing tetrafunctional (meth) acrylate include α, β, ψ, ω-tetrakis {(meth) acryloyloxy} -αH, αH, βH, γH, γH, χH, χH, ψH, ωH, ωH-perfluoroalkane and the like are preferable. The perfluoroalkane group is preferably a linear one having 1 to 14 carbon atoms. The fluorine-containing tetrafunctional (meth) acrylate can be used alone or as a mixture. As a specific example of the fluorine-containing silicon compound, (1H, 1H, 2H, 2H-perfluoroalkyl) trimethoxysilane and the like are preferable. The perfluoroalkyl group is preferably a linear, branched or cyclic group having 1 to 10 carbon atoms.

  As the polymer of the above-mentioned fluorine-containing organic compound or the polymer of other fluorine-containing organic compounds, a linear polymer such as a homopolymer of a fluorine-containing organic compound, a copolymer, or a copolymer with a non-fluorine-based organic compound is used. Examples thereof include a polymer, a polymer containing a carbocyclic ring or a heterocyclic ring in the chain, a cyclic polymer, and a comb polymer. A conventionally well-known thing can be used as said non-fluorine-type organic compound, For example, silicon compounds, such as monofunctional or polyfunctional (meth) acrylate, tetraethoxysilane, etc. are mentioned.

  Further, the antireflection layer 15 may contain other components in addition to the above compounds as long as the effects of the present invention are not impaired. Other components are not particularly limited, and for example, inorganic or organic pigments, polymers, polymerization initiators, photopolymerization initiators, polymerization inhibitors, antioxidants, dispersants, surfactants, light stabilizers, leveling An additive such as an agent can be mentioned. Further, any amount of solvent can be added as long as it is dried after film formation by the wet coating method.

  The antireflection layer 15 can be formed by performing a curing reaction by irradiation with an active energy ray such as an ultraviolet ray or an electron beam or heating, if necessary, after being formed by a wet coating method. Such a curing reaction using active energy rays is preferably performed in an atmosphere of an inert gas such as nitrogen or argon.

Next, the near infrared shielding layer 17 will be described.
The near-infrared absorbing dye contained in the near-infrared shielding layer 17 is preferably a diimonium salt containing a sulfonimide represented by the following general formula (1) as an anion component.

ここで、ジイモニウム塩とは、一般式（１）で第３級アミンがカチオン化されたイモニウム構造を分子内に２つ有するカチオン成分と、スルホンイミドのアニオン成分とがイオン結合された化合物をいう。

Here, the diimonium salt is a compound in which a cation component having two immonium structures in which a tertiary amine is cationized in the general formula (1) and an anion component of sulfonimide are ionically bonded. .

In the general formula (1), R ¹ and R ² in the anion component are each a fluoroalkyl group which may be the same or different, or a fluoroalkylene group formed by combining them with each other. There are no particular restrictions on the number of atoms or the number of carbon atoms. Among these R ¹ and R ² , a C 1-8 perfluoroalkyl group represented by the following general formula (2) is preferable, and a C 1-4 perfluoroalkyl group is more preferable.

一般式（２）中、ｎ及びｎ’は、１〜８の整数を表す。

In general formula (2), n and n 'represent the integer of 1-8.

  Preferred specific examples of such dimonium salts include bis (trifluoromethanesulfone) imide, bis (pentafluoroethanesulfone) imide having the same perfluoroalkanesulfonyl group, and pentafluoroethanesulfone trifluoromethanesulfonimide having different perfluoroalkanesulfonyl groups. And nonafluoromethanesulfone heptafluoropropanesulfonimide. Among these, bis (trifluoromethanesulfonyl) imide or bis (pentafluoroethanesulfonyl) imide having the same perfluoroalkanesulfonyl group and n and n ′ being 1 or 2 is more preferable in terms of near infrared absorption ability. .

Further, another preferred example of R ¹ and R ² in the anion component in the general formula (1) is represented by the general formula (3), and the number of carbon atoms formed by the combination of R ¹ and R ² is 2 ˜12 perfluoroalkylene groups. This anion component is preferable in terms of further improving the heat resistance of the near infrared absorbing dye.

一般式（３）中、ｍは、２〜１２の整数を表す。

In general formula (3), m represents an integer of 2 to 12.

Here, m is preferably 2 to 8, and 1,3-disulfonylhexafluoropropyleneimide in which m is 3 is particularly preferable.
R in the general formula (1) is a substituent selected from the group consisting of an alkyl group, a halogenated alkyl group, a cyanoalkyl group, an aryl group, a hydroxyl group, a phenyl group and a phenylalkylene group, May be the same or different. Among these, an alkyl group having 1 to 8 carbon atoms or a side chain or an alkyl group, a halogenated alkyl group, a cyanoalkyl group or the like is preferable, and a linear alkyl group or a halogenated alkyl group having 2 to 6 carbon atoms is particularly preferable. . Specific examples of the straight-chain alkyl group and halogenated alkyl group having 2 to 6 carbon atoms include ethyl group, 2,2,2-trifluoroethyl group, propyl group, 3,3,3-trifluoropropyl group, butyl Group, 4,4,4-trifluorobutyl group, 4,4,4-trichlorobutyl group, perfluorobutyl group, perchlorobutyl group, amyl group, isopropyl group, isobutyl group, isoamyl group and the like.

  Moreover, as another preferable example of R in General formula (1), the phenylalkylene group represented by following General formula (4) is preferable, and it is especially preferable that carbon number of the alkylene group is 1-8. In the case of such R, the heat resistance of the near-infrared absorbing dye is improved.

