KR20160117165A - Transparent conductive film - Google Patents

Abstract

The purpose of the present invention is to provide a laminate used to form a transparent conductive layer; and a transparent conductive film using the same. The laminate has etching resistance in a low refractive layer, can stably prevent the visualization of the pattern shape of a transparent conductive layer, and secures excellent adhesion between the laminate and the transparent conductive layer or the like. The laminate used to form a transparent conductive layer has an optical control layer on at least one surface of a base film. The optical control layer is formed by sequentially laminating a high refractive layer with a refractive index of 1.6 or greater and a low refractive layer with a refractive index of 1.45 or smaller on the base film. The low refractive layer is formed by photo-curing a composition used to form a low refractive layer, which includes (A) 100 parts by weight of an active energy ray-curable resin containing a water-repellent resin and (B) 2-120 parts by weight of a silica particle.

Description

Transparent conductive film {TRANSPARENT CONDUCTIVE FILM}

The present invention relates to a laminate for forming a transparent conductive layer and a transparent conductive film.

Particularly, a laminate for forming a transparent conductive layer which is excellent in etching resistance in a low refractive index layer and which can stably impregnate the pattern shape of the transparent conductive layer and has excellent adhesion with the transparent conductive layer, And the transparent conductive film used.

BACKGROUND ART [0002] A touch panel capable of inputting information by directly contacting an image display unit is conventionally arranged by placing a light-transmitting input device on a display.

As typical examples of such a touch panel, there are a resistive film type touch panel in which two transparent electrode substrates are arranged while providing their gaps so that the respective transparent electrode layers are opposed to each other, and a change in capacitance caused between the transparent electrode film and the finger There is a capacitive touch panel using a touch panel.

Among them, the capacitive touch panel includes a glass sensor in which a transparent conductive layer is layered on a glass substrate, and a transparent conductive layer is formed on the transparent plastic film substrate There is a film sensor formed by laminating on a substrate.

Particularly in a film sensor, a grid-like pattern is often formed by arranging two transparent conductive films each having a transparent conductive layer patterned in a line so that the respective patterns cross each other.

However, when the transparent conductive layer is patterned in this manner, the boundary portion between the pattern portion and the non-pattern portion is liable to be visually observed, and the appearance of the capacitive touch panel is deteriorated.

Therefore, a technique for solving such a problem is disclosed (see, for example, Patent Documents 1 and 2).

That is, Patent Document 1 discloses a laminated film having a resin layer on at least one side of a polyester film, wherein the resin layer contains at least a silica particle (B) and an acrylic resin (D) (Meth) acrylate monomer represented by the following general formula (1): wherein the number average particle diameter of the silica particles is 30 nm or more and 120 nm or less, and the acrylic resin (D) (d-1) represented by the following general formula (2) and a (meth) acrylate monomer (d-2) represented by the following general formula (2), wherein the minimum reflectance of the laminated film on the side of the resin layer is 2.0% Discloses an optical laminated film.

(In the general formula (1), the R ¹ group represents a hydrogen atom or a methyl group, and n in the general formula (1) represents an integer of 9 or more and 34 or less)

(In the general formula (2), the R ¹ group represents a hydrogen atom or a methyl group, and the R ² group represents a functional group containing two or more saturated carbon rings)

Patent Document 2 discloses a transparent film substrate having at least one undercoat layer on one side or both sides of a transparent film substrate and having a transparent conductor layer and a transparent conductor layer patterned, A step of forming an undercoat layer formed on a transparent film substrate by an organic material on one surface or both surfaces of a transparent film substrate; a step of forming a transparent conductive film on an undercoat layer by a sputtering method A step of forming a transparent conductor layer by a photolithography method, and a step of patterning the transparent conductor layer by etching.

It is also described that the above-mentioned undercoat layer is composed of two layers, and the outermost undercoat layer is formed as an SiO ₂ film formed by coating silica sol.

Japanese Patent Application Laid-Open No. 2013-52676 (claims) Japanese Patent Application Laid-Open No. 2011-142089 (claims)

However, in the optical laminated film disclosed in Patent Document 1, when the transparent conductive layer is patterned by etching, the resin layer on which the transparent conductive layer is formed is likely to be eroded by the etching solution, It is difficult to stably incapacitate the liquid crystal display device.

More specifically, in recent years, in accordance with the increase in the production of smart phones and the like, it is required to speed up the etching process. Particularly, in the alkali treatment for removing the residual photoresist which is the final step of the etching treatment, Lt; RTI ID = 0.0 >% < / RTI > of aqueous sodium hydroxide solution may be used.

When such a severe alkali treatment is performed, the silica particles in the resin layer in the optical laminated film disclosed in Patent Document 1 tend to melt or fall off, and as a result, the pattern shape of the transparent conductive layer It has become difficult to make it impossible to make it invisible.

Also in the case of the transparent conductive film obtained by the production method disclosed in Patent Document 2, silica particles in the SiO ₂ film are likely to melt or fall off when a severe alkali treatment is carried out. As a result, There has been a problem that it is difficult to stably make the pattern shape of the transparent conductive layer invisible.

