TW201622982A - Transparent multilayer film and touch panel display - Google Patents

Abstract

A transparent multilayer film wherein a first highly adhesive layer and a high refractive index layer are sequentially laminated on one surface of a transparent resin layer, while a second highly adhesive layer, a hard coat layer and a low refractive index layer are sequentially laminated on the other surface of the transparent resin layer. The first and second highly adhesive layers are adjusted to have a refractive index of 1.5-1.7 and a thickness of 30-200 nm; the high refractive index layer is adjusted to have a refractive index of 1.6-1.8 and a thickness of 120-2,000 nm; and the low refractive index layer is adjusted to have a refractive index of 1.2-1.5 and a thickness of 10-200 nm. The thus-obtained transparent multilayer film is provided with a patterned transparent conductive layer, and is capable of suppressing a pattern becoming visible due to color difference, while having a thin thickness and high light transmissivity, even if the transparent multilayer film has a simple structure. In cases where this transparent multilayer film is used in a capacitive touch panel display that internally has a void layer, the formation of a water mark is prevented even if the haze is low. In cases where this transparent multilayer film is applied to a high-definition display device, glare is able to be suppressed.

Description

Transparent laminated film and touch panel display

The present invention relates to a transparent laminated film which can be used for a display device (touch panel display or the like) having a patterned transparent conductive layer, and a capacitance type touch panel display including the same.

With the advancement of an electronic display as a Man Machine Interface, a dialog type input system is becoming widespread, and a device that integrates a touch panel (coordinate input device) and a display is widely used in ATM (automatic withdrawal) Machine), merchandise management, outdoor work (field, sales), navigation display, entertainment machines, etc. A lightweight display such as a liquid crystal display. Since a thin display can be made without a keyboard, the use of a touch panel in a mobile device is also increasing. The touch panel is a device that inputs predetermined information by a finger or a pen or the like by inputting a predetermined position on a computer or the like, and can be classified into an optical method, an ultrasonic method, and an electrostatic capacity by a position detection method. Mode, resistive film method, etc.

Among these methods, the electrostatic capacitance method is a method of detecting the position by using a change in electrostatic capacitance. However, in recent years, a projection type electrostatic capacitance type touch panel using an ITO grid method is superior in terms of functionality. Mobile phone, mobile phone, electronic paper, tablet PC (PC), tablet (pen tablet), game machine, etc. The machine is being used and is being injected. Especially in smart phones or tablet PCs, high-definition display devices are beginning to spread. In addition, a TV equipped with a touch panel on a display of a high-definition television (4K TV) having four times the number of pixels of a full high-definition television (FHDTV) is being developed. A high-resolution pen input device in the construction or medical field.

Therefore, such a device also requires optical characteristics such as high transparency or anti-glare property. In particular, in a device having a gap (void layer) inside, when a display surface is touched by a finger or a pen, a phenomenon (black dot) in which the opposing faces of the void layer are in close contact with each other and becomes black is generated. This phenomenon is called water mark (WM). However, since the capacitance type touch panel has many devices having a void layer, it is also required to have waterproof grain (AWM) properties.

Therefore, the electrostatic capacitance type touch panel also requires a high degree of optical characteristics. However, in the electrostatic capacitance type touch panel, the transparent conductive layer is entirely patterned on the display portion, and the pattern is easily generated due to the color difference between the pattern portion and the non-pattern portion. A phenomenon that is recognized (the so-called "see pattern" or "see outline" phenomenon). As a method for suppressing the phenomenon of seeing a profile, a method of combining a high refractive index layer and a low refractive index layer as an index matching layer is generally used. However, in this method, since the laminated high refractive index layer and the low refractive index layer are used as the refractive index matching layer, the layer structure of the touch panel is complicated, and it is difficult to cope with the demand for thinning in recent years. Therefore, a method of using a high refractive index layer alone as an index matching layer has also been proposed.

Japanese Laid-Open Patent Publication No. 2012-25066 (Patent Document 1) discloses a transparent conductive film which is a transparent film in which a hard coat layer and an intermediate layer are sequentially laminated from one surface of a transparent base film, and the intermediate layer is formed. The titanium oxide microparticles or the zirconia microparticles and the active energy ray-curable resin are contained, and the light having a wavelength of 400 nm has a refractive index of 1.65 to 1.90 and a film thickness of 60 to 115 nm, and the patterned tin indium oxide layer is laminated on the intermediate layer. On the outside, the light having a wavelength of 400 nm of the tin indium oxide layer has a refractive index of 1.85 to 2.35 and a film thickness of 5 to 50 nm. This document describes a laminated hard coat layer, an antiglare layer, an anti-fingerprint layer, a self-healing layer, an antireflection layer or an antiglare reflective layer as a functional layer on the other side of the transparent base film.

However, the transparent conductive film cannot exhibit high optical characteristics. For example, even if an anti-glare antireflection layer is used as a functional layer, glare cannot be effectively suppressed. Moreover, it is also difficult to have both low haze and waterproof texture (AWM).

Advanced technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2012-25066 (Application No.)

Accordingly, it is an object of the present invention to provide a transparent laminated film having a patterned transparent conductive layer and having a thin structure and high light transmittance even in a simple structure, and capable of suppressing recognition of a pattern due to chromatic aberration. And a capacitive touch panel display having the film.

Another object of the present invention is to provide an electrostatic capacitance type touch panel display having a void layer therein, which can prevent the occurrence of water marks even at a low haze, and can suppress glare even when applied to a high-definition display device. A transparent laminated film and a capacitive touch panel display having the same.

The inventors of the present invention have intensively studied in order to achieve the above-mentioned problems, and as a result, it has been found that a first easy-to-layer layer having a specific refractive index and thickness, and a specific refractive index and thickness are sequentially laminated on one surface of the transparent resin layer. The high refractive index layer further has a second easy-to-adhere layer having a specific refractive index and thickness, a hard coat layer, and a specific refractive index and a low thickness on the other surface of the transparent resin layer. The transparent laminated film of the refractive index layer has a patterned transparent conductive layer, and is thin and highly transmissive even in a simple structure, and can suppress recognition of a pattern caused by chromatic aberration, and is completed. this invention.

In other words, the transparent laminated film-based transparent resin layer of the present invention has a first easy-adhesion layer and a high refractive index layer laminated on one surface of the transparent resin layer, on the other side of the transparent resin layer. a transparent laminated film of a second easy-adhesion layer, a hard coat layer, and a low-refractive-index layer, wherein the first and second easy-adhesion layers each have a refractive index of 1.5 to 1.7 and a thickness of 30 to 200 nm. The high refractive index layer has a refractive index of 1.6 to 1.8 and a thickness of 120 to 2000 nm, and the low refractive index layer has a refractive index of 1.2 to 1.5 and a thickness of 10 to 200 nm. The transparent laminated film of the present invention may have a haze of about 0.05 to 1%. In the transparent laminate film of the present invention, the surface of the low refractive index layer may have a measurement region The arithmetic mean roughness Ra1 calculated at 10 μm × 10 μm is 0.7 nm or more and less than 5 nm, and the arithmetic mean roughness Ra2 calculated in the measurement region of 500 μm × 500 μm is a concave-convex structure of 10 to 50 nm. The hard coat layer may be formed of a curable resin, a thermoplastic resin, and a cured product of a curable composition of metal oxide particles having an average primary particle diameter of 1 to 50 nm. On the high refractive index layer, a transparent conductive layer having a refractive index of 1.8 to 2.3 and a thickness of 10 to 60 nm and a transparent adhesive layer having a refractive index of 1.4 to 2.3 may be sequentially laminated. The transparent laminated film of the present invention may have a reflection chromatic aberration ΔE of 10 or less due to the presence or absence of a transparent conductive layer represented by the following formula.

ΔE=((L _a ^* -L _b ^* ) ² +(a _a ^* -a _b ^* ) ² +(b _a ^* -b _b ^* ) ² ) ^1/2

(In the _{^{formula, L a *, a a *}} , b a * is laminated portion of the transparent conductive layer 10 ° reflective ^{L *, a *, b *} , L b *, a b *, b b * of the transparent electroconductive layer-non The 10° reflection of the laminated portion is L ^* , a ^* , b ^* ).

The transparent laminated film of the present invention may have a total light transmittance of 90% or more. The water contact angle of the surface of the low refractive index layer may be about 65 to 80 degrees. The high refractive index layer may be formed of a curable composition containing inorganic fine particles.

The present invention also includes a capacitance type touch panel display including the transparent laminated film.

Further, in the present specification, the thickness of each layer means the average thickness, and can be measured by an instantaneous multi-photometric system ("MCPD-3700" manufactured by Otsuka Electronics Co., Ltd.).

In the present invention, a first easy-to-adhere layer having a specific refractive index and thickness, a high refractive index layer having a specific refractive index and a thickness, and a transparent resin are further laminated on one surface of the transparent resin layer. On the other side of the layer, a second transparent layer having a specific refractive index and thickness, a hard coat layer, and a transparent laminated film having a specific refractive index and a thickness of a low refractive index layer are sequentially laminated. The patterned transparent conductive layer has a thin wall and high light transmittance even in a simple structure, and can suppress recognition of a pattern caused by chromatic aberration. Further, in the electrostatic capacitance type touch panel display having the void layer therein, the transparent laminated film of the present invention can prevent the occurrence of water ripple even in the case of low haze, and can suppress glare even when applied to a high-definition display device.