一般式（４）中、Ａは、炭素数１〜１８の直鎖又は側鎖を有するアルキレン基を表し、環Ｂは置換基を有していてもよいベンゼン環を表す。さらに、一般式（４）のフェニルアルキレン基におけるフェニル基は、置換基を有していなくてもよく、或いはアルキル基、水酸基、スルホン酸基、アルキルスルホン酸基、ニトロ基、アミノ基、アルコキシ基、ハロゲン化アルキル基及びハロゲンからなる群から選ばれる少なくとも１種の置換基を有していてもよい。これらのうち、置換基を有していないフェニル基が好ましく、具体的にはベンジル基、フェネチル基、フェニルプロピレン基、フェニル‐α‐メチルプロピレン基、フェニル‐β‐メチルプロピレン基、フェニルブチレン基、フェニルペンチレン基、フェニルオクチレン基等が挙げられ、ベンジル基及びフェネチル基が最も好ましい。

In general formula (4), A represents an alkylene group having a straight chain or a side chain having 1 to 18 carbon atoms, and ring B represents a benzene ring which may have a substituent. Furthermore, the phenyl group in the phenylalkylene group of the general formula (4) may not have a substituent, or an alkyl group, a hydroxyl group, a sulfonic acid group, an alkylsulfonic acid group, a nitro group, an amino group, an alkoxy group. , At least one substituent selected from the group consisting of halogenated alkyl groups and halogens. Of these, a phenyl group having no substituent is preferable, and specifically, a benzyl group, a phenethyl group, a phenylpropylene group, a phenyl-α-methylpropylene group, a phenyl-β-methylpropylene group, a phenylbutylene group, A phenylpentylene group, a phenyloctylene group, etc. are mentioned, A benzyl group and a phenethyl group are the most preferable.

  In addition, as a diimonium salt, a compound that exhibits a blue shift effect can shift the absorption wavelength of light by the diimonium salt to the short wavelength side (visible light side), and has sufficient transmittance in the near infrared region. It is preferable at the point which can be suppressed to. Here, the blue shift effect means that the near-infrared absorbing dye is a diimonium salt containing the sulfonimide represented by the general formula (1) as an anion component, so that the light absorption spectrum is changed to the absorption spectrum of the conventional diimonium salt. Compared to the effect of shifting to the shorter wavelength side.

  Examples of the diimonium salt having a blue shift effect include bis {bis (trifluoromethanesulfone) imidic acid} -N, N, N ′, N′-tetrakis (p-dibenzylaminophenyl) -p-phenylenediimonium, Bis (1,3-disulfonylhexafluoropropylimidic acid) -N, N, N ′, N′-tetrakis (p-dibenzylaminophenyl) -p-phenylenediimonium, bis {bis (trifluoromethanesulfone) imidic acid } -N, N, N ′, N′-tetrakis {p-di (4-fluoride) benzylaminophenyl} -p-phenylenediimonium, bis (1,3-disulfonylhexafluoropropylimidate) -N, N, N ′, N′-tetrakis {p-di (4-fluoride) benzylaminophenyl} -p-phenyle Diimonium, bis {bis (trifluoromethanesulfonyl) imidic acid} -N, N, N ′, N′-tetrakis {p-di (2,2,2-trifluoroethyl) aminophenyl} -p-phenylenediimonium, bis {Bis (trifluoromethanesulfonyl) imidic acid} -N, N, N ′, N′-tetrakis {p-di (4,4,4-trifluorobutyl) aminophenyl} -p-phenylenediimonium, bis {bis ( Trifluoromethanesulfonyl) imidic acid} -N, N, N ′, N′-tetrakis {p-di (4,4,4-trichlorobutyl) aminophenyl} -p-phenylenediimonium, bis {bis (trifluoromethanesulfonyl) Imido acid} -N, N, N ′, N′-tetrakis {p-di (perfluorobutyl) aminophenyl} -p- Enylene diimmonium, bis (1,3-disulfonylhexafluoropropylimidic acid) -N, N, N ′, N′-tetrakis {p-di (2,2,2-trifluoroethyl) aminophenyl} -p -Phenylenediimonium, bis (1,3-disulfonylhexafluoropropylimidic acid) -N, N, N ', N'-tetrakis {p-di (4,4,4-trifluorobutyl) aminophenyl} -p -Phenylenediimonium, bis (1,3-disulfonylhexafluoropropylimidic acid) -N, N, N ', N'-tetrakis {p-di (4,4,4-trichlorobutyl) aminophenyl} -p- Phenylenediimonium, bis (1,3-disulfonylhexafluoropropylimidic acid) -N, N, N ′, N′-tetrakis {p-di (par Fluorobutyl) aminophenyl} -p-phenylenediimonium and the like. These diimonium salts can be used alone or in admixture of two or more.

  Although the said diimonium salt can be used independently, unless the effect of this invention is impaired, it can also be used in combination with another near-infrared absorption pigment | dye suitably. Other near-infrared absorbing dyes are not particularly limited. For example, polymethine, cyanine, phthalocyanine, naphthalocyanine, dithiol metal complex, naphthoquinone, anthroquinone, triphenylmethane, aminium, diimmonium And the like. Examples of commercially available dyes include NK-5060, NK-5706, NK-8758 (above, manufactured by Hayashibara Biochemical Laboratories), KAYASORBIR-022, KAYASORBIRG-023, and KAYASORBIRG-040. (Nippon Kayaku Co., Ltd.), e-ex color IR1, e-ex color IR3, e-ex color 810K, e-ex color 812K, e-ex color 814K, e-ex color 905B (above, manufactured by Nippon Shokubai Co., Ltd.) ), SIR-128, SIR-130, SIR-132, SIR-159 (above, manufactured by Mitsui Chemicals, Inc.), CIR-1080, CIR-1081 (above, manufactured by Nippon Carlit Co., Ltd.), and the like.