In view of the above, the inventors of the present invention have found that, in forming the low refractive index layer which is the outermost layer of the laminate for forming a transparent conductive layer, the active energy ray curable resin containing a water- , And a composition for forming a low refractive index layer in which silica fine particles are blended in a predetermined range, the above-mentioned problem can be solved, and the present invention has been completed.

That is, an object of the present invention is to provide a transparent conductive layer having excellent etching resistance in a low refractive index layer, capable of stably invisibly patterning a transparent conductive layer, And a transparent conductive film using the same.

According to the present invention, there is provided a laminate for forming a transparent conductive layer having an optical adjustment layer on at least one surface of a base film, wherein the optical adjustment layer comprises a high refractive index layer having a refractive index of 1.6 or more and a refractive index of 1.45 Wherein the low refractive index layer is formed by laminating in order a low refractive index layer having a refractive index lower than that of the low refractive index layer and a low refractive index layer, There is provided a laminate for forming a laminated structure, and the above-described problems can be solved.

(A) 100 parts by weight of an active energy ray-curable resin containing a water-repellent resin

(B) 2 to 120 parts by weight of fine silica particles

That is, in the case of the laminate for forming a transparent conductive layer of the present invention, the composition for forming a low refractive index layer used for forming the low refractive index layer as the outermost layer includes an active energy ray curable resin containing a water repellent resin, , The active energy ray-curable resin containing such a water-repellent resin contains silica particles in a relatively small range, so that even when an etching treatment including a severe alkali treatment is performed, the silica fine particles in the low refractive index layer (Hereinafter, this effect may be referred to as " etching resistance " in some cases).

The refractive index of the low refractive index layer, which is increased by adding the silica fine particles in a relatively small range, is lowered to a predetermined range by a water repellent resin having a relatively low refractive index to obtain a predetermined refractive index required for the low refractive index layer .

As a result, the pattern shape of the transparent conductive layer can be stably invisible.

The surface free energy of the low refractive index layer, which is lowered by the inclusion of the water-repellent resin, is increased to a predetermined range by the fine surface irregularities formed by the fine silica particles, A predetermined adhesion can be obtained.

In forming the transparent conductive layer-forming laminate of the present invention, it is preferable that the volume average particle diameter (D50) of the fine silica particles as the component (B) is within a range of 20 to 70 nm.

By such a constitution, a predetermined refractive index can be obtained without lowering the transparency in the low refractive index layer.

In forming the transparent conductive layer-forming laminate of the present invention, the fine silica particles as the component (B) are preferably hollow silica fine particles.

By such a constitution, the refractive index of the silica fine particles is further lowered, so that even if the amount is small, the refractive index of the low refractive index layer can be adjusted to a predetermined refractive index more efficiently.

In forming the transparent conductive layer-forming laminate of the present invention, it is preferable that the fine silica particles as the component (B) are reactive fine silica particles.

By such a constitution, since the silica fine particles can be firmly fixed to the low refractive index layer, the etching resistance can be improved more effectively.

In forming the transparent conductive layer-forming laminate of the present invention, the water-repellent resin constituting a part of the active energy ray-curable resin containing the water-repellent resin as the component (A) is preferably a fluorine resin.

By such a constitution, it is possible to more effectively protect the fine silica particles in the low refractive index layer, so that the etching resistance can be more effectively improved and the refractive index of the low refractive index layer can be lowered more effectively to a predetermined range have.

In forming the transparent conductive layer-forming laminate of the present invention, the surface free energy in the low refractive index layer is preferably set to a value of 37 mN / m or more.

By such a constitution, it is possible to more effectively obtain the predetermined adhesion to the transparent conductive layer or the like required for the low refractive index layer while improving the etching resistance.

In forming the transparent conductive layer-forming laminate of the present invention, it is preferable that the film thickness of the low refractive index layer is within a range of 20 to 150 nm.

With this structure, sufficient etching resistance can be obtained, and accordingly, the pattern shape of the transparent conductive layer can be more stably prevented even under a severe etching treatment condition.

According to another aspect of the present invention, there is provided a transparent conductive film comprising an optical adjustment layer and a transparent conductive layer laminated in order on at least one surface of a base film, wherein the optical adjustment layer has a refractive index of 1.6 or more And a low refractive index layer having a refractive index of 1.45 or less are stacked in this order, and the low refractive index layer is formed by laminating a composition for forming a low refractive index layer, which comprises the following components (A) to (B) Wherein the transparent conductive film is a transparent conductive film.

(A) 100 parts by weight of an active energy ray-curable resin containing a water-repellent resin

(B) 2 to 120 parts by weight of fine silica particles

That is, in the case of the transparent conductive film of the present invention, since the laminate for forming a predetermined transparent conductive layer is used, the low-refractive index layer has excellent etching resistance, and even if a severe etching process is performed, It can be stably incapacitated and excellent adhesion to the transparent conductive layer and the like can be obtained.

In forming the transparent conductive film of the present invention, it is preferable that the transparent conductive layer is patterned by etching.

Even in this case, since the etching resistance in the low refractive index layer is excellent, the pattern shape of the transparent conductive layer can be stably invisible.