Form for implementing the invention Transparent resin layer

The transparent laminate film of the present invention contains a transparent resin layer (or a substrate layer). As the transparent resin layer, a plastic film or sheet (unstretched or stretched plastic film) formed of a transparent resin excellent in flexibility and crack resistance compared to glass can be used. As the transparent resin, the same resin as the thermoplastic resin exemplified in the item of the hard coat layer described later can be used. The preferred transparent resin may, for example, be a cellulose derivative [cellulose acetate such as cellulose triacetate (TAC) or cellulose diacetate] or a polyester resin [PET, polybutylene terephthalate]. Diester (PBT), polyarylate tree Lipid, etc., polyfluorene-based resin [polyfluorene, polyether oxime, etc.], polyether ketone resin [polyether ketone, polyether ether ketone, etc.], polycarbonate resin (bisphenol A polycarbonate, etc.) , polyolefin resin (polyethylene, polypropylene, etc.), cyclic polyolefin resin [TOPAS (TOPAS) (registered trademark), ARTON (ARTON) (registered trademark), ZEONEX (ZEONEX) (registered trademark), etc.] A halogen-containing resin (polyvinylidene chloride or the like), a (meth)acrylic resin (such as a polymethyl methacrylate resin), a styrene resin (such as polystyrene), a vinyl acetate or a vinyl alcohol Resin (polyvinyl alcohol, etc.), etc. The plastic film formed by such a transparent resin can be extended in one or two axes.

The optically isotropic transparent plastic film contains, for example, a polyester or a cellulose derivative, and is particularly excellent in a balance between heat resistance and transparency, and is preferably a poly C _2-4 such as PET or PEN. A film formed by alkyl aryl ester. Further, the transparent resin layer may be a film extending through two axes.

The transparent resin layer may contain various conventional additives, such as stabilizers (antioxidants, ultraviolet absorbers, etc.), surfactants, water-soluble polymers, leveling agents, fillers, crosslinking agents, coupling agents, colorants, Flame retardant, slip agent, wax, preservative, viscosity modifier, tackifier, defoamer, etc. The ratio of the additive is, for example, about 0.01 to 10% by weight (particularly 0.1 to 5% by weight) based on the entire transparent resin layer.

The refractive index of the transparent resin layer is, for example, 1.5 to 1.8, preferably 1.55 to 1.75, and more preferably 1.6 to 1.7.

Further, in the present invention, the refractive index can be measured using a Metricon® coupler (Prism coupler) at a wavelength of 633 nm in accordance with JIS K 7142.

The thickness (average thickness) of the transparent resin layer is, for example, 20 to 200 μm, preferably 25 to 150 μm, and more preferably 30 to 120 μm (especially 40 to 100 μm). When the transparent resin layer is too thin, water ray is likely to occur when used in a touch panel, and when it is too thick, manufacturing of a thinning device becomes difficult.

1st easy layer

A first easy-adhesion layer is laminated on one surface of the transparent resin layer. The first easy-to-adhere layer usually contains an adhesive resin.

The adhesive resin may, for example, be an olefin resin [for example, polyethylene, ethylene-acrylate copolymer, ethylene-methacrylate copolymer, ethylene-(meth)acrylic copolymer, ionic polymer resin, Ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyethylene resin such as ethylene-acrylonitrile-acrylic acid copolymer, amorphous polypropylene resin, etc.], vinyl chloride resin (vinyl chloride-vinyl acetate) Ester copolymer, etc.), vinylidene chloride resin (vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-(meth)acrylate copolymer, vinylidene chloride-acrylonitrile copolymer, etc.), acrylic acid a resin (for example, a homopolymer or a copolymer of a (meth)acrylic monomer (for example, (meth)acrylic acid, (meth)acrylic acid ester), such a (meth)acrylic monomer and copolymerization a copolymer of a monomer (a styrene monomer, a vinyl ester monomer such as vinyl acetate, an unsaturated dicarboxylic acid or an ester thereof, etc.), or a vinyl acetate resin [polyvinyl acetate, vinyl acetate) Ester and other copolymerizable monomers (olefin monomers, (meth)acrylic acid a copolymer of an unsaturated dicarboxylic acid or an ester thereof, etc.], a styrene resin [for example, a styrene-(meth)acrylate copolymer, a styrene-(meth)acrylate-(methyl) Acrylic copolymer, etc.], polyester resin [Low molecular weight polyester resin, aliphatic polyester resin, amorphous polyester resin (for example, amorphous aliphatic or aromatic polyester), etc.], urethane resin (thermoplastic amine group) An acid ester polymer (such as a styrene-butadiene copolymer) or a polymer containing an imine group (a polyalkylenimine such as polyethyleneimine) )Wait.

These adhesive resins may be used alone or in combination of two or more. These adhesive resins can be appropriately selected depending on the type of the transparent resin layer, but an acrylic resin, a polyester resin, a urethane resin or the like is usually used.

The first easy-adhesion layer can be formed of a curable resin exemplified in the item of the high refractive index layer to be described later. For example, it can be used as an easy-adhesion layer by forming a layer containing a curable resin having a high adhesion to the transparent resin layer among the curable resin as a film.

The refractive index of the first easy-adhesion layer is, for example, 1.5 to 1.7, preferably 1.52 to 1.69, more preferably 1.55 to 1.68 (especially 1.6 to 1.67).

The thickness (average thickness) of the first easy-adhesion layer is, for example, 30 to 200 nm, preferably 40 to 180 nm, and more preferably 50 to 150 nm.

High refractive index layer

A high refractive index layer is further laminated on the first easy adhesion layer. The high refractive index layer mainly has an index matching function, and even if the device has a patterned transparent conductive layer, it helps to suppress the recognition of the pattern due to chromatic aberration. As the high refractive index layer, a transparent curable composition containing inorganic fine particles can be used.

Curable resin

The curable composition usually contains a curable resin as a resin component. The curable resin (curable monomer or curable resin precursor) is a compound having a functional group which is reacted by heat or an active energy ray (ultraviolet rays, electron beam, etc.) or the like, and can be used by heat or Various hardening compounds which form a resin (especially a hardened or crosslinked resin) by hardening or crosslinking an active energy ray or the like. The curable resin may, for example, be a thermosetting compound or a resin [a low molecular weight compound having an epoxy group, a polymerizable group, an isocyanate group, an alkoxyalkyl group, a decyl group or the like (for example, an epoxy system). Resin, unsaturated polyester resin, urethane resin, polyfluorene resin, etc.), photocurable compound (photocurable monomer, oligo which can be cured by active light (such as ultraviolet rays) The photocurable compound such as an ultraviolet curable compound such as a polymer or the like may be an EB (electron beam) curable compound or the like. In addition, a photocurable compound such as a photocurable monomer, an oligomer, or a photocurable resin having a low molecular weight may be referred to as a "photocurable resin".

The photocurable compound contains, for example, a monomer, an oligomer (or a resin, especially a low molecular weight resin). The monomer can be classified into, for example, a monofunctional monomer having one polymerizable group and a polyfunctional monomer having at least two polymerizable groups.

Examples of the monofunctional monomer include a (meth)acrylic monomer such as (meth)acrylate, a vinyl monomer such as vinyl pyrrolidone, and isodecyl (meth)acrylate. A (meth) acrylate having a bridged cyclic hydrocarbon group such as an adamantyl (meth) acrylate.

The polyfunctional monomer contains a polyfunctional monomer having 2 to 8 polymerizable groups, and examples of the bifunctional monomer include ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylic acid. Alkanediol di(meth)acrylate such as ester, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate; (poly)oxyalkylene glycol di(methyl) such as ethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyoxytetramethylene glycol di(meth)acrylate An acrylate having a bridged cyclic hydrocarbon group such as tricyclodecane dimethanol di(meth)acrylate or adamantane di(meth)acrylate.

Examples of the 3-8 functional monomer include glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trimethylolethane tri(meth)acrylate. Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

As the oligomer or the resin, (meth) acrylate or epoxy (meth) acrylate (bisphenol A type epoxy) of bisphenol A-alkylene oxide adduct can be exemplified. Acrylate, novolak type epoxy (meth) acrylate, etc.), polyester (meth) acrylate (for example, aliphatic polyester (meth) acrylate, aromatic polyester (meth) acrylate Ester (etc.), (poly)urethane (meth) acrylate (polyester urethane (meth) acrylate, polyether urethane (meth) acrylate, etc.) , polyoxyl (meth) acrylate, and the like. These (meth) acrylate oligomers or resins may contain a copolymerizable monomer such as a styrene monomer, a vinyl ester monomer, maleic anhydride, maleic acid or fumaric acid. These photocurable compounds may be used alone or in combination of two or more.

Among these curable resins, the ultraviolet curable resin is preferably a polyfunctional (meth) acrylate such as pentaerythritol tri(meth)acrylate or dipentaerythritol hexa(meth)acrylate.

The molecular weight of the curable resin is, for example, 5,000 or less (for example, 100 to 5,000), preferably 2,000 or less (for example, 200 to 2,000), and more preferably 1,000 or less (for example, 300 to 1,000). The molecular weight is a weight average molecular weight measured by polystyrene in gel permeation chromatography (GPC), and a low molecular weight can be calculated from a molecular formula.

Inorganic microparticles

The particle size of the inorganic fine particles may be a nanometer size. Specifically, the number average primary particle diameter may be selected from the range of about 1 to 100 nm, for example, 2 to 50 nm, preferably 3 to 40 nm, more preferably It is about 5 to 30 nm (especially 8 to 20 nm). When the particle diameter of the inorganic fine particles is too small, there is a fear that the light scattering becomes small, and the effect of suppressing the recognition of the pattern due to the chromatic aberration becomes small. When the particle size is too large, the light scattering is increased, and the transparency is also lowered.

Further, in the present invention, the average particle diameter of the inorganic fine particles can be measured by a conventional method using a particle size distribution meter, for example, a particle size measuring device ("PAR-III" manufactured by Otsuka Electronics Co., Ltd.) based on a dynamic light scattering method.