  The method for forming the near-infrared shielding layer 17 on the transparent substrate film 11 is not particularly limited, and a method that can be uniformly formed is preferable. For example, the method of forming the solution containing a near-infrared absorption pigment | dye by the wet coating method is mentioned. When forming the near-infrared shielding layer 17, it can carry out using the organic binder which dissolved or disperse | distributed the said near-infrared absorption pigment | dye. Examples of the organic binder include polyolefins such as polyethylene and polypropylene; polystyrene compounds such as polystyrene and poly (α-methylstyrene); styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylic acid copolymers, Styrene copolymers such as styrene-acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; poly (meth) methyl acrylate, poly (meth) ethyl acrylate, Poly (meth) acrylates such as poly (meth) acrylate propyl, poly (meth) acrylate butyl, poly (meth) acrylate cyclohexyl, etc .; polyethers such as polyoxymethylene and polyethylene oxide; polyethylene succinate, polybutylene Adipate, Polyurethane; polycarbonate resins; polylactic acid, polyglycolic acid, polycaprolactone, polyesters such as polyethylene terephthalate and epoxy resins. These can be used alone or in admixture of two or more.

  The near infrared shielding layer 17 may contain other components in addition to the organic binder as long as the effects of the present invention are not impaired. The other components are not particularly limited, and examples include additives such as polymerization inhibitors, antioxidants, dispersants, surfactants, surface modifiers, light stabilizers, etc. Any solvent can be added as long as it is post-dried. Further, the thickness of the near infrared shielding layer 17 is preferably about 2 to 20 μm. When the thickness of the near infrared shielding layer 17 is less than 2 μm, it is difficult to sufficiently develop the near infrared shielding function, which is not preferable. On the other hand, when the thickness exceeds 20 μm, problems such as a decrease in the bending resistance of the near infrared shielding layer 17 occur, which is not preferable.

  The near-infrared shielding layer 17 has a transmittance in the near-infrared region with a light wavelength of 800 to 1000 nm of preferably 40% or less, and more preferably 30% or less. If the transmittance exceeds 40%, it is not preferable from the viewpoint that a near infrared ray shielding function cannot be sufficiently provided and a peripheral device such as a remote control device may malfunction.

  The near-infrared shielding layer 17 preferably contains a dye for correcting the color tone in order to improve the color purity and contrast of the emission color of the display. Such a color correction dye may be a general dye having a desired absorption wavelength in the visible light region, for example, squarylium, azomethine, cyanine, xanthene, azo, tetraazaporphyrin, pyromethene. Mention may be made of generally available dyes such as systems.

  Now, to explain the operation of the present embodiment, when preparing the hard coat film 10, for example, a coating liquid as an adhesive is applied on a polyester film as the transparent base film 11 to form the adhesive layer 12, A hard coat film 10 is obtained by applying a hard coat layer coating solution thereon and then curing it by irradiating with ultraviolet rays. In the obtained hard coat film 10, since the difference in refractive index between the transparent base film 11 and the hard coat layer 13 is suppressed within 0.02, the interface between the transparent base film 11 and the hard coat layer 13 is suppressed. The interference of the reflected light at is suppressed, and rainbow-colored unevenness (interference fringes) can be suppressed. Furthermore, since the thickness of the adhesive layer 12 formed of, for example, a copolyester resin is set to an extremely thin thickness of 5 to 30 nm, interference of reflected light by the adhesive layer 12 can be avoided, and at the same time, the copolyester Due to the adhesiveness of the resin, the transparent base film 11 made of a polyester film and the hard coat layer 13 are sufficiently bonded.

The effects exhibited by the above embodiment will be described collectively below.
In the hard coat film 10 of the present embodiment, the difference in refractive index between the transparent base film 11 and the hard coat layer 13 is set within 0.02, and the film thickness of the adhesive layer 12 is 5 to 30 nm. Is set. Therefore, the adhesion of the hard coat layer 13 to the transparent substrate film 11 can be improved while suppressing the generation of interference fringes.

  -Since the said transparent base film 11 is a polyethylene terephthalate, while being easy to shape | mold to predetermined thickness, acquisition is easy and reduction of manufacturing cost can be aimed at.

  -Since the metal oxide fine particles are contained in the hard coat layer 13, the difference in refractive index between the transparent substrate film 11 and the hard coat layer 13 can be easily set within 0.02. .

  The antireflection layer 15 is further laminated on the hard coat layer 13 to exhibit antireflection performance, and the antireflection film 14 can be suitably used for an electronic image display device.

  -The near-infrared shielding layer 17 is laminated on the transparent base film 11 on the side opposite to the side on which the antireflection layer 15 is provided, so that the performance of near-infrared shielding can be expressed and reflected. The preventive near-infrared shielding film 16 can be suitably used for an electronic image display device.

Hereinafter, the embodiment will be described more specifically with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples. The performance of the hard coat film 10 in each example was evaluated according to the following method.
(A) Optical characteristics (a-1) Evaluation of interference fringes In order to eliminate the influence of back surface reflection, a sample was produced by painting the surface opposite to the surface on which the hard coat layer 13 was provided with a black paint. When the sample was visually observed using a three-wavelength fluorescent lamp as a light source in a dark room, the intensity of interference fringes was evaluated.