1 (a) and 1 (b) are diagrams for explaining the structure of a laminate for forming a transparent conductive layer of the present invention.
Fig. 2 is a view for explaining the relationship between the blending amount of the fine silica particles and the etching resistance and surface free energy in the low refractive index layer. Fig.
Fig. 3 is a view for explaining the structure of the transparent conductive film of the present invention. Fig.

[First Embodiment]

The first embodiment of the present invention is a laminated body 10 for forming a transparent conductive layer having an optical adjustment layer 2 on at least one surface of a base film 4 as shown in Fig. The optical adjusting layer 2 is formed by laminating a high refractive index layer 2b having a refractive index of 1.6 or more and a low refractive index layer 2a having a refractive index of 1.45 or less in this order from the side of the base film 4 , And the low refractive index layer (2a) are obtained by photo-curing a composition for forming a low refractive index layer containing the following components (A) to (B).

(A) 100 parts by weight of an active energy ray-curable resin containing a water-repellent resin

(B) 2 to 120 parts by weight of fine silica particles

1 (a), the transparent conductive layer-forming laminate 10 having the hard coat layer 3 on both sides of the base film 4 is shown as an example. However, the hard coat layer 3 is omitted can do.

Further, in Fig. 1 (a), the particles in each layer represent silica fine particles or metal oxide particles.

Hereinafter, a first embodiment of the present invention will be described in detail with reference to the drawings.

1. Base film

(1) Type

The type of the base film is not particularly limited, and a known base film may be used as the optical base material.

For example, a polyester film such as polyethylene terephthalate (PET), polybutylene terephthalate and polyethylene naphthalate (PEN), a polyethylene film, a polypropylene film, a cellophane, a diacetylcellulose film, a triacetylcellulose film, Polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, poly A plastic film such as an ether sulfone film, a polyether imide film, a polyimide film, a fluororesin film, a polyamide film, an acrylic resin film, a norbornene resin film, and a cycloolefin resin film.

Among these, from the viewpoint of heat resistance, a polyester film, a polycarbonate film, a polyimide film, a norbornene resin film, and a cycloolefin resin film are more preferable.

In addition, from the viewpoint of achieving both transparency and film strength and flexibility, a PET film is particularly preferable.

(2) Thickness

It is also preferable that the film thickness of the base film is within a range of 20 to 200 mu m.

This is because when the film thickness of the base film is less than 20 占 퐉, the strength of the base film is lowered, so that the deflection during the annealing process in the presence and absence of the transparent conductive layer in the optical adjustment layer Can not be effectively suppressed from occurring. On the other hand, if the film thickness of the base film exceeds 200 탆, optical properties such as transparency in the base film may deteriorate.

Therefore, the thickness of the base film is more preferably in the range of 30 to 180 占 퐉, and more preferably in the range of 50 to 150 占 퐉.

The term " annealing treatment " refers to a treatment for crystallizing a transparent conductive layer in a laminated state on a laminate for forming a transparent conductive layer by heat treatment in order to improve the electrical conductivity of the transparent conductive layer in the transparent conductive film it means.

2. Hard coating layer

As shown in Fig. 1 (a), in forming the transparent conductive layer-forming laminate 10 of the present invention, it is preferable to provide the hard coat layer 3 on both sides or one side of the base film 4 .

The reason for this is that by providing such a hard coating layer, it is possible to prevent scratching of the base film and deterioration of optical properties in the production process of the laminate for forming a transparent conductive layer, This is because it is possible to suppress occurrence of a phenomenon in which the base films adhere to each other when the film is rolled up in a roll (hereinafter, this effect is sometimes referred to as " anti-blocking property ").

(1) Material materials

Further, it is preferable that the hard coat layer is composed of a cured product of a composition containing fine silica particles and an active energy ray-curable resin as a material.

This is because the anti-blocking property can be imparted by including the silica fine particles and the active energy ray-curable resin, so that not only the improvement in the winding property can be expected but also the adhesiveness with the high refractive index layer as the upper layer of the hard coat layer So that it can be stacked strongly.

(1) -1 active energy ray curable resin

The active energy ray-curable resin used for forming the hard coat layer means a polymerizable compound having both energy in an electromagnetic wave or a charged particle beam, that is, a polymerizable compound which is crosslinked or cured by irradiation with ultraviolet rays or electron beams, Examples thereof include a photopolymerizable prepolymer and a photopolymerizable monomer.

Examples of the photopolymerizable prepolymer include radical polymerization type and cation polymerization type. Examples of the radically polymerizable type photopolymerizable prepolymer include polyester acrylate type, epoxy acrylate type, urethane acrylate type, polyol acrylate type, and the like. .

The polyester acrylate-based prepolymer may be obtained by, for example, esterifying a hydroxyl group of a polyester oligomer having a hydroxyl group at both ends with condensation of a polyhydric carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, And a compound obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid.

Examples of the epoxy acrylate-based prepolymer include compounds obtained by esterification with oxirane rings of a relatively low molecular weight bisphenol-type epoxy resin or novolak-type epoxy resin with (meth) acrylic acid.

Examples of the urethane acrylate-based prepolymer include compounds obtained by esterifying a polyurethane oligomer obtained by the reaction of a polyether polyol or a polyester polyol with a polyisocyanate with (meth) acrylic acid.