The shape of the inorganic fine particles is not particularly limited, and examples thereof include a spherical shape, an ellipsoidal shape, a polygonal shape (a polygonal pyramid shape, a rectangular parallelepiped shape, a rectangular parallelepiped shape, etc.), a plate shape, a rod shape, an amorphous shape, and the like, but are equiaxively The scattered light and the point at which the visibility can be improved are preferably an isotropic shape such as a slightly spherical shape.

As the inorganic compound constituting the inorganic fine particles, for example, a metal monomer or a metal oxide is preferably a metal oxide from the viewpoint of enhancing the refractive index.

Examples of the metal oxide include metal oxides of Group 4A of the periodic table (for example, titanium oxide, zirconium oxide, etc.), metal oxides of Group 5A (vanadium oxide, etc.), and metal oxides of Group 6A (molybdenum oxide). , tungsten oxide, etc.), Group 7A metal oxides (manganese oxide, etc.), Group 8 metal oxides (nickel oxide, iron oxide, etc.), Group 1B metal oxides (copper oxide, etc.), Group 2B metal oxides A material (such as zinc oxide), a metal oxide of Group 3B (such as alumina or indium oxide), a metal oxide of Group 4B (such as cerium oxide or tin oxide), a metal oxide of Group 5B (such as cerium oxide), or the like. These metal oxides may be used alone or in combination of two or more.

Among these metal oxides, the refractive index of the high refractive index layer can be increased in a small proportion, and the increase in haze can be suppressed even if the amount of addition is increased, and a periodic table of titanium oxide or zirconium oxide is preferable. Group 4A metal oxide, particularly preferably zirconia.

The inorganic fine particles (especially titanium oxide and zirconium oxide) are preferably particles which are not subjected to surface treatment from the viewpoint of suppressing aggregation.

The ratio of the inorganic fine particles is, for example, 170 to 700 parts by weight, preferably 200 to 500 parts by weight, and more preferably about 233 to 500 parts by weight, per 100 parts by weight of the curable resin. When the ratio of the inorganic fine particles is too small, the refractive index cannot be raised, and when it is too large, there is a fear that the mechanical properties are lowered.

Other additives

The curable composition may contain a curing agent depending on the type of the curable resin. For example, the thermosetting resin may contain a curing agent such as an amine or a polyvalent carboxylic acid, and the photocurable resin may contain a photopolymerization initiator. As the photopolymerization initiator, conventional components such as acetophenone or propiophenone, diphenylethylenedione, benzoin, benzophenone, thioxanthone can be exemplified. , acylphosphine oxides (acylphosphine oxide) and the like. The content of the curing agent such as a light curing agent is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight (particularly 1 to 5 parts by weight) per 100 parts by weight of the curable resin. ), about 3 to 8 parts by weight.

Further, the curable composition may contain a hardening accelerator. The photocurable resin may contain a photocuring accelerator, for example, a tertiary amine (dialkylamino benzoate or the like), a phosphine photopolymerization accelerator, or the like. The ratio of the curing accelerator may be 0.001 to 50 parts by weight, preferably 0.005 to 30 parts by weight, and more preferably about 0.01 to 10 parts by weight, per 100 parts by weight of the curable resin.

The curable composition may contain a conventional additive exemplified in the item of the transparent resin layer. The ratio of the additive is, for example, about 0.01 to 10% by weight (particularly 0.1 to 5% by weight) based on the entire high refractive index layer.

Characteristics of high refractive index layer

The refractive index of the high refractive index layer is, for example, 1.6 to 1.8, preferably 1.65 to 1.78, more preferably 1.7 to 1.76 (especially 1.72 to 1.75). When the refractive index is too small, there is a fear that the effect of suppressing the recognition of the pattern due to chromatic aberration becomes small, and when it is too large, the transparency may be lowered.

The thickness (average thickness) of the high refractive index layer is, for example, 120 to 2000 nm, preferably 150 to 1500 nm (for example, 200 to 1000 nm), and more preferably 300 to 800 nm (especially 400 to 600 nm). When the high refractive index layer is too thin, pattern recognition due to chromatic aberration occurs, and when it is too thick, it becomes difficult to reduce the thickness of the device, and the transparency may be lowered.

Transparent conductive layer

On the aforementioned high refractive index layer, a transparent conductive layer may be further laminated. The transparent conductive layer may include, for example, a metal oxide containing indium oxide-tin oxide-based composite oxide (ITO), fluorine-doped tin oxide (FTO), InO ₂ , SnO ₂ , ZnO, or the like, or gold, A layer of a metal such as silver, platinum, or palladium (especially a metal oxide layer such as an ITO film). Such a transparent conductive layer can be formed by a conventional method such as sputtering, evaporation, chemical vapor deposition, or the like (usually sputtering).

The transparent conductive layer is formed into a planar shape in an analogous manner in accordance with the type of the touch panel, and is formed in a stripe shape in a digital manner. In the method of forming the transparent conductive layer into a planar shape or a stripe shape, for example, after the transparent conductive layer is entirely formed on the glass substrate, it is patterned into a planar shape, a striped shape, or a lattice shape by etching (square or diamond shape). a method, a method of forming a pattern in advance, and the like. The transparent laminated film of the present invention is preferably a patterned transparent conductive layer in order to effectively suppress the phenomenon of seeing a profile.

The refractive index of the transparent conductive layer is, for example, 1.8 to 2.3, preferably 1.85 to 2.25, and more preferably about 1.9 to 2.2.

The thickness (average thickness) of the transparent conductive layer is, for example, 10 to 60 nm, preferably 15 to 50 nm, and more preferably about 20 to 40 nm.

Transparent adhesive layer

A transparent adhesive layer may be further laminated on the transparent conductive layer. The transparent adhesive layer can be formed by a transparent adhesive resin. The transparent adhesive resin may, for example, be a conventional adhesive resin or an adhesive resin.

The adhesive resin may, for example, be a thermoplastic resin (polyolefin, cyclic polyolefin, acrylic resin, styrene resin, vinyl acetate resin, polyester, polyamide, thermoplastic polyurethane). Etc., thermosetting resin (epoxy resin, phenolic resin, polyurethane, unsaturated polyester, vinyl ester resin, diallyl phthalate resin, polyfunctional (meth) acrylate, A urethane (meth) acrylate, a poly methoxy (meth) acrylate, a polyoxy oxy resin, an amine based resin, a cellulose derivative, etc.). These adhesive resins may be used alone or in combination of two or more.

Examples of the adhesive resin include a terpene resin, a rosin-based resin, a petroleum resin, a rubber-based adhesive, a modified polyolefin, an acrylic adhesive, and a polyoxygen-based adhesive. These adhesive resins may contain a crosslinkable group (isocyanate group, hydroxyl group, carboxyl group, amine group, epoxy group, methylol group, alkoxyalkyl group, etc.). These adhesive resins may be used alone or in combination of two or more.

Among these transparent binder resins, acrylic adhesives and polyoxynoxy adhesives (especially acrylic adhesives) are preferred from the viewpoint of excellent optical properties and workability.

As the acrylic pressure-sensitive adhesive, for example, an adhesive containing an acrylic copolymer containing C _2-10 alkyl acrylate such as ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate as a main component can be used. The copolymerizable monomer of the acrylic copolymer may, for example, be a (meth)acrylic monomer [for example, (meth)acrylic acid, methyl (meth)acrylate, or hydroxyethyl (meth)acrylate) , hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, etc. , a polymerizable nitrile compound [for example, (meth)acrylonitrile or the like], an unsaturated dicarboxylic acid or a derivative thereof (for example, maleic anhydride, itaconic acid, etc.), a vinyl ester (for example, vinyl acetate, C) An acid vinyl group or the like, an aromatic vinyl group (for example, styrene or the like), or the like.

For the polyoxynene-based adhesive, for example, a polyoxyxene rubber component [containing a monofunctional R ₃ SiO _1/2 (wherein R represents an alkyl group such as a methyl group, an aryl group such as a phenyl group, etc.) The same as below) with tetrafunctional SiO ₂ MQ resin, etc. and polyoxyxyl resin component (difunctional R ₂ SiO alone or in combination with difunctional R ₂ SiO and monofunctional R ₃ SiO _1/2 An oily or gelatinous component, etc.) an adhesive dissolved in an organic solvent or the like. The aforementioned polyoxyxene rubber component can be crosslinked.

The transparent adhesive layer may contain a conventional additive exemplified in the item of the transparent resin layer in the ratio described in the item of the transparent resin layer.

The refractive index of the transparent adhesive layer is, for example, 1.3 to 1.7, preferably 1.4 to 1.6, and more preferably about 1.45 to 1.55.

The thickness (average thickness) of the transparent adhesive layer is, for example, 1 to 100 μm, preferably 2 to 80 μm, and more preferably 3 to 70 μm (especially 5 to 50 μm).

2nd easy layer

A second easy-adhesion layer is laminated on the other surface of the transparent resin layer. The second easy-adhesion layer is formed of a resin component exemplified as the first easy-adhesion layer, and may be the same resin component as the first easy-to-adhere layer or may be a different resin component. The refractive index of the second easy-adhesion layer is, for example, 1.3 to 1.7, preferably 1.45 to 1.65, more preferably about 1.55 to 1.62. The thickness of the second easy-adhesion layer may be selected from the same range as the first easy-to-layer layer, or may be different from the first easy-to-layer layer.

Hard coating

A hard coat layer is further laminated on the second easy-to-attach layer. As the hard coat layer, a transparent curable composition containing a curable resin can be used.