◎: No interference fringes are visible, ○: Weak interference fringes are visible, ×: Strong interference fringes are visible.
(A-2) Measurement of minimum reflectance In order to eliminate the influence of back surface reflection, a sample in which the surface opposite to the surface provided with the hard coat layer 13 was painted with a black paint was prepared. Using the UV-visible spectrophotometer (manufactured by JASCO Corporation, V-560), the spectral reflectance spectrum of 5 ° and −5 ° of the light wavelength 400 to 800 nm was measured for the obtained sample, and the reflectance spectrum The minimum reflectance (%) was read.
(A-3) Measurement of near-infrared transmittance A sample was measured using an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, V-560), and near-infrared transmittance at each wavelength of 800 nm, 900 nm, and 1000 nm ( %).
(B) Physical characteristics (b-1) Adhesiveness A cross-cut peeling tape test was performed on the surface side provided with the hard coat layer 13 in accordance with JIS D0202-1998. Using cellophane tape (manufactured by Nichiban Co., Ltd., CT24), the film was adhered to the film and then peeled off. Judgment is represented by the number of squares that do not peel out of 100 squares, and the case where peeling does not occur is 100/100, and the case where peeling completely occurs is represented as 0/100.
[Preparation of coating liquid as adhesive for forming adhesive layer (hereinafter referred to as adhesive coating liquid)]
(1) Synthesis of copolyester resin (A)
100 parts by mass of dimethyl terephthalate, 100 parts by mass of dimethyl isophthalate, 30.3 parts by mass of ethylene glycol, 150 parts by mass of neopentyl glycol, 0.1 part by mass of zinc acetate and 0.1 part by mass of antimony trioxide are used in a transesterification reaction vessel. The resulting mixture was heated to 180 ° C. and reacted for 4 hours to conduct a transesterification reaction. Thereafter, 5 parts by mass of 5-sodium sulfoisophthalic acid was added, and an esterification reaction was performed at 240 ° C. for 1 hour. Next, the temperature was raised to 250 ° C., the inside of the system was reduced in pressure to 1 mmHg (133 Pa), and a polycondensation reaction was performed for 2 hours to obtain a copolyester resin (A).
(2) Synthesis of cross-linking agent (B) Charge 300 parts by mass of ion-exchanged water into a flask and heat to 60 ° C. under a nitrogen stream, and add 0.3 part by mass of ammonium persulfate and 0.3 part by mass of sodium hydrogen nitrite. Added. Thereafter, a mixture of 20.2 parts by mass of methyl methacrylate, 21.2 parts by mass of 2-isopropenyl-2-oxazoline, 45.5 parts by mass of polyethylene oxide methacrylic acid and 10.2 parts by mass of acrylamide was added dropwise over 4 hours. Stirring was continued for 1 hour after completion of the dropwise addition to obtain a 25% by mass aqueous dispersion of the crosslinking agent (B).
(3) Preparation of adhesive coating solution 65 parts by mass of a 30% by mass aqueous dispersion of the copolyester resin (A), 40 parts by mass of a 25% by mass aqueous dispersion of the crosslinking agent (B) and ion-exchanged water 450 parts by mass was mixed to obtain an adhesive coating solution.
(Preparation of transparent substrate film A)
The biaxially stretched polyester film (polyethylene terephthalate film provided with an adhesive film on one side, manufactured by Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm, refractive index 1.65) is bonded to the surface without the adhesive film. The agent coating solution was applied by a gravure coating method. When the cross section of the film was observed with an SEM, the thickness of the adhesive layer 12 was 15 nm as a dry film thickness.
(Preparation of transparent substrate film B)
An adhesive coating liquid was applied to the surface of the biaxially stretched polyester film used in the production of the transparent base film A without an adhesive film by a gravure coating method. When the cross section of the film was observed by SEM, the film thickness of the adhesive layer was 5 nm.
(Preparation of transparent substrate film C)
An adhesive coating liquid was applied to the surface of the biaxially stretched polyester film used in the production of the transparent base film A without an adhesive film by a gravure coating method. When the cross section of the film was observed by SEM, the film thickness of the adhesive layer was 30 nm.
(Preparation of transparent substrate film D)
An adhesive coating liquid was applied to the surface of the biaxially stretched polyester film used in the production of the transparent base film A without an adhesive film by a gravure coating method. When the cross section of the film was observed by SEM, the film thickness of the adhesive layer was 40 nm.
(Preparation of hard coat layer coating solution A)
Antimony-doped tin oxide 30% by mass methyl ethyl ketone dispersion (antimony-doped tin oxide average particle size 98 nm, manufactured by Ishihara Sangyo Co., Ltd., SNS-10M) 83 parts by mass, polyfunctional acrylate compound (hexafunctional dipentaerythritol hexaacrylate) And pentafunctional dipentaerythritol pentaacrylate, average functional group number 5.5, Nippon Kayaku Co., Ltd., DPHA) 75 parts by mass and UV radical initiator (Ciba Specialty Chemicals Co., Ltd., Irgacure 184) 5 parts by mass was stirred and mixed to obtain a hard coat layer coating solution A.
(Preparation of hard coat layer coating solution B)
Antimony-doped tin oxide 30 mass% methyl ethyl ketone dispersion (antimony-doped tin oxide average particle size 98 nm, manufactured by Ishihara Sangyo Co., Ltd., SNS-10M) 73 parts by mass, polyfunctional acrylate compound (hexafunctional dipentaerythritol hexaacrylate) And pentafunctional dipentaerythritol pentaacrylate, average functional group number 5.5, Nippon Kayaku Co., Ltd., DPHA 78 parts by mass and UV radical initiator (Ciba Specialty Chemicals Co., Ltd., Irgacure 184) 5 parts by mass was stirred and mixed to obtain a hard coat layer coating solution B.
(Preparation of hard coat layer coating solution C)
Antimony-doped tin oxide 30 mass% methyl ethyl ketone dispersion (antimony-doped tin oxide average particle size 98 nm, manufactured by Ishihara Sangyo Co., Ltd., SNS-10M) 57 parts by mass, polyfunctional acrylate compound (hexafunctional dipentaerythritol hexaacrylate) And pentafunctional dipentaerythritol pentaacrylate, average number of functional groups 5.5, Nippon Kayaku Co., Ltd., DPHA) 83 parts by mass and UV radical initiator (Ciba Specialty Chemicals Co., Ltd., Irgacure 184) 5 parts by mass was stirred and mixed to obtain a hard coat layer coating solution C.
(Preparation of low refractive index layer coating solution A)
104 parts by mass of perfluoro- (1,1,9,9-tetrahydro-2,5-bisfluoromethyl-3,6-dioxanonenol) and bis (2,2,3,3,4,4,4) 5,5,6,6,7,7-dodecafluoroheptanoyl) peroxide-containing fluorine-containing allyl ether polymer (number average molecular weight 72) obtained by polymerization reaction of 11 parts by mass of an 8% by mass perfluorohexane solution Fluorine-containing reactive heavy having a polymerizable double bond from 5 parts by mass, 43 parts by mass of methyl ethyl ketone (MEK), 1 part by mass of pyridine, and 1 part by mass of α-fluoroacrylic acid fluoride. A combined solution (solid content 13% by mass, α-fluoroacryloyl group introduction rate 40 mol%) was prepared. Also, hollow silica sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name: ELCOM NY-1001 SIV, 25% dispersion of hollow silica sol with isopropyl alcohol, average particle size: 60 nm) 2000 parts by mass, γ-acryloyloxypropyltrimethoxysilane 70 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., KBM5103) and 80 parts by mass of distilled water were mixed to prepare modified hollow silica fine particles (sol) (average particle size: 60 nm). And 50 parts by mass of the fluorine-containing reactive polymer solution, 50 parts by mass of the modified hollow silica fine particles, 2 parts by mass of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.), and 2000 parts by mass of isopropyl alcohol. And a low refractive index layer coating solution A was obtained.
(Preparation of low refractive index layer coating solution B)
1,10-Diacryloyloxy-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecane, 70 parts by mass, dipenta Mix 10 parts by mass of erythritol hexaacrylate, 60 parts by mass of silica gel fine particle dispersion (manufactured by Nissan Chemical Industries, Ltd., XBA-ST), and 5 parts by mass of photopolymerization initiator (manufactured by Nippon Kayaku Co., Ltd., KAYACURE BMS). Thus, a low refractive index layer coating solution B was obtained.
(Preparation of near-infrared shielding layer coating solution A)
As a near-infrared absorbing dye, diimonium salt (manufactured by Nippon Carlit Co., Ltd., 5.0 parts by mass of CIR-1085F, 100 parts by mass of acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., Dianal BR-80) as a binder resin, and as a solvent 450 parts by mass of methyl ethyl ketone and 450 parts by mass of toluene were mixed, stirred and dissolved to obtain a near-infrared shielding layer coating solution A.
(Preparation of near-infrared shielding layer coating solution B)
Diimonium salt (Nippon Carlit Co., Ltd., CIR-1085F) 5.0 parts by mass as a near-infrared absorbing dye, Squalic acid derivative (Kyowa Hakko Chemical Co., Ltd., SD-1566) 0.2 mass as a specific wavelength absorbing dye Part, acrylic resin (Mitsubishi Rayon Co., Ltd., Dainar BR-80) 100 parts by weight as binder resin, 450 parts by weight of methyl ethyl ketone and 450 parts by weight of toluene as a solvent are mixed and stirred to dissolve, near-infrared shielding layer It was set as the coating liquid B.
(Example 1)
The hard coat layer coating solution A is applied on the adhesive layer 12 of the transparent base film A by a gravure coating method so as to have a dry film thickness of about 5 μm, and then cured by irradiating with ultraviolet rays with an energy of 400 mJ / cm ^2. By doing so, the hard coat film 10 was produced. The refractive index of the hard coat layer 13 was 1.64. The evaluation results for this hard coat film 10 are shown in Table 1.
(Example 2)
A hard coat film 10 was produced in the same manner as in Example 1 except that the transparent base film B was used in place of the transparent base film A in Example 1. The refractive index of the hard coat layer 13 was 1.64. The evaluation results are shown in Table 1.
(Example 3)
In Example 1, the hard coat film 10 was produced like Example 1 except having used the transparent base film C instead of the transparent base film A. FIG. The refractive index of the hard coat layer 13 was 1.64. The evaluation results are shown in Table 1.
Example 4
A hard coat film 10 was produced in the same manner as in Example 1, except that the hard coat layer coating solution B was used in place of the hard coat layer coating solution A in Example 1. The refractive index of the hard coat layer 13 was 1.63. The evaluation results are shown in Table 1.
(Comparative Example 1)
In Example 1, instead of the transparent substrate film A, an adhesive film of a biaxially stretched polyester film (polyethylene terephthalate film provided with an adhesive film on one side, manufactured by Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm) A hard coat film was produced in the same manner as in Example 1 except that the surface having no surface was used. The refractive index of the hard coat layer was 1.64. The evaluation results are shown in Table 1.
(Comparative Example 2)
In Example 1, a hard coat film was produced in the same manner as in Example 1 except that the transparent base film D was used instead of the transparent base film A. The refractive index of the hard coat layer was 1.64. The evaluation results are shown in Table 1.
(Comparative Example 3)
A hard coat film was produced in the same manner as in Example 1 except that the hard coat layer coating solution C was used in place of the hard coat layer coating solution A. The refractive index of the hard coat layer was 1.60. The evaluation results are shown in Table 1.