Examples of the polyol acrylate-based prepolymer include compounds obtained by esterifying a hydroxyl group of a polyether polyol with (meth) acrylic acid.

These polymerizable prepolymers may be used singly or in combination of two or more kinds.

On the other hand, as the cationic polymerization type photopolymerizable prepolymer, an epoxy resin is usually used.

Examples of such epoxy resins include compounds obtained by epoxidizing polyvalent phenols such as bisphenol resin and novolac resin with epichlorohydrin or the like, compounds obtained by oxidizing a linear olefin compound or cyclic olefin compound with a peroxide or the like .

Examples of the photopolymerizable monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di Acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di Acrylate, isocyanurate di (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, ethylene oxide modified di (meth) acrylate, allylated cyclohexyl di (Meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid And polyfunctional acrylates such as modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone modified dipentaerythritol hexa (meth) acrylate.

These photopolymerizable monomers may be used alone, or two or more of them may be used in combination.

(1) -2 Photopolymerization initiator

Further, since the active energy ray-curable resin can be effectively cured by an active energy ray, particularly ultraviolet rays, it is also preferable to use a photopolymerization initiator in combination with the desired one.

Examples of such photopolymerization initiators include radically polymerizable photopolymerizable prepolymers and photopolymerizable monomers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, Benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy- Propan-1-one, 4- (2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- (Hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2- Ethyl anthraquinone, 2-tert-butyl anthraquinone, 2-amino anthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2- chlorothioxanthone, 2,4-dimethylthioxanthone, Thio Tone, and the like benzyl dimethyl ketal, acetophenone dimethyl ketal, p- dimethylamine benzoic acid ester.

Examples of the photopolymerization initiator for the cationic polymerization-type photopolymerizable prepolymer include an onium such as an aromatic sulfonium ion, an aromatic oxosulfonium ion, and an aromatic iodonium ion, and a photopolymerization initiator such as tetrafluoroborate, hexafluorophosphate, Hexafluoroarsenate, hexafluoroantimonate, hexafluoroarsenate and the like, and the like.

These may be used alone, or two or more kinds may be used in combination.

The blending amount of the photopolymerization initiator is preferably within a range of 0.2 to 10 parts by weight, more preferably within a range of 1 to 5 parts by weight, based on 100 parts by weight of the above-mentioned active energy ray curable resin.

(1) -3 Silica fine particles

As the silica fine particles, fine silica particles to which an organic compound containing a polymerizable unsaturated group is bonded, or ordinary colloidal silica fine particles which do not have such a polymerizable unsaturated group-containing organic compound can be used.

As the silica fine particles to which the polymerizable unsaturated group-containing organic compound is bonded, a silanol group on the surface of the fine silica particles having a volume average particle size (D50) of about 0.005 to 1 mu m is preferable. The silanol group having a functional group capable of reacting with the silanol group Containing polymerizable unsaturated group and an organic compound containing a polymerizable unsaturated group.

Examples of the above-mentioned polymerizable unsaturated group include a radical polymerizable acryloyl group and a methacryloyl group.

As the conventional colloidal silica fine particles not having the polymerizable unsaturated group-containing organic compound, silica fine particles having a volume average particle diameter of about 0.005 to 1 mu m, preferably about 0.01 to 0.2 mu m, Colloidal silica formed by suspending in a colloidal state in a solvent can be suitably used.

The average particle size of the fine silica particles can be obtained by using, for example, a laser diffraction scattering type particle size distribution measuring apparatus, which can be required by, for example, a zeta potential measurement method, or based on an SEM image.

The blending amount of the fine silica particles is preferably 5 to 400 parts by weight, more preferably 20 to 150 parts by weight, and still more preferably 30 to 100 parts by weight based on 100 parts by weight of the active energy ray curable resin.

(2) Composition for forming hard coat layer

The hard coat layer is preferably formed by preparing a composition for forming a hard coat layer, coating, drying and curing as described below.

The composition is prepared by adding, if necessary, an active energy ray-curable resin, a photopolymerization initiator, fine silica particles, and various additive components to be used in desired proportions in predetermined ratios, and dissolving or dispersing them .

Examples of various additives include antioxidants, ultraviolet absorbers, (near) infrared absorbers, silane coupling agents, light stabilizers, leveling agents, antistatic agents and antifoaming agents.

Examples of the solvent to be used include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, alcohols such as methanol, ethanol, propanol and butanol, , Ketones such as methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate, and cellosolve solvents such as ethyl cellosolve.

The concentration and viscosity of the composition for forming a hard coat layer prepared as described above are not particularly limited and may be appropriately selected depending on the situation.

Therefore, from the viewpoint of easily adjusting the film thickness of the composition for forming a hard coat layer to be obtained in a predetermined range, it is preferable to dilute the composition so as to have a solid concentration of 0.05 to 10 wt%, and dilute to 0.1 to 8 wt% desirable.

(3) Thickness

The thickness of the hard coat layer is preferably in the range of 1 to 15 占 퐉.

The reason for this is that when the film thickness of the hard coat layer is less than 1 占 퐉, the holding function for thermal shrinkage of the base film by the annealing process becomes insufficient and the occurrence of curling can not be suppressed in some cases. On the other hand, when the film thickness of the hard coat layer exceeds 15 mu m, outgassing from the hard coat layer is likely to occur due to the annealing process.