Curable resin

The curable resin exemplified in the first hard coat layer can be used as the curable resin contained in the hard coat layer. A preferred curable resin is a photocurable compound which can be cured for a short period of time, for example, an ultraviolet curable compound (monomer, oligomer or resin which can be a low molecular weight) or an EB curable compound. In particular, a curable resin which is practically advantageous is an ultraviolet curable resin.

In addition, in order to improve the scratch resistance of the hard coat layer, the curable resin has a polymerizable group having two or more functional groups (for example, about 2 to 10 functional groups), preferably three or more functional groups (for example, about three to eight functional groups). The curable resin is particularly preferably a polyfunctional (meth) acrylate, for example, a trifunctional or higher (particularly 4 to 8 functional) (meth) acrylate (for example, dipentaerythritol hexa(meth) acrylate or the like). .

In addition, it is preferable to combine a curable resin having a polymerizable group having 4 or less functional groups (preferably 2 to 4 functional groups, more preferably 3 to 4 functional groups) from the point of hard coating property or the like, and having 5 A curable resin having a functional group or more (for example, a 5- to 10-functional, preferably a 5- to 8-functional, more preferably a 5- to 7-functional) polymerizable group. In particular, it is possible to combine 2 to 4 functional (meth) acrylates (especially 3 to 4 functional (meth) acrylates such as pentaerythritol tri(meth) acrylate], and 5 to 8 functional (meth) acrylates. [In particular, a 5- to 7-functional (meth) acrylate such as dipentaerythritol hexa(meth) acrylate].

A curable resin having a polymerizable group having 4 or less functional groups (for example, a 2-4 functional (meth) acrylate), and a curable resin having a polymerizable group having 5 or more functional groups (for example, 5 to 10 functional (meth)acrylic acid) The weight ratio of the ester is the former/the latter = 99/1 to 1/99, preferably 90/10 to 10/90, further preferably 70/30 to 30/70 (especially 60/40 to 40/60). )about. In the present invention, the hard coatability can be improved by combining a specific functional group of the curable resin in such a ratio.

Thermoplastic resin

In addition to the curable resin, the curable composition may be blended with a thermoplastic resin, for example, a reactive group that does not have a curing reaction involving the curable resin (especially, an ethylene property) in order to improve mechanical properties such as flexibility. A thermoplastic resin having a polymerizable group such as a saturated bond.

For the thermoplastic resin, for example, a styrene resin [polystyrene, a copolymer of styrene and a (meth)acrylic monomer, an AS resin, a styrene-butadiene copolymer, etc.], ( Methyl)acrylic resin [poly(meth)acrylate such as polymethyl methacrylate, methyl methacrylate-(meth)acrylic acid copolymer, methyl methacrylate-(meth)acrylate copolymerization , methyl methacrylate-acrylate-(meth)acrylic acid copolymer, (meth)acrylate-styrene copolymer (MS resin, etc.), (meth)acrylic acid-methyl (meth)acrylate- (Iso-decyl methacrylate copolymer, etc.), organic acid vinyl ester resin [ethylene-vinyl acetate copolymer, vinyl acetate-vinyl chloride copolymer, vinyl acetate-(meth) acrylate copolymer, Polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl acetal resin, etc.], vinyl ether resin (polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl propyl ether, polyvinyl Tributyl ether, etc., halogen-containing resin [polyvinyl chloride, polyvinylidene fluoride, vinyl chloride-acetic acid B Ester copolymer, vinyl chloride-(meth)acrylate copolymer, vinylidene chloride-(meth)acrylate copolymer, etc.], olefin resin [homopolymer of olefin such as polyethylene or polypropylene, ethylene- Vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, alicyclic olefin resin, etc., polycarbonate resin (double bisphenol a type polycarbonate), polyester resins (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate or the like aryl C _2-4 alkylene group An ester, an amorphous polyester such as a C _2-4 alkyl aryl ester-based copolyester, or the like, or a polyamidamide resin (polyamide 46, polyamine 6, polyamine 66, polyamide 610) , polyamines 612, polyamines, polyamines such as polyamines, etc.), thermoplastic polyurethane resins (polyester urethane resins, etc.), polyfluorenes Resin (polyether oxime, polyfluorene, etc.), polyphenylene ether resin (polymer of 2,6-xylenol, etc.), cellulose derivative (cellulose ester, etc.), polyoxyl resin (polydimethylation) Oxane, polymethylphenyl sulfoxane ), rubber or elastomer (diene rubber such as polybutadiene or polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylic rubber, urethane) Rubber, polyoxyethylene rubber, etc.). These thermoplastic resins may be used alone or in combination of two or more.

Among these thermoplastic resins, a styrene resin, a (meth)acrylic resin, an alicyclic olefin resin, a polyester resin, a cellulose derivative, or the like is usually used, but it is excellent in transparency and heat resistance, and It is also possible to improve the mechanical properties such as flexibility, and is preferably a cellulose derivative.

The cellulose derivative contains cellulose esters, cellulose ethers, and cellulose urethanes.

Examples of the cellulose esters include, for example, aliphatic organic acid esters (cellulose acetate, cellulose acetate triacetate, etc.; cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate) C _2-6 acylate such as acid cellulose, aromatic acid ester (C _7-12 aromatic carboxylic acid ester such as cellulose phthalate or cellulose benzoate), inorganic acid Esters (for example, nitrocellulose, cellulose phosphate, cellulose sulfate, etc.) and the like. The cellulose ester may be a mixed acid ester of acetic acid, cellulose nitrate or the like.

In the case of cellulose ethers, for example, cyanoethyl cellulose; hydroxyethyl _2-4 alkyl cellulose such as hydroxyethyl cellulose or hydroxypropyl cellulose; methyl cellulose, ethyl cellulose, etc. C _1-6 alkyl cellulose; carboxymethyl cellulose or a salt thereof, benzyl cellulose, ethoxylated alkyl cellulose, and the like. As the cellulose urethane, for example, cellulose phenyl urethane or the like can be exemplified.

These cellulose derivatives may be used alone or in combination of two or more. Among these cellulose derivatives, cellulose esters, particularly cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate are preferred. Cellulose C _2-6 telluride. Among them, in addition to high solubility in a solvent and easy preparation of a coating liquid, the viscosity of the coating liquid can be easily adjusted by a small amount of addition, and excessive aggregation of fine particles in the coating liquid can be suppressed and storage can be improved. The stability is preferably cellulose C _2-4 telluride such as cellulose diacetate, cellulose acetate propionate or cellulose acetate butyrate (especially cellulose acetate C _3-4等 such as cellulose acetate propionate. Compound).

The ratio of the thermoplastic resin is, for example, 0.1 to 30 parts by weight, preferably 0.1 to 10 parts by weight (for example, 0.3 to 5 parts by weight), more preferably 0.5 to 3 parts by weight (particularly 0.8), based on 100 parts by weight of the curable resin. ~2 parts by weight). In the present invention, by adjusting the ratio of the thermoplastic resin, it is possible to adjust the balance between the scratch resistance, the mechanical properties such as the absorbing absorbability and the cushioning property, and when it is within this range, the balance between the two is excellent.

Metal oxide microparticles

In addition to the curable resin and the thermoplastic resin, the curable composition preferably contains metal oxide fine particles in order to impart AWM properties to the low refractive index layer. By doping the hard coat layer with a small amount of metal oxide fine particles than the high refractive index layer, convection occurs and the distribution of the metal oxide in the resin component becomes uneven, whereby the resin component is embossed to form a minute uneven structure. . Such a concavo-convex structure suppresses the occurrence of water ripple on the surface of the low refractive index layer which follows its shape, and suppresses the occurrence of glare. Furthermore, the metal oxide microparticles are transparent In addition to excellent properties and scratch resistance, adhesion to the low refractive index layer can also be improved.

In the metal oxide fine particles, the metal oxide fine particles exemplified in the high refractive index layer may be used alone or in combination of two or more. Among the metal oxide fine particles, metal oxides containing antimony, tin, and zinc, such as antimony trioxide, antimony tetroxide, antimony pentoxide, antimony-containing antimony oxide (yttrium-doped tin oxide), tin oxide, and the like are preferable. Zinc oxide or the like is particularly preferably selected from the group consisting of at least one type of fine particles containing antimony tin oxide, antimony oxide, tin oxide, and zinc oxide (particularly, antimony-containing tin oxide particles (ATO particles)).

The metal oxide fine particles may be in the form of a dispersion dispersed in a solvent. Examples of the solvent include water, alcohols (lower alcohols such as methanol, ethanol, isopropanol, butanol, and cyclohexanol), and ketones (acetone, methyl ethyl ketone, and methyl isobutyl). Ketone, cyclohexanone, etc.), esters (methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, etc.), ethers (diethyl ether, two Alkane, tetrahydrofuran, etc., aliphatic hydrocarbons (such as hexane), alicyclic hydrocarbons (such as cyclohexane), aromatic hydrocarbons (benzene, etc.), halocarbons (dichloromethane, dichloroethylene) Ethane, etc., celecoxime (methyl acesulfame, ethyl acesulfame, etc.), cyanidin acetate, guanamine (dimethylformamide, dimethylacetamide, etc.) Wait. These solvents may be used alone or in combination of two or more. Among these solvents, a lower alcohol such as ethanol or isopropyl alcohol is usually used (for example, by weight ratio, ethanol/isopropyl alcohol = 90/10 to 50/50 (especially 80/20 to 60/40). Mixed solvent). The concentration of the metal oxide fine particles in the dispersion is, for example, 0.1 to 50% by weight, preferably 1 to 40% by weight, and more preferably about 5 to 30% by weight. The surface of the metal oxide fine particles can be subjected to a conventional surface treatment in order to disperse in such a solvent.