表１に示す結果より、実施例１〜４においては、接着層１２の膜厚が５〜３０ｎｍの範囲であることから、透明基材フィルム１１に対するハードコート層１３の密着性を保持しつつ、干渉縞の発生を十分に抑えることができた。一方、比較例１では接着層が設けられていないため、透明基材フィルムに対するハードコート層の密着性が全く不良であった。比較例２では接着層の膜厚が３０ｎｍよりも厚いため、干渉縞が強く見えることがわかった。また、比較例３のように接着層の膜厚が５〜３０ｎｍの範囲であっても、ハードコート層と透明基材フィルムの屈折率差が０．０２よりも大きいため、干渉縞が強く見えることがわかった。
（実施例５）
実施例１で作製したハードコートフィルム１０のハードコート層１３上に低屈折率層塗布液Ａを、光学膜厚が１１０〜１２５ｎｍになるようにグラビアコート法で塗布し、乾燥後、窒素雰囲気下で４００ｍＪ／ｃｍ^２の出力で紫外線を照射して硬化させることにより、反射防止性フィルムを１１作製した。反射防止性フィルム１４についての評価結果を表２に示す。
（実施例６）
実施例５において、ハードコートフィルム１０として実施例１で作製したものに代えて実施例２で作製したものを用いた以外は実施例５と同様にして、反射防止性フィルム１４を作製した。その評価結果を表２に示す。
（実施例７）
実施例５において、ハードコートフィルム１０として実施例１で作製したものに代えて実施例３で作製したものを用いた以外は実施例５と同様にして、反射防止性フィルム１４を作製した。その評価結果を表２に示す。
（実施例８）
実施例５において、低屈折率層塗布液Ａに代えて低屈折率層塗布液Ｂを用いた以外は実施例５と同様にして、反射防止性フィルム１４を作製した。その評価結果を表２に示す。
（比較例４）
実施例５において、ハードコートフィルムとして実施例１で作製したものに代えて比較例１で作製したものを用いた以外は実施例５と同様にして、反射防止性フィルムを作製した。その評価結果を表２に示す。
（比較例５）
実施例５において、ハードコートフィルムとして実施例１で作製したものに代えて比較例２で作製したものを用いた以外は実施例５と同様にして、反射防止性フィルムを作製した。その評価結果を表２に示す。
（比較例６）
実施例５において、ハードコートフィルムとして実施例１で作製したものに代えて比較例３で作製したものを用いた以外は実施例５と同様にして、反射防止性フィルムを作製した。その評価結果を表２に示す。