Therefore, the thickness of the hard coat layer is more preferably in the range of 1.5 to 10 mu m, and more preferably in the range of 2 to 5 mu m.

3. Optical adjustment layer

(1) High refractive index layer

(1) -1 Refractive index

And the refractive index of the high refractive index layer is set to a value of 1.6 or more.

This is because, when the refractive index of the high refractive index layer is less than 1.6, a difference in refractive index with respect to the low refractive index layer is not obtained, and the pattern shape of the transparent conductive layer is likely to be visually recognized. On the other hand, when the refractive index of the high refractive index layer becomes excessively large, the film of the high refractive index layer may become fragile.

Therefore, the refractive index of the high refractive index layer is more preferably in the range of 1.61 to 2, more preferably in the range of 1.63 to 1.8.

(1) -2 material material

It is also preferable that the high refractive index layer is composed of a cured product of a composition comprising metal oxide fine particles as a material and an active energy ray curable resin.

This is because the inclusion of the metal oxide fine particles and the active energy ray-curable resin facilitates adjustment of the refractive index in the high refractive index layer.

Examples of the metal oxide include tantalum oxide, zinc oxide, indium oxide, hafnium oxide, cerium oxide, tin oxide, niobium oxide, indium tin oxide (ITO), and antimony tin oxide (ATO).

From the viewpoint of realizing high refractive index without lowering transparency, it is particularly preferable that at least one kind selected from titanium oxide and zirconium oxide is used.

These metal oxides may be used alone, or two or more of them may be used in combination.

The volume average particle diameter (D50) of the metal oxide fine particles is preferably in the range of 0.005 mu m to 1 mu m.

The volume average particle size (D50) of the metal oxide fine particles can be determined by, for example, a measurement method using a zeta potential measurement method, a laser diffraction scattering type particle size distribution measurement device, a SEM It can also be based on images.

The active energy ray-curable resin and the photopolymerization initiator used in the high refractive index layer may be those exemplified in the description of the hard coat layer.

The blending amount of the metal oxide fine particles is preferably 20 to 2000 parts by weight, more preferably 80 to 1,000 parts by weight, and further preferably 150 to 400 parts by weight, based on 100 parts by weight of the active energy ray curable resin.

(1) -3 composition for forming a high refractive index layer

It is preferable that the high refractive index layer is formed by preparing a composition for forming a high refractive index layer in advance, coating, drying and curing as described below.

The composition is prepared by adding, if necessary, an active energy ray-curable resin, a photopolymerization initiator, a metal oxide fine particle, and various additive components to be used by a desired ratio in a suitable solvent, and dissolving or dispersing .

The concentration of the various additives, the solvent, the composition for forming the high refractive index layer, and the like are the same as those in the description of the hard coat layer.

(1) -4 film thickness

The thickness of the high refractive index layer is preferably 20 to 130 nm.

This is because when the film thickness of the high refractive index layer is less than 20 nm, the film of the high refractive index layer becomes fragile and the shape of the layer can not be maintained. On the other hand, when the film thickness of the high refractive index layer exceeds 130 nm, the pattern shape of the transparent conductive layer tends to be visually recognized.

Therefore, the film thickness of the high refractive index layer is more preferably 23 to 120 nm, and more preferably 30 to 110 nm.

(2) Low Refractive Index Layer

(2) -1 Refractive index

And the refractive index of the low refractive index layer is set to a value of 1.45 or less.

This is because, when the refractive index of the low refractive index layer exceeds 1.45, a difference in refractive index with respect to the high refractive index layer is not obtained, and the pattern shape of the transparent conductive layer is likely to be visually recognized. On the other hand, if the refractive index of the low refractive index layer becomes excessively small, the film of the low refractive index layer may become fragile.

Therefore, the refractive index of the low refractive index layer is more preferably in the range of 1.3 to 1.44, and more preferably in the range of 1.35 to 1.43.

(2) -2 material material

The low refractive index layer in the present invention is characterized in that a composition for forming a low refractive index layer containing the following components (A) to (B) as a material is photocured.

(A) 100 parts by weight of an active energy ray-curable resin containing a water-repellent resin

(B) 2 to 120 parts by weight of fine silica particles

This is because the composition for forming a low refractive index layer used for forming the low refractive index layer contains a relatively small amount of silica fine particles in the active energy ray curable resin containing a water repellent resin, It is possible to effectively prevent the fine silica particles in the low refractive index layer from melting or falling off.

More specifically, as shown in Fig. 1 (a), when the blending amount of the fine silica particles in the low refractive index layer 2a is small, the presence of the matrix portion made of resin becomes large, It is possible to effectively prevent the silica fine particles from being effectively protected, melted, or dropped out of the matrix portion.

On the other hand, as shown in Fig. 1 (b), when the blending amount of the fine silica particles in the low refractive index layer 2a 'is large, the presence of the matrix portion made of resin becomes small, , The silica fine particles are not sufficiently protected by the matrix portion, and it becomes easy to melt or fall off.