The shape of the metal oxide fine particles is not particularly limited, and examples thereof include a spherical shape, an ellipsoidal shape, a polygonal shape (polygonal pyramid shape, a rectangular parallelepiped shape, a rectangular parallelepiped shape, etc.), a plate shape, a rod shape, an amorphous shape, and the like, which are formed from the surface. The point of the uniform uneven structure is preferably an equilateral shape such as a slightly spherical shape.

The number average primary particle diameter of the metal oxide fine particles is, for example, 1 to 50 nm, preferably 1.5 to 40 nm (for example, 2 to 30 nm), and more preferably 3 to 15 nm (particularly 5 to 10 nm). When the primary particle diameter is too small, it is difficult to form a concavo-convex structure on the surface of the hard coat layer. When the primary particle diameter is too large, it is difficult to form a minute uneven structure, and the wavelength of the light is also larger, which may cause glare. The reason for the occurrence. In the present invention, by using particles having a large particle diameter, a hard coat layer is produced under specific conditions using particles having a nanometer size, and a minute uneven structure can be formed.

The ratio of the metal oxide fine particles is, for example, 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.15 to 3 parts by weight (particularly 0.2 to 1 part by weight) per 100 parts by weight of the curable resin. . When the ratio of the fine particles is too small, it is difficult to form a concavo-convex structure on the surface of the hard coat layer, and when it is too large, it becomes difficult to form a minute uneven structure. In the present invention, even if the proportion of the fine particles is small, a concavo-convex structure capable of achieving AWM properties can be formed. Therefore, the optical display device including the transparent laminated film of the present invention has low haze and can suppress glare.

The ratio of the thermoplastic resin is, for example, 100 to 1000 parts by weight, preferably 150 to 500 parts by weight, and more preferably 200 to 400 parts by weight, based on 100 parts by weight of the metal oxide fine particles.

Other additives

The curable composition may be a ratio of the high refractive index layer and the transparent resin layer, and the hardener, the hardening accelerator, and the transparent resin layer exemplified in the item of the high refractive index layer. Additives. The proportion of the additive is, for example, about 0.01 to 10% by weight (particularly 0.1 to 5% by weight) based on the entire hard coat layer.

Hard coating properties

The refractive index of the hard coat layer is, for example, 1.4 to 1.6, preferably 1.45 to 1.57, and more preferably about 1.49 to 1.54.

The thickness (average thickness) of the hard coat layer is, for example, 100 to 2000 nm, preferably 300 to 1800 nm, and more preferably 500 to 1,500 nm (especially 800 to 1200 nm). When the hard coat layer is too thin, the productivity of the transparent laminated film is lowered, and when it is too thick, the thickness of the device becomes difficult.

Low refractive index layer

A low refractive index layer is further laminated on the aforementioned hard coat layer. The low refractive index layer can reduce the reflectance at the surface and increase the transmittance of the outgoing light to the outside. Further, by adding metal oxide fine particles to the hard coat layer, when a specific uneven structure is formed, the low refractive index layer suppresses glare and also enhances AWM properties.

For the low-refractive-index layer, a conventional low-refractive-index layer can be used, for example, a low-refractive-index layer described in JP-A-2001-000623, JP-A-2008-58723, and the like. The low refractive index layer usually includes a low refractive index resin, a combination of a curable resin exemplified in the high refractive index layer, a fluorine-containing compound or a low refractive index inorganic filler, and the like.

Examples of the low refractive index resin include fluororesins such as methylpentene resin, diethylene glycol bis(allyl carbonate) resin, polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF). Wait.

Further, the low refractive index layer is usually preferably a fluorine-containing compound or a low refractive index inorganic filler. When a fluorine-containing compound or a low refractive index inorganic filler is used, the refractive index of the low refractive index layer can be lowered as desired.

The fluorine-containing compound includes a fluorine atom and a functional group (a crosslinking group such as a crosslinkable group or a polymerizable group) which reacts with heat or an active energy ray (such as ultraviolet rays or electron beams). Or, and a fluorine-containing resin precursor of a fluorine-containing resin (especially a hardened or crosslinked resin) can be formed by hardening or crosslinking by heat or an active energy ray or the like.

The fluorine-containing resin precursor is exemplified by a thermosetting compound or a resin containing a fluorine atom [having a fluorine atom and a reactive group (epoxy group, isocyanate group, carboxyl group, hydroxyl group, etc.), and a polymerizable group). a low molecular weight compound (such as a vinyl group, an allyl group or a (meth) acrylonitrile group), or a photocurable compound or resin containing a fluorine atom which is hardened by active light (such as ultraviolet rays) (photocurable content) An ultraviolet curable compound such as a fluorine monomer or oligomer, or the like).

The above-mentioned thermosetting compound or resin may, for example, be a low molecular weight resin obtained by using at least a fluorine-containing monomer, for example, a fluorine-containing polyol (particularly a diol) is used as a part of the polyol component constituting the monomer. Or all of the epoxy-based fluorine-containing resin; similarly, a fluorine atom-containing polyol and/or a fluorine atom-containing polycarboxylic acid component is used instead of a part or all of the polyol and/or the polycarboxylic acid component. The unsaturated polyester-based fluorine-containing resin; a urethane-based fluorine-containing resin obtained by substituting a part or all of a polyol and/or a polyisocyanate component with a fluorine atom-containing polyol and/or a polyisocyanate component. These thermosetting compounds or resins may be used alone or in combination of two or more.

The photocurable compound contains, for example, a monomer, an oligomer (or a resin, especially a low molecular weight resin), and as the monomer, a monofunctional single such as exemplified in the item of the aforementioned high refractive index layer can be exemplified. a fluorine-containing monomer of a polyfunctional monomer and a vinyl monomer such as a fluorinated alkyl ester of (meth)acrylic acid, such as a (meth)acrylic monomer or a fluoroolefin Or a monofunctional monomer; a di(meth)acrylate of a fluorinated alkylene glycol such as 1-fluoro-1,2-di(meth)acryloxyethylene or the like]. Further, as the oligomer or the resin, a fluorine atom-containing oligomer or resin corresponding to the oligomer or resin exemplified in the above-mentioned high refractive index layer can be used. These photocurable compounds may be used alone or in combination of two or more.

The ratio of the fluorine-containing compound in the low refractive index layer is, for example, 1% by weight or more, for example, about 5 to 90% by weight based on the entire low refractive index layer.

For the inorganic filler having a low refractive index, for example, a filler described in the above-mentioned Japanese Patent Laid-Open Publication No. 2001-100006 can be used, but a low refractive index filler such as vermiculite or magnesium fluoride is preferable. It is a rock. The hollow vermiculite described in Japanese Laid-Open Patent Publication No. 2001-233611, and the like. The hollow vermiculite not only has a large effect of improving the penetration rate, but also has an excellent effect of improving the AWM property.

The number average primary particle diameter of the inorganic filler is 100 nm or less, preferably 80 nm or less (for example, 10 to 80 nm), and more preferably about 20 to 70 nm.

The ratio of the low refractive index inorganic filler in the low refractive index layer may be, for example, 1% by weight or more, for example, about 5 to 90% by weight based on the entire low refractive index layer. Further, the inorganic filler having a low refractive index can be surface-modified by a coupling agent (titanium coupling agent, decane coupling agent). Further, the low refractive index layer may contain other inorganic fillers in order to increase the strength of the coating film.

The low refractive index layer preferably has a fine concavo-convex structure on the surface from the point of improving the AWM property. The uneven structure of the low refractive index layer is usually formed by following the uneven structure of the hard coat layer.

More specifically, the low refractive index layer preferably has a relatively small uneven structure on the surface, and the arithmetic mean roughness Ra1 calculated in the measurement region of 10 μm × 10 μm is 0.7 nm or more and less than 5 nm (for example, 0.75 nm or more and less than 2 nm), especially Even if it is a fine concavo-convex structure of less than 1.5 nm, it can exhibit AWM properties, preferably 0.8 nm or more and less than 1.5 nm, and more preferably 0.85 to 1.4 nm (especially 0.9 to 1.2 nm). When Ra1 is too small, the AWM property is lowered, and when it is too large, glare is likely to occur in a high-definition display.

The low refractive index layer has a larger uneven structure (wavy undulation) in addition to the fine concavo-convex structure, and the arithmetic mean roughness Ra2 calculated in the measurement region of 500 μm × 500 μm is 10 to 50 nm (for example, 11 to 45 nm). In particular, even if it is a fine concavo-convex structure of 30 nm or less, it can exhibit AWM properties, preferably 10 to 30 nm. Further preferably, it is about 11 to 20 nm. When the Ra2 is too small, the AWM property is lowered, and when it is too large, glare is likely to occur in a high-definition display. In addition to Ra1 having a fine concavo-convex structure, Ra2 having a undulating structure in such a range can suppress both WM properties and glare.

The average interval Sm of the concavities and convexities is, for example, 10 to 300 μm, preferably 20 to 250 μm, and more preferably 50 to 200 μm. When the Sm is too small, due to the pixel size of the high-definition display, there is a possibility of glare after drying. On the other hand, when Sm is too large, in addition to the decrease in AWM properties, glare may occur.

The arithmetic mean slope Δa of the concavo-convex structure is, for example, 0.01 to 1°, preferably 0.02 to 0.5°, and more preferably about 0.03 to 0.1°. When Δa is too large, glare is likely to occur in a high-definition display, and when it is too small, there is a fear that the AWM property is lowered.

The ten-point average roughness Rz of the uneven structure is 10 to 200 nm, preferably 30 to 150 nm, and more preferably 50 to 100 nm. When the Rz is too small, the AWM property is lowered, and when it is too large, glare is likely to occur in a high-definition display.

Further, in the present invention, these Ra, Sm, Δa and Rz can be measured in accordance with the method of JIS B0601.