From the results shown in Table 1, in Examples 1 to 4, since the film thickness of the adhesive layer 12 is in the range of 5 to 30 nm, while maintaining the adhesion of the hard coat layer 13 to the transparent substrate film 11, The generation of interference fringes could be sufficiently suppressed. On the other hand, since the adhesive layer was not provided in the comparative example 1, the adhesiveness of the hard-coat layer with respect to a transparent base film was completely unsatisfactory. In Comparative Example 2, it was found that the interference fringes look strong because the thickness of the adhesive layer is greater than 30 nm. Moreover, even if the film thickness of the adhesive layer is in the range of 5 to 30 nm as in Comparative Example 3, the interference fringes look strong because the refractive index difference between the hard coat layer and the transparent substrate film is larger than 0.02. I understood it.
(Example 5)
The low refractive index layer coating liquid A is applied on the hard coat layer 13 of the hard coat film 10 produced in Example 1 by a gravure coating method so that the optical film thickness becomes 110 to 125 nm, dried, and then in a nitrogen atmosphere. 11 were produced by irradiating and curing ultraviolet rays with an output of 400 mJ / cm ² . The evaluation results for the antireflection film 14 are shown in Table 2.
(Example 6)
In Example 5, an antireflective film 14 was produced in the same manner as in Example 5 except that the hard coat film 10 used in Example 2 was used instead of the hard coat film 10 produced in Example 1. The evaluation results are shown in Table 2.
(Example 7)
In Example 5, an antireflective film 14 was produced in the same manner as in Example 5 except that the hard coat film 10 was replaced with the hard coat film 10 prepared in Example 1, except that the hard coat film 10 was prepared in Example 3. The evaluation results are shown in Table 2.
(Example 8)
In Example 5, an antireflective film 14 was produced in the same manner as in Example 5 except that the low refractive index layer coating solution B was used in place of the low refractive index layer coating solution A. The evaluation results are shown in Table 2.
(Comparative Example 4)
In Example 5, an antireflection film was produced in the same manner as in Example 5 except that the hard coat film was produced in Comparative Example 1 instead of the one produced in Example 1. The evaluation results are shown in Table 2.
(Comparative Example 5)
In Example 5, an antireflection film was produced in the same manner as in Example 5 except that the hard coat film was produced in Comparative Example 2 instead of that produced in Example 1. The evaluation results are shown in Table 2.
(Comparative Example 6)
In Example 5, an antireflection film was produced in the same manner as in Example 5 except that the hard coat film was produced in Comparative Example 3 instead of that produced in Example 1. The evaluation results are shown in Table 2.