The refractive index of the low refractive index layer, which is increased by adding the silica fine particles in a relatively small range, is lowered to a predetermined range by a water repellent resin having a relatively low refractive index to obtain a predetermined refractive index required for the low refractive index layer .

As a result, the pattern shape of the transparent conductive layer formed on the refractive index adjustment layer can be stably invisible.

Further, the surface free energy of the low refractive index layer, which is lowered by the inclusion of the water-repellent resin, is increased to a predetermined range by the fine surface irregularities formed by the fine silica particles, Can be obtained.

Each component will be described below.

(i) Component (A): an active energy ray-curable resin containing a water-repellent resin

The component (A) is an active energy ray-curable resin containing a water-repellent resin.

As the active energy ray-curable resin constituting the component (A), the photopolymerizable prepolymer exemplified in the description of the hard coat layer and the photopolymerizable monomer may be used as an enemy.

The water repellent resin constituting the component (A) is not particularly limited as long as it is a resin having water repellency, and conventionally known water repellent resins can be used.

More specifically, if the surface free energy of a resin film formed of a water repellent resin alone is within a range of 10 to 30 mN / m, it can be suitably used as a water repellent resin in the present invention.

Specific examples of the water-repellent resin include silicone resins, and fluororesins such as polyvinylidene fluoride, fluorine-based acrylic resin and polyfluoroethylene.

Among them, a fluororesin is preferably used, and a reactive fluororesin is particularly preferable.

This is because if the fluororesin is used, the fine silica particles in the low refractive index layer can be more effectively protected, and the etching resistance can be more effectively improved.

When the content of the water-repellent resin is 100% by weight of the entirety of the component (A), the content is preferably within a range of 50 to 90% by weight.

This is because when the content of the water-repellent resin is less than 50% by weight, it is difficult to effectively protect the fine silica particles in the low refractive index layer, and furthermore, it may become difficult to improve the etching resistance . This is because it may be difficult to make the refractive index of the low refractive index layer sufficiently low. On the other hand, when the content of the water-repellent resin exceeds 90% by weight, the surface free energy of the low refractive index layer becomes excessively low, and it is difficult to obtain a desired adhesion to the transparent conductive layer or the like required for the refractive index layer This is because there is a case to be made.

Therefore, when the content of the water-repellent resin is 100% by weight based on 100% by weight of the entirety of the component (A), it is more preferably in the range of 60 to 85% by weight, and more preferably in the range of 70 to 80% More preferable.

(Ii) Component (B): silica fine particles

The component (B) is a silica fine particle.

The kind of such fine silica particles is not particularly limited, but hollow silica fine particles are preferably used.

This is because the hollow silica fine particles contain air in the hollow portion inside thereof, so that the refractive index as a whole of the fine silica particles is further lowered and the refractive index of the low refractive index layer can be adjusted to a predetermined refractive index more efficiently even with a small blending amount to be.

The term " hollow silica fine particles " means fine silica particles having cavities inside the particles.

The silica fine particles are preferably reactive silica fine particles.

This is because the silica fine particles can be firmly fixed to the low refractive index layer in the case of the reactive silica fine particles, so that the etching resistance can be more effectively improved.

The term " reactive silica fine particles " is a fine silica particle to which a polymerizable unsaturated group-containing organic compound is bonded, and includes a polymerizable unsaturated group-containing organosiloxane having a functional group capable of reacting with the silanol group, Or by reacting a compound of the formula

Examples of the above polymerizable unsaturated group include radical polymerizable acryloyl groups and methacryloyl groups.

The volume average particle diameter (D50) of the fine silica particles is preferably set to a value within a range of 20 to 70 nm.

This is because a predetermined refractive index can be obtained without lowering the transparency in the low refractive index layer by setting the volume average particle diameter (D50) of the silica fine particles to a value within this range.

That is, when the volume average particle size (D50) of the silica fine particles is less than 20 nm, it is difficult to sufficiently secure the cavity inside the particle, particularly in the case of hollow silica fine particles, and the refractive index of the low refractive index layer is lowered This is because there is a case where the effect of causing the problem is insufficient. On the other hand, when the volume average particle size (D50) of the silica fine particles exceeds 70 nm, scattering of light tends to occur, and transparency in the low refractive index layer tends to be lowered.

Therefore, the volume average particle diameter (D50) of the fine silica particles is more preferably in the range of 30 to 60 nm, and more preferably in the range of 40 to 50 nm.

The volume average particle size (D50) of the fine silica particles can be determined by, for example, a zeta potential measurement method, a laser diffraction scattering type particle size distribution measurement device, or a SEM image It can also be obtained.

The blending amount of the fine silica particles is set to a value within a range of 2 to 120 parts by weight based on 100 parts by weight of the active energy ray curable resin containing the water-repellent resin as the component (A).

This is because when the blending amount of the silica fine particles is less than 2 parts by weight, it is difficult to sufficiently lower the refractive index of the low refractive index layer, or it becomes difficult to form sufficient surface unevenness on the surface of the low refractive index layer, And it may be difficult to obtain a predetermined adhesion to the layer or the like. On the other hand, when the blending amount of the silica fine particles exceeds 120 parts by weight, there is a case where the fine silica particles in the low refractive index layer are melted or fall off easily when the etching treatment including the severe alkali treatment is performed It is because.