The surface of the low refractive index layer is also excellent in wettability, and the water contact angle is 80 or less (e.g., 65 to 80), for example, 69 to 80, preferably 70 to 75, and further preferably 71 to 74. about. When the water contact angle is too low, the slidability is lowered, so that the scratch resistance is lowered. Further, in the present invention, the water contact angle can be measured using an automatic ‧ dynamic contact angle meter, and in detail, it can be measured by the method described in the examples below.

The refractive index of the low refractive index layer is, for example, 1.2 to 1.5, preferably 1.25 to 1.45, and more preferably about 1.3 to 1.4.

The thickness (average thickness) of the low refractive index layer is, for example, 10 to 200 nm, preferably 30 to 180 nm, and more preferably 50 to 150 nm (especially 80 to 120 nm).

Transparent laminated film and manufacturing method thereof

The transparent laminated film of the present invention is excellent in optical characteristics, and the reflection color difference ΔE due to the presence or absence of the transparent conductive layer represented by the following formula may be 10 or less, for example, 0.1 to 10, preferably 0.5 to 9, more preferably It is about 1~5 (especially 2~4). When ΔE is too high, there is a fear that the effect of suppressing the recognition of the pattern due to chromatic aberration becomes small.

ΔE=((L _a ^* -L _b ^* ) ² +(a _a ^* -a _b ^* ) ² +(b _a ^* -b _b ^* ) ² ) ^1/2

(In the _{^{formula, L a *, a a *}} , b a * is laminated portion of the transparent conductive layer 10 ° reflective ^{L *, a *, b *} , L b *, a b *, b b * of the transparent electroconductive layer-non The 10° reflection of the laminated portion is L ^* , a ^* , b ^* ).

Further, L _a ^* , L _b ^* , a _a ^* , b _a ^* , a _b ^* , b _b ^* can be measured using an integrating sphere reflection intensity measuring device ("U-3300" manufactured by Hitachi High-Technologies Co., Ltd.).

The transparent laminated film of the present invention (the laminated film having no transparent conductive layer) may have a total light transmittance of 80% or more (especially 90% or more), for example, 80 to 100%, in a thickness of 100 μm in accordance with JIS K7361. Preferably, it is 85 to 99%, and further preferably about 90 to 95%.

The transparent laminated film of the present invention (the laminated film having no transparent conductive layer) has a small haze of 100 μm in thickness according to JIS K7136. The haze ratio is, for example, 0.05 to 1%, preferably 0.1 to 0.8% (e.g., 0.12 to 0.5%), and more preferably 0.13 to 0.3% (especially 0.15 to 0.25%). In the present invention, by having such a low haze value, glare can be suppressed even in a high-definition display, and visibility can be improved.

The transparent laminated film of the present invention can be further combined with other optical elements (for example, various optical elements disposed in the optical path such as a glass substrate, a polarizing plate, a phase difference plate, and a light guide plate).

The transparent laminated film of the present invention can be produced, for example, by laminating layers on a transparent resin layer having an easy-to-attach layer.

Specifically, the hard coat layer may be coated with a curable composition on the surface of one side of the transparent resin layer (on the second easy-adhesion layer), and the coated hardenable composition may be dried to irradiate the active material. The energy line is produced by a hardening step of hardening.

In the coating step, the curable composition usually contains a mixture of a curable resin, a thermoplastic resin, and metal oxide fine particles and a solvent (particularly a liquid composition such as a uniform solution). In a preferred embodiment, a composition comprising a photocurable resin, a thermoplastic resin, metal oxide fine particles, a photopolymerization initiator, and a solvent capable of dissolving the photocurable resin and the thermoplastic resin is used as the mixture. .

The solvent may be selected depending on the type and solubility of the curable resin and the thermoplastic resin, and may be any solvent that can dissolve the solid component (curable resin, thermoplastic resin, reaction initiator, and other additives) at least uniformly. As such a solvent, for example, a ketone (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), an ether (second) can be exemplified. Alkane, tetrahydrofuran, etc.), aliphatic hydrocarbons (such as hexane), alicyclic hydrocarbons (such as cyclohexane), aromatic hydrocarbons (toluene, xylene, etc.), halocarbons (dichloromethane, dichloroethylene) Ethane, etc., esters (methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (ethanol, isopropanol, butanol, cyclohexanol, etc.), celluloids (methyl Bismuth, ethyl cyproterone, propylene glycol monomethyl ether (1-methoxy-2-propanol), celecoxime, hydrazine (dimethyl hydrazine, etc.), guanamine Classes (dimethylformamide, dimethylacetamide, etc.) and the like. These solvents may be used alone or in combination of two or more, or may be a mixed solvent. Among these solvents, preferred are ketones such as methyl ethyl ketone or cyclohexanone, alcohols such as butanol or 1-methoxy-2-propanol, which may be mixed. For example, the ketone and the former alcohol/the latter may be 90/10 to 10/90, preferably 80/20 to 40/60, and more preferably 70/30 to 50/50 ( Weight ratio) mixed. Further, an alkane ketone such as methyl ethyl ketone or a cycloalkanone such as cyclohexanone may be used in the former/the latter = 95/5 to 50/50 (especially 90/10 to 70/30). The ratio (weight ratio) is mixed. Further, an alkanol such as butanol or a celesta group such as 1-methoxy-2-propanol can be used as the former/the latter = 5/95 to 50/50 (especially 10/90 to 30/70). ) The ratio of the left and right (weight ratio) is mixed. In the present invention, the degree of aggregation of the metal oxide fine particles can be controlled by appropriately combining the solvents. In the present invention, in particular, by combining the solvents in such a ratio, a surface structure having a fine concavo-convex structure and a corrugated structure can be formed on the surface of the hard coat layer.

The concentration of the solute (curable resin, thermoplastic resin, metal oxide fine particles, reaction initiator, and other additives) in the mixed solution can be selected within a range that does not impair the castability, coatability, and the like, for example, 1 to 80% by weight. % is preferably from 5 to 60% by weight, more preferably from 15 to 40% by weight (especially from 20 to 40% by weight).

As the coating method, a conventional method such as a roll coater, an air knife coater, a knife coater, a rod coater, a reverse coater, a bar coater, and a notch can be mentioned. A wheel coater, a dipping, an extrusion coater, a die coater, a gravure coater, a micro gravure coater, a screen printing coater method, a dipping method, a spray method, a spinner method, and the like. Among these methods, a bar coater method, a gravure coater method, or the like is usually used. Further, the coating liquid may be applied in plural times if necessary.

In the coating step, after further mixing or coating the mixed liquid, the solvent is evaporated. The evaporation of the solvent is usually carried out at a temperature of, for example, 40 to 150 ° C, preferably 50 to 120 ° C, more preferably 60 to 100 ° C depending on the boiling point of the solvent.

In the hardening step, the applied curable composition is finally hardened by active light (ultraviolet rays, electron beams, etc.) or heat to form a hard coat layer. The curing of the curable resin may be combined with heating, light irradiation, or the like depending on the type of the curable resin.

The heating temperature can be selected from an appropriate range, for example, about 50 to 150 °C. The light irradiation can be selected depending on the type of the photocurable component, and the like, and ultraviolet rays, electron beams, or the like can be usually used. A common exposure source is usually an ultraviolet irradiation device.

In the case of a light source, for example, a UV light source, a deep ultraviolet light source, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a halogen lamp, a laser light source (a krypton-cadmium laser, a pseudo-molecular laser, etc.) can be used. )Wait. The amount of irradiation light (irradiation energy) varies depending on the thickness of the coating film, and can be selected from the range of about 10 to 10,000 mJ/cm ² (for example, 50 to 1000 mJ/cm ² ), and may be, for example, 10 to 5000 mJ/cm ² , preferably. It is 30 to 3000 mJ/cm ² , and more preferably 50 to 1000 mJ/cm ² or so.

Further, light irradiation can be carried out in an inert gas atmosphere if necessary. In particular, in the case of photocuring, the curing of the curable resin can be carried out not only immediately, but also by the heat from the inside of the transparent resin layer, and the analysis of low molecular weight of the oligomer or the like can be suppressed.

In the case of forming a high refractive index layer or in the case of forming a low refractive index layer on a hard coat layer, active light rays can usually also be used after coating or casting a coating liquid in the same manner as a hard coat layer. It is formed by hardening or the like. The method of forming the easy-adhesion layer or the transparent adhesive layer can also be carried out by a conventional method, and a method of applying or casting a coating liquid in the same manner as the above-described hard coat layer can be used.

In the present invention, in order to improve the adhesion between the layers, surface treatment can be provided for each layer. As the surface treatment, a conventional surface treatment such as corona discharge treatment, flame treatment, plasma treatment, ozone or ultraviolet irradiation treatment, or the like can be exemplified.

The transparent conductive layer is not particularly limited as long as it can form a film containing a metal or a metal compound, and can be formed by a conventional film formation method. As the film formation method, for example, a physical vapor deposition (PVD) method [for example, a vacuum evaporation method, a flash evaporation method, an electron beam evaporation method, an ion beam evaporation method, an ion plating method (for example, HCD) can be exemplified. Method, electron beam RF method, arc discharge method, etc.), sputtering method (for example, DC discharge method, high frequency (RF) discharge method, magnetron method, etc.), molecular line epitaxy method, laser ablation method, etc. A chemical vapor deposition (CVD) method (for example, a thermal CVD method, a plasma CVD method, an MOCVD method (organic metal vapor deposition method), a photo CVD method, etc.), an ion beam mixing method, an ion implantation method, or the like. Among these film forming methods, a physical vapor phase such as a vacuum vapor deposition method, an ion plating method, or a sputtering method is usually used. The deposition method, the chemical vapor deposition method, and the like are preferably a sputtering method or a plasma CVD method (especially, a sputtering method).