表２に示したように、実施例５〜８においては、ハードコート層１３上に低屈折率層を塗布した結果、反射防止性フィルム１４としても、密着性及び干渉縞の評価が良好であることがわかった。一方、比較例４では反射防止性フィルムにおいて接着層が設けられていないため、透明基材フィルムに対するハードコート層の密着性が全く得られなかった。比較例５では反射防止性フィルムにおいて接着層の膜厚が３０ｎｍよりも厚いため、干渉縞が強く見られた。さらに、比較例６では反射防止性フィルムにおいて接着層の膜厚が５〜３０ｎｍの範囲であっても、ハードコート層と透明基材フィルムの屈折率差が０．０２を越えているため、干渉縞が強く見える結果であった。
（実施例９）
実施例５で作製した反射防止性フィルム１４の反射防止層１５とは反対側の透明基材フィルム１１上に、近赤外線遮蔽層塗布液Ａを、乾燥膜厚１０μｍになるようにグラビアコート法により成膜して近赤外線遮蔽層１７を形成した。その後、１００℃で１０分間乾燥することにより、反射防止性近赤外線遮蔽フィルム１６を作製した。得られた反射防止性近赤外線遮蔽フィルム１６についての評価結果を表３に示す。
（実施例１０）
実施例９において、反射防止性フィルム１４を実施例５で作製したものに代えて実施例６で作製したものを用いた以外は実施例９と同様にして、反射防止性近赤外線遮蔽フィルム１６を作製した。その評価結果を表３に示す。
（実施例１１）
実施例９において、反射防止性フィルム１４を実施例５で作製したものに代えて実施例７で作製したものを用いた以外は実施例９と同様にして、反射防止性近赤外線遮蔽フィルム１６を作製した。その評価結果を表３に示す。
（実施例１２）
実施例９において、反射防止性フィルム１４を実施例５で作製したものに代えて実施例８で作製したものを用いた以外は実施例９と同様にして、反射防止性近赤外線遮蔽フィルム１６を作製した。その評価結果を表３に示す。
（実施例１３）
実施例５で作製した反射防止性フィルム１４の反射防止層１５とは反対側の透明基材フィルム１１上に、近赤外線遮蔽層塗布液Ｂを、乾燥膜厚１０μｍになるようにグラビアコート法により成膜した後、１２０℃で５分間乾燥することにより、反射防止性近赤外線遮蔽フィルム１６を作製した。その評価結果を表３に示す。
（比較例７）
実施例９において、反射防止性フィルムとして実施例５で作製したものに代えて比較例４で作製したものを用いた以外は実施例９と同様にして、反射防止性近赤外線遮蔽フィルムを作製した。その評価結果を表３に示す。
（比較例８）
実施例９において、反射防止性フィルムとして実施例５で作製したものに代えて比較例５で作製したものを用いた以外は実施例９と同様にして、反射防止性近赤外線遮蔽フィルムを作製した。その評価結果を表３に示す。
（比較例９）
実施例９において、反射防止性フィルムとして実施例５で作製したものに代えて比較例６で作製したものを用いた以外は実施例９と同様にして、反射防止性近赤外線遮蔽フィルムを作製した。その評価結果を表３に示す。

As shown in Table 2, in Examples 5 to 8, as a result of applying the low refractive index layer on the hard coat layer 13, the antireflection film 14 also has good evaluation of adhesion and interference fringes. I understood it. On the other hand, in Comparative Example 4, since no adhesive layer was provided in the antireflection film, no adhesion of the hard coat layer to the transparent substrate film was obtained. In Comparative Example 5, since the thickness of the adhesive layer in the antireflection film was thicker than 30 nm, interference fringes were strongly observed. Further, in Comparative Example 6, even if the film thickness of the adhesive layer in the antireflection film is in the range of 5 to 30 nm, the difference in refractive index between the hard coat layer and the transparent substrate film exceeds 0.02, which causes interference. The result was that the stripes looked strong.
Example 9
On the transparent base film 11 opposite to the antireflection layer 15 of the antireflection film 14 produced in Example 5, the near-infrared shielding layer coating liquid A is applied by a gravure coating method so as to have a dry film thickness of 10 μm. A near-infrared shielding layer 17 was formed by film formation. Then, the antireflective near-infrared shielding film 16 was produced by drying for 10 minutes at 100 degreeC. Table 3 shows the evaluation results of the obtained antireflection near-infrared shielding film 16.
(Example 10)
In Example 9, an antireflection near-infrared shielding film 16 was prepared in the same manner as in Example 9 except that the antireflection film 14 prepared in Example 6 was used instead of the one prepared in Example 5. Produced. The evaluation results are shown in Table 3.
(Example 11)
In Example 9, the antireflection near-infrared shielding film 16 was prepared in the same manner as in Example 9 except that the antireflection film 14 produced in Example 7 was used instead of the one produced in Example 5. Produced. The evaluation results are shown in Table 3.
Example 12
In Example 9, an antireflection near-infrared shielding film 16 was prepared in the same manner as in Example 9 except that the antireflection film 14 prepared in Example 8 was used instead of the one prepared in Example 5. Produced. The evaluation results are shown in Table 3.
(Example 13)
On the transparent substrate film 11 opposite to the antireflection layer 15 of the antireflection film 14 produced in Example 5, the near-infrared shielding layer coating liquid B is applied by a gravure coating method so as to have a dry film thickness of 10 μm. After the film formation, the film was dried at 120 ° C. for 5 minutes to produce an antireflection near-infrared shielding film 16. The evaluation results are shown in Table 3.
(Comparative Example 7)
In Example 9, an antireflection near-infrared shielding film was produced in the same manner as in Example 9 except that the antireflection film used in Comparative Example 4 was used instead of the one produced in Example 5. . The evaluation results are shown in Table 3.
(Comparative Example 8)
In Example 9, an antireflection near-infrared shielding film was produced in the same manner as in Example 9 except that the antireflection film used in Comparative Example 5 was used instead of the one produced in Example 5. . The evaluation results are shown in Table 3.
(Comparative Example 9)
In Example 9, an antireflection near-infrared shielding film was produced in the same manner as in Example 9 except that the antireflection film was prepared in Comparative Example 6 instead of the one produced in Example 5. . The evaluation results are shown in Table 3.