Therefore, the blending amount of the fine silica particles is more preferably within a range of 30 to 110 parts by weight, and more preferably within a range of 50 to 100 parts by weight with respect to 100 parts by weight of an active energy ray curable resin containing a water-repellent resin as the component (A) Is more preferable.

Next, using FIG. 2, the relationship between the amount of silica fine particles blended and the etching resistance and surface free energy in the low refractive index layer will be described.

2 shows characteristic curves A and A 'in which the abrasion resistance (relative value) in the low refractive index layer is adopted as the left ordinate and the mixing curves A and A' in the abscissa, And the surface free energy (mN / m) in the refractive index layer is employed. The characteristic curves A and B are characteristic curves when an active energy ray-curable resin containing a water-repellent resin is used as the component (A), and the characteristic curve A 'is the activity curve of the water- This is a characteristic curve when an energy ray-curable resin is used.

In addition, specific measurement methods of etching resistance and surface free energy in the low refractive index layer will be described in Examples.

The relative value of the etch resistance is a relative value of the change in reflectance (%) before and after the alkali treatment in the laminate for forming a transparent conductive layer, measured as described in the examples, relative to the following criteria .

4: The value of the reflectance change amount is 0.5% or less

1: Value at which the change in reflectance exceeds 0.5%

First, as understood from the characteristic curve A, the value of the etch resistance tends to drop sharply as the amount of the silica fine particles to be blended increases.

More specifically, excellent etching resistance can be stably maintained in the range of the blending amount of the fine silica particles of not more than 120 parts by weight, but if the blending amount of the fine silica particles exceeds 120 parts by weight, I understand.

On the other hand, as understood from the characteristic curve A ', when the component (A) forming the matrix does not contain the water-repellent resin, the etching resistance is already lowered at the point of 20 parts by weight of the fine silica particles I understand.

Further, as understood from the characteristic curve B, the value of the surface free energy tends to gradually increase with an increase in the amount of the silica fine particles to be blended.

Therefore, from the characteristic curves A, A 'and B, it is necessary to use an ultraviolet ray-curable resin containing a water-repellent resin as the component (A) for forming the matrix and to adjust the compounding amount of the silica fine particles to It is understood that it should be a value of 120 parts by weight or less.

In order to obtain surface free energy (for example, 37 mN / m or more) for obtaining a predetermined adhesion to the transparent conductive layer or the like required for the low refractive index layer, it is understood that the blending amount of the silica fine particles should be 2 parts by weight or more do.

(2) -3 Composition for forming a low refractive index layer

The low refractive index layer is formed by preparing a composition for forming a low refractive index layer in advance, coating, drying and curing as described below.

The composition may contain an active energy ray-curable resin containing a water-repellent resin as the above-mentioned component (A) in a suitable solvent, and fine particles of silica as a component (B), a photopolymerization initiator, Followed by dissolving or dispersing the mixture.

The concentration and viscosity of various additives, solvents, and compositions for forming a low refractive index layer are the same as those in the description of the hard coat layer.

(2) -4 film thickness

It is also preferable that the film thickness of the low refractive index layer is within a range of 20 to 150 nm.

This is because, by setting the film thickness of the low refractive index layer to a value within this range, the pattern shape of the transparent conductive layer can be more stably invisible and sufficient etching resistance can be obtained.

That is, when the film thickness of the low refractive index layer is less than 20 nm, the film of the low refractive index layer becomes fragile and the etching resistance becomes insufficient in some cases. On the other hand, when the film thickness of the low refractive index layer exceeds 150 nm, the pattern shape of the transparent conductive layer tends to be visually recognized.

Therefore, the film thickness of the low refractive index layer is more preferably in the range of 25 to 120 nm, and more preferably in the range of 30 to 100 nm.

(2) -5 surface free energy

Further, it is preferable that the surface free energy measured under the condition of 23 캜 according to JIS K 6768 in the low refractive index layer is a value of 37 mN / m or more.

The reason for this is that by making the surface free energy of the low refractive index layer within this range, predetermined adhesion to the transparent conductive layer and the like required for the low refractive index layer can be more effectively obtained while improving the etching resistance to be.

That is, when the surface free energy is less than 37 mN / m, it may be difficult to obtain a predetermined adhesion to the transparent conductive layer or the like. On the other hand, if the surface free energy becomes excessively large, the adhesion to the protective film laminated on the transparent conductive layer-forming laminate for surface protection becomes excessively strong, In some cases.

Therefore, the surface free energy measured in accordance with JIS K 6768 in the low refractive index layer is more preferably in the range of 40 to 65 mN / m, more preferably in the range of 45 to 60 mN / m Do.

4. Manufacturing Method of Laminate for Transparent Conductive Layer

The laminate for forming a transparent conductive layer of the present invention can be obtained, for example, by a manufacturing method including the following steps (a) to (b).

(a) a step of forming a hard coating layer on both surfaces of a base film

(b) a step of forming an optical adjustment layer on one hard coat layer

Hereinafter, the parts overlapping with those described so far will be omitted, and only the other parts will be described in detail.