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by the examples. The transparent laminated film obtained in the examples and the comparative examples was evaluated according to the following items.

Average thickness of each layer

The average thickness of each layer was measured using an instantaneous multi-photometric system (MCPD-3700 manufactured by Otsuka Electronics Co., Ltd.).

Refractive index

The refractive index of each layer was measured by a refractometer (Metricon type 2010 稜鏡 coupler) manufactured by Metricon Co., Ltd. under the conditions of 407 nm, 633 nm (He-Ne laser), and 826 nm in accordance with JIS K7142.

Full light transmittance and haze

The haze was measured in accordance with JIS K7361 using a haze meter (manufactured by Nippon Denshoku Co., Ltd., trade name "NDH-5000W") in accordance with JIS K7361.

Reflection color difference △E

The reflection chromatic aberration ΔE is calculated based on the Lab value measured by an integrating sphere reflection intensity measuring device ("U-3300" manufactured by Hitachi High-Technologies Co., Ltd.).

Reflectivity

The black film was bonded to the high refractive index layer side of the transparent laminated film, and the integrated reflectance (conversion of visual sensitivity) was measured using an integrating sphere reflection intensity measuring device ("U-3300" manufactured by Hitachi High-Technologies Co., Ltd.).

Glare evaluation

The glare in the display surface was determined by attaching the transparent laminated film obtained in the examples and the comparative examples to a transparent glass plate having a thickness of 3 mm via an adhesive layer of a transparent laminated film, and placing it on a 5 inch LCD. On the screen (the number of pixels is 1920×1080, the resolution is 440 ppi), the surface of the transparent laminated film was faced with the screen, and the screen was set to green display, and the glare when viewed from the front of the screen was visually evaluated based on the following criteria.

◎: I don't feel glare.

○: A little glare is felt.

△: I feel glare.

×: Strong glare is felt.

Waterproof pattern (AWM)

A 0.7 mm transparent glass plate was bonded to the transparent laminated film through the adhesive layer of the transparent laminated film obtained in the examples and the comparative examples. Next, a 10-inch-sized polarizing plate having a gap of 1 cm in width and 0.2 mm in the outer periphery and a low-refractive-index layer (second hard coat layer) of the transparent laminated film were placed to face each other and overlap each other. Finally, the center portion of the transparent glass plate was pressed with a load of 20 N/cm ² for 10 seconds, and the state after the release for 10 seconds was evaluated according to the following criteria.

◎: The transparent laminated film and the transparent glass plate are not in close contact.

○: The transparent laminated film and the transparent glass plate are only adhered in some portions.

×: Both are in close contact.

Water contact angle of the side surface of the low refractive index layer

The contact angle of each liquid of about 3 μL was measured and averaged on the side surface of the low refractive index layer using an automatic ‧ dynamic contact angle meter ("DCA-UZ" manufactured by Kyowa Interface Science Co., Ltd.).

Arithmetic mean roughness Ra1

The arithmetic of the surface (concave-convex surface) on the low refractive index layer side (second hard coat layer side) of the transparent laminated film was measured by the following procedure from the adhesive layer side of the transparent laminated film obtained in the examples and the comparative examples in accordance with JIS B0601. Average roughness. In other words, a scanning probe microscope (manufactured by SII NanoTechnology Co., Ltd.) was used, and a cantilever was used as a probe, and the measurement mode was set to Tapping mode, and the measurement area was set to 10 μm × 10 μm to capture an image. For the obtained image, the analytical software attached to the scanning probe microscope was used, and Flaatten treatment (0 times) and Planefit treatment (XY) were performed once as an incremental process for removing undulations, and an arithmetic mean was calculated. Roughness Ra1.

Arithmetic mean roughness Ra2

In accordance with JIS B0601, the arithmetic mean roughness Ra2 was measured using a non-contact surface shape measurement system ("VertScan 2.0" manufactured by Ryoka Systems Co., Ltd.) and a measurement area of 500 μm × 500 μm.

Coating solution (Production Example 1 of Hard Coating Liquid Solution: HC-1a or HC-2a)

50 parts by weight of dipentaerythritol hexaacrylate ("DPHA" manufactured by DAICEL-ALLNEX Co., Ltd.), 50 parts by weight of pentaerythritol triacrylate ("PETRA" manufactured by DAICEL-ALLNEX), and 1.2 parts by weight of propylene acetate Acid cellulose ("CAP" by Eastman), Dissolved in 131 parts by weight of methyl ethyl ketone (MEK), 65 parts by weight of 1-methoxy-2-propanol (MMPG), 22 parts by weight of 1-butanol (BuOH), and 24 parts by weight of a ring In a mixed solvent of ketone. 2 parts by weight of a photopolymerization initiator ("IRGACURE 184" manufactured by BASF Japan Co., Ltd.) and 1 part by weight of a photopolymerization initiator ("IRGACURE 907" manufactured by BASF Japan Co., Ltd.) were added to the solution to dissolve. . Further, 1.5 parts by weight of ATO particle dispersion ("ELCOM SH-1212ATV" manufactured by Nippon Wax Chemical Co., Ltd., primary particle size 8 nm, 20% by weight of alcohol (ethanol/isopropanol = 80) was added to the solution. /20 (weight ratio) of a mixed solvent) dispersion, and stirring for 1 hour, preparation of the hard-coat coating liquid: HC-1a (or HC-2a).

(Production Example 2 of Hard Coating Liquid Solution: HC-1b or HC-2b)

A hard coat coating liquid: HC-1b (or HC-2b) was prepared in the same manner as in Production Example 1 except that the amount of the ATO particle dispersion was changed to 0.5 part by weight.

(Production Example 3 of Hard Coating Liquid Solution: HC-1c or HC-2c)

A hard coat was prepared in the same manner as in Production Example 1, except that 1.5 parts by weight of the "K-001" manufactured by Sekisui Chemical Co., Ltd. and a solid content of 20% by weight was used instead of 1.5 parts by weight of the ATO particle dispersion liquid. Layer coating liquid: HC-1c (or HC-2c).

(Production Example 4 of Hard Coating Liquid Solution: HC-1d or HC-2d)

A hard coat coating liquid: HC-1d (or HC-2d) was prepared in the same manner as in Production Example 1 except that the amount of the ATO particle dispersion was changed to 20 parts by weight.

(High refractive index layer coating liquid: IM layer)

Coating agent containing photocurable resin ("Lioduras TYZ" manufactured by Toyo Ink Co., Ltd., containing zirconia fine particles of nanometer size)

(low refractive index layer coating liquid: LR layer)

A commercially available hollow fine-particle fine particle dispersion ("ELCOMP-5063", solid content: 3% by weight) was used.

Further, in the following comparative examples and examples, the thickness of the high refractive index layer was adjusted by adjusting the concentration of the coating liquid.

Comparative example 1

As a transparent resin layer, a PET film ("UH13" manufactured by Toray Industries, Inc., and a PET film having an easy-adhesion layer, having a thickness of 50 μm) was used, and the HC-1a layer coating liquid was applied thereto using a bar coater #8. After one side of the film, it was dried at 80 ° C for 1 minute. The coated film was subjected to ultraviolet curing treatment by an ultraviolet irradiation device (manufactured by Ushio Electric Co., Ltd., high-pressure mercury lamp, ultraviolet irradiation amount: 500 mJ/cm ² ) to form an HC-1a layer. The thickness of the HC-1a layer in the obtained transparent laminated film was 1.0 μm.

Further, the HC-2a layer coating liquid was applied onto the other surface of the PET film using a bar coater #8, and then dried at 80 ° C for 1 minute. The coated film was subjected to ultraviolet curing treatment by an ultraviolet irradiation device (manufactured by Ushio Electric Co., Ltd., high-pressure mercury lamp, ultraviolet irradiation amount: 500 mJ/cm ² ) to form an HC-2a layer, thereby obtaining a transparent laminated film. The thickness of the HC-2a layer in the obtained transparent laminated film was 1.0 μm.

Comparative example 2

The LR layer coating liquid was applied onto the HC-2a layer of the transparent laminated film obtained in Comparative Example 1 using a bar coater #4, and dried at 120 ° C for 1 minute. Then, the coated film was subjected to ultraviolet curing treatment by an ultraviolet irradiation device (manufactured by Ushio Electric Co., Ltd., high-pressure mercury lamp, ultraviolet irradiation amount: 500 mJ/cm ² ) to form a low refractive index layer. The thickness of the LR layer in the obtained transparent laminated film was 100 nm.

Comparative example 3

A PET film (a PET film having an easy-adhesion layer and a thickness of 50 μm, manufactured by Toray Industries, Inc.) was used as the transparent resin layer, and the IM layer coating liquid was applied to one side of the film by a bar coater #5. After the surface, it was dried at 80 ° C for 2 minutes. The coated film was subjected to ultraviolet curing treatment by an ultraviolet irradiation device (manufactured by Ushio Electric Co., Ltd., high-pressure mercury lamp, ultraviolet irradiation amount: 500 mJ/cm ² ) to form an IM layer, thereby obtaining a transparent laminated film. The thickness of the IM layer in the obtained transparent laminated film was 0.9 μm.

Example 1

A PET film (a PET film having an easy-adhesion layer and a thickness of 50 μm, manufactured by Toray Industries, Inc.) was used as the transparent resin layer, and the IM layer coating liquid was applied to one side of the film by a bar coater #5. After the surface, it was dried at 80 ° C for 2 minutes. The coated film was subjected to ultraviolet curing treatment by an ultraviolet irradiation device (manufactured by Ushio Electric Co., Ltd., high-pressure mercury lamp, ultraviolet irradiation amount: 500 mJ/cm ² ) to form an IM layer, thereby obtaining a transparent laminated film. The thickness of the IM layer in the obtained transparent laminated film was 0.5 μm.