表３に示した結果より、実施例９〜１３においては、反射防止性近赤外線遮蔽フィルム１６として、密着性及び干渉縞の評価が良好であった。一方、比較例７では反射防止性近赤外線遮蔽フィルムにおいて接着層が設けられていないため、透明基材フィルムに対するハードコート層の密着性が全く発現されなかった。比較例８では反射防止性近赤外線遮蔽フィルムにおいて接着層の膜厚が３０ｎｍよりも厚いため、干渉縞が強く見られた。さらに、比較例９では反射防止性近赤外線遮蔽フィルムにおいて接着層の膜厚が５〜３０ｎｍであっても、ハードコート層と透明基材フィルムの屈折率差が０．０２を越えていると、干渉縞が強く見える結果であった。

From the results shown in Table 3, in Examples 9 to 13, as the antireflection near-infrared shielding film 16, the evaluation of adhesion and interference fringes was good. On the other hand, in Comparative Example 7, since the adhesive layer was not provided in the antireflection near-infrared shielding film, the adhesion of the hard coat layer to the transparent substrate film was not expressed at all. In Comparative Example 8, since the film thickness of the adhesive layer in the antireflection near-infrared shielding film was thicker than 30 nm, interference fringes were strongly observed. Furthermore, in Comparative Example 9, even if the film thickness of the adhesive layer in the antireflection near-infrared shielding film is 5 to 30 nm, when the refractive index difference between the hard coat layer and the transparent substrate film exceeds 0.02, The interference fringes looked strong.

In addition, this embodiment can also be changed and embodied as follows.
-As a polyester film which forms the transparent base film 11, a polyethylene naphthalate film, a polybutylene terephthalate film, etc. can also be used.

-An acrylic resin, a nylon resin, etc. can also be used as an adhesive agent which forms the contact bonding layer 12. FIG.
When the adhesive layer 12 is provided on the transparent base film 11, a pretreatment agent (primer) such as a silane coupling agent is applied on the transparent base film 11 in advance to improve adhesion. it can.

Further, the technical idea that can be grasped from the embodiment will be described below.
The hard coat film according to claim 2, wherein the polyester film is a polyethylene terephthalate film. When constituted in this way, in addition to the effect of the invention according to claim 2, it is easy to mold, obtain easily, and reduce the manufacturing cost.

  The hard coat film according to claim 3, wherein the metal oxide fine particles have an average particle diameter of 10 to 150 nm. When comprised in this way, the effect of the invention which concerns on Claim 3 can be exhibited more effectively.

  -The film thickness of the said contact bonding layer is 10-20 nm, The hard coat film as described in any one of Claims 1-3 characterized by the above-mentioned. When comprised in this way, the effect of the invention which concerns on any one of Claims 1-3 can be exhibited most effectively.

  The hard coat film according to any one of claims 1 to 3, wherein the adhesive forming the adhesive layer is formed of a copolyester resin. When comprised in this way, in addition to the effect of the invention which concerns on any one of Claims 1-3, the adhesiveness of the hard-coat layer with respect to a transparent base film can be improved.

  The hard coat film according to any one of claims 1 to 3, wherein the adhesive forming the adhesive layer contains a crosslinking agent. When comprised in this way, in addition to the effect of the invention which concerns on any one of Claims 1-3, the abrasion resistance of the contact bonding layer surface can be improved.

(A) is sectional drawing which shows the hard coat film in embodiment, (b) is sectional drawing which shows an antireflection film, (c) is sectional drawing which shows an antireflection near-infrared shielding film.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Hard coat film, 11 ... Transparent base film, 12 ... Adhesive layer, 13 ... Hard coat layer, 14 ... Antireflection film, 15 ... Antireflection layer, 16 ... Antireflection near-infrared shielding film, 17 ... Near Infrared shielding layer.

Claims (5)

The transparent base film is formed by laminating a hard coat layer via an adhesive layer, the refractive index difference between the transparent base film and the hard coat layer is within 0.02, and the thickness of the adhesive layer Is a hard coat film characterized by being 5-30 nm. The hard coat film according to claim 1, wherein the transparent substrate film is a polyester film. The hard coat film according to claim 1, wherein the hard coat layer contains metal oxide fine particles. An antireflection film, comprising an antireflection layer further laminated on the hard coat layer of the hard coat film according to any one of claims 1 to 3. The antireflection film according to claim 4, wherein the antireflection film is formed by laminating a near-infrared shielding layer on a transparent base film opposite to the side on which the antireflection layer is provided. Near-infrared shielding film.

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