The transparent conductive layer-forming laminate of the present invention does not have a hard coat layer as an essential constituent requirement. In the following description, a case where a hard coat layer is formed will be described as an example.

(1) Step (a): Step of forming a hard coat layer

By coating the above-mentioned composition for forming a hard coat layer on both surfaces of a base film by a conventionally known method to form a coating film, drying the coating film, and irradiating it with an active energy ray to cure the coating film, do.

Examples of the application method of the composition for forming a hard coat layer include bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.

The drying conditions are preferably 10 to 10 minutes at 60 to 150 캜.

Examples of the active energy ray include ultraviolet rays and electron rays.

As a light source of ultraviolet rays, a high-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, a xenon lamp, and the like can be used. The irradiation amount is preferably 100 to 500 mJ / cm 2.

On the other hand, as the light source of the electron beam, an electron beam accelerator and the like can be exemplified, and it is preferable that the dose is usually 150 to 350 kV.

(2) Step (b): Step of forming the optical adjustment layer

Subsequently, a high refractive index layer is formed on the formed hard coating layer (directly on the base film when no hard coating layer is formed).

That is, the high refractive index layer can be formed by coating and drying the composition for forming a high refractive index layer described above and irradiating an active energy ray to cure the composition in the same manner as the hard coating layer is formed on the base film .

Then, a low refractive index layer is further formed on the formed high refractive index layer.

That is, the low refractive index layer can be formed by coating and drying the composition for forming a low refractive index layer described above and irradiating an active energy ray to cure the composition in the same manner as the formation of the hard coating layer on the base film .

[Second Embodiment]

A second embodiment of the present invention is a transparent conductive film comprising a base film 4 and an optical adjustment layer 2 and a transparent conductive layer 1 laminated in this order on at least one surface of the base film 4, Refractive index layer 2b having a refractive index of 1.6 or more and a low refractive index layer 2a having a refractive index of 1.45 or less are arranged in this order from the side of the base film 4 And the low refractive index layer (2a) is a transparent conductive film (100) which is obtained by photo-curing a composition for forming a low refractive index layer containing the following components (A) to (B).

(A) 100 parts by weight of an active energy ray-curable resin containing a water-repellent resin

(B) 2 to 120 parts by weight of fine silica particles

Hereinafter, the second embodiment of the present invention will be described in detail with respect to only the other parts, omitting parts overlapping with those of the above.

1. Transparent conductive layer

(1) Material materials

In the transparent conductive film of the present invention, the material of the transparent conductive layer is not particularly limited as long as it has both transparency and conductivity, and examples thereof include indium oxide, zinc oxide, tin oxide, indium tin oxide (ITO) Tin antimony oxide, zinc aluminum oxide, indium zinc oxide, and the like.

In particular, ITO is preferably used as a material material.

This is because, in the case of ITO, a transparent conductive layer having excellent transparency and conductivity can be formed by adopting an appropriate film forming condition.

(2) Pattern shape

Further, it is preferable that the transparent conductive layer is formed in a pattern shape such as a line shape or a lattice shape by etching.

It is preferable that the line width of the portion where the transparent conductive layer is present and the line width of the portion where the transparent conductive layer does not exist are substantially equal to each other.

The line width is usually 0.1 to 10 mm, preferably 0.2 to 5 mm, and particularly preferably 0.5 to 2 mm.

The line widths in the above-described line-shaped or lattice-like shape are not limited to the constant case, and for example, those that lead to shapes required for the capacitive touch panel can be freely selected.

Specifically, there can be mentioned a pattern shape in which a rhombus portion and a line portion repeat repeatedly, and such pattern shape is also included in the category of " line image ".

(3) Thickness

The thickness of the transparent conductive layer is preferably 5 to 500 nm.

This is because when the thickness of the transparent conductive layer is less than 5 nm, not only the transparent conductive layer becomes fragile but also sufficient conductivity may not be obtained. On the other hand, when the thickness of the transparent conductive layer exceeds 500 nm, the color tint due to the transparent conductive layer becomes strong, and the pattern shape may be easily recognized.

Therefore, the thickness of the transparent conductive layer is more preferably 15 to 250 nm, and more preferably 20 to 100 nm.

2. Manufacturing method of transparent conductive film

The optical adjusting layer obtained in the step (b) in the above-mentioned method for producing a transparent conductive layer-forming laminate may be formed by a known method such as vacuum evaporation, sputtering, CVD, ion plating, spraying, By forming the transparent conductive layer by the method, a transparent conductive film can be obtained.

Examples of the sputtering method include a conventional sputtering method using a compound or a reactive sputtering method using a metal target.

At this time, it is also preferable to introduce oxygen, nitrogen, water vapor, or the like as the reactive gas, or to use ozone addition, ion assist, or the like in combination.

The transparent conductive layer may be formed by forming a resist mask in a predetermined pattern by a photolithography method and then performing etching treatment by a known method to form a line pattern or the like .

As the etching solution, an aqueous solution of an acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid is preferably used.

From the viewpoint of expediting the etching treatment, the solution used for the alkali treatment for removing the residual photoresist which is the final step of the etching treatment is a solution at a temperature of 10 to 50 占 폚, a concentration of 1 to 10 wt%, a pH of 13.4 to 14.4 Of a strong base