Further, the HC-2a layer coating liquid was applied onto the other surface of the PET film using a bar coater #8, and then dried at 80 ° C for 1 minute. The coated film was subjected to ultraviolet curing treatment by an ultraviolet irradiation device (manufactured by Ushio Electric Co., Ltd., high-pressure mercury lamp, ultraviolet irradiation amount: 500 mJ/cm ² ) to form an HC-2a layer, thereby obtaining a transparent laminated film. The thickness of the HC-2a layer in the obtained transparent laminated film was 1.0 μm.

Further, the LR layer coating liquid was applied onto the HC-2a layer of the obtained transparent laminated film using a bar coater #4, and dried at 80 ° C for 1 minute. Then, the coated film was subjected to ultraviolet curing treatment by an ultraviolet irradiation device (manufactured by Ushio Electric Co., Ltd., high-pressure mercury lamp, ultraviolet irradiation amount: 500 mJ/cm ² ) to form a low refractive index layer. The thickness of the LR layer in the obtained transparent laminated film was 100 nm.

Example 2

A transparent laminated film was obtained in the same manner as in Example 1 except that the thickness of the IM layer was changed to 0.7 μm.

Example 3

A transparent laminated film was obtained in the same manner as in Example 1 except that the thickness of the IM layer was changed to 0.9 μm.

Example 4

A transparent laminated film was obtained in the same manner as in Example 1 except that the refractive index of the IM layer was changed to 1.70.

Comparative example 4

A transparent resin layer (a PET film having an easy-to-adhere layer and a thickness of 50 μm) was used as the transparent resin layer, and the HC-1b layer coating liquid was applied to one side of the film by a bar coater #8. After the surface, it was dried at 80 ° C for 1 minute. The coated film was subjected to ultraviolet curing treatment by an ultraviolet irradiation device (manufactured by Ushio Electric Co., Ltd., high-pressure mercury lamp, ultraviolet irradiation amount: 500 mJ/cm ² ) to form an HC-1b layer. The thickness of the HC-1b layer in the obtained transparent laminated film was 1.0 μm.

Further, the HC-2b layer coating liquid was applied onto the other surface of the PET film using a bar coater #8, and then dried at 80 ° C for 1 minute. The coated film was subjected to ultraviolet curing treatment by an ultraviolet irradiation device (manufactured by Ushio Electric Co., Ltd., high-pressure mercury lamp, ultraviolet irradiation amount: 500 mJ/cm ² ) to form an HC-2b layer, thereby obtaining a transparent laminated film. The thickness of the HC-2b layer in the obtained transparent laminated film was 1.0 μm.

Comparative Example 5

A transparent laminated film was obtained in the same manner as in Comparative Example 4 except that the HC-1c layer and the HC-2c layer were used instead of the HC-1b layer and the HC-2b layer.

Comparative Example 6

The LR layer coating liquid was applied onto the HC-2c layer of the transparent laminated film obtained in Comparative Example 5 using a bar coater #4, and dried at 120 ° C for 1 minute. Then, the coated film was subjected to ultraviolet curing treatment by an ultraviolet irradiation device (manufactured by Ushio Electric Co., Ltd., high-pressure mercury lamp, ultraviolet irradiation amount: 500 mJ/cm ² ) to form a low refractive index layer. The thickness of the LR layer in the obtained transparent laminated film was 100 nm.

Comparative Example 7

A PET film (a PET film having an easy-adhesion layer and a thickness of 50 μm, manufactured by Toray Industries, Inc.) was used as the transparent resin layer, and the HC-1d layer coating liquid was applied to the film by a bar coater #8. After the side faces, it was dried at 80 ° C for 1 minute. The coated film was subjected to ultraviolet curing treatment by an ultraviolet irradiation device (manufactured by Ushio Electric Co., Ltd., high-pressure mercury lamp, ultraviolet irradiation amount: 500 mJ/cm ² ) to form an HC-1d layer. The thickness of the HC-1d layer in the obtained transparent laminated film was 1.0 μm.

Further, the HC-2d layer coating liquid was applied onto the other surface of the PET film using a bar coater #8, and then dried at 80 ° C for 1 minute. The coated film was subjected to ultraviolet curing treatment by an ultraviolet irradiation device (manufactured by Ushio Electric Co., Ltd., high-pressure mercury lamp, ultraviolet irradiation amount: 500 mJ/cm ² ) to form an HC-2d layer, thereby obtaining a transparent laminated film. The thickness of the HC-2d layer in the obtained transparent laminated film was 1.0 μm.

The LR layer coating liquid was applied onto the HC-2d layer of the obtained transparent laminated film using a bar coater #4, and dried at 120 ° C for 1 minute. Then, the coated film was subjected to ultraviolet curing treatment by an ultraviolet irradiation device (manufactured by Ushio Electric Co., Ltd., high-pressure mercury lamp, ultraviolet irradiation amount: 500 mJ/cm ² ) to form a low refractive index layer. The thickness of the LR layer in the obtained transparent laminated film was 100 nm.

After measuring the total light transmittance and haze of the transparent laminated film obtained in the comparative examples and the examples, InO ₂ and SnO were formed on the HC-1a-1d layer or the IM layer of the transparent laminated film obtained in the comparative examples and the examples. _After the composite oxide (ITO) of 2 was subjected to a sputtering treatment to form a transparent conductive layer, the ITO film was removed by immersion in 1 N hydrochloric acid to form a region where the transparent conductive layer was not formed. In addition, a coating liquid for an adhesive layer ("LUCIACS CS9621T" manufactured by Nitto Denko Corporation) was attached to the ITO film to form a transparent adhesive layer having a thickness of 25 μm. The reflection color difference ΔE of the transparent laminated film obtained in Comparative Examples 1 to 3 and the examples was measured. The results obtained are shown in Table 1. Further, the reflectance, glare, AWM properties, water contact angle, and surface roughness Ra of the transparent laminated films obtained in Comparative Examples 4 to 7 and the examples were measured. The results obtained are shown in Table 2.

As is clear from the results of Table 1, the transparent laminated film of the example was higher in transparency and smaller in color difference ΔE than in the comparative example.

As is clear from the results of Table 2, the transparent laminated film of the example was lower in haze than in the comparative example, and the glare was small and the AWM property was also excellent.

[Industry use possibility]

The transparent laminated film of the present invention can be used for various optical display devices which are used for patterning a transparent conductive layer, and can be used, for example, in personal computers, televisions, mobile phones (smart phones), electronic paper, game machines, mobile machines. A touch panel (resistive film type touch) used in combination with a display device (a liquid crystal display device, a plasma display device, an organic or inorganic EL display device, etc.) in a display unit of an electric or electronic device or a computer such as a watch or a computer Panel, electrostatic capacity touch panel, etc.). In particular, due to excellent visibility, a projection type electrostatic capacitance type touch panel using an ITO grid method is useful.

Claims (10)

A transparent laminated film which is a transparent resin layer and sequentially has a first easy-adhesion layer and a high refractive index layer on one surface of the transparent resin layer, on the other side of the transparent resin layer a transparent laminated film of a second easy-adhesion layer, a hard coat layer, and a low refractive index layer, wherein the first and second easy-adhesion layers each have a refractive index of 1.5 to 1.7 and a thickness of 30 to 200 nm, and the high refractive index The refractive index layer has a refractive index of 1.6 to 1.8 and a thickness of 120 to 2000 nm, and the low refractive index layer has a refractive index of 1.2 to 1.5 and a thickness of 10 to 200 nm. The transparent laminated film of claim 1, wherein the haze is 0.05 to 1%. The transparent laminated film according to claim 1 or 2, wherein the surface of the low refractive index layer has an arithmetic mean roughness Ra1 calculated in a measurement region of 10 μm × 10 μm of 0.7 nm or more and less than 5 nm, and an arithmetic mean calculated in a measurement region of 500 μm × 500 μm. The roughness Ra2 is a concave-convex structure of 10 to 50 nm. The transparent laminated film according to any one of claims 1 to 3, wherein the hard coat layer is a cured product containing a curable resin, a thermoplastic resin, and a hardenable composition of metal oxide particles having an average primary particle diameter of 1 to 50 nm. form. The transparent laminated film according to any one of claims 1 to 4, wherein the transparent conductive layer having a refractive index of 1.8 to 2.3 and a thickness of 10 to 60 nm is sequentially laminated on the high refractive index layer, and the refractive index is Transparent layer of 1.4~2.3. The transparent laminated film according to claim 5, wherein the reflection color difference ΔE due to the presence or absence of the transparent conductive layer represented by the following formula is 10 or less, ΔE = ((L _a ^{* -} L _b ^* ) ² + (a _a ^* - a _b ^* ) ² + (b _a ^* - _{b b} ^* ) ² ) ^1/2 (wherein, L _a ^* , a _a ^* , b _a ^* are 10° reflection L ^* of the transparent conductive layer portion ^{, a *, b *, L} b *, a b *, b b * 10 ° reflection of the non-laminated portion of the transparent conductive layer ^{L *, a *, b *} ). The transparent laminated film according to any one of claims 1 to 6, wherein the total light transmittance is 90% or more. The transparent laminated film according to any one of claims 1 to 7, wherein the surface of the low refractive index layer has a water contact angle of 65 to 80°. The transparent laminated film according to any one of claims 1 to 8, wherein the high refractive index layer is formed of a cured product of a curable composition containing inorganic fine particles. An electrostatic capacitance type touch panel display comprising the transparent laminated film according to any one of claims 1 to 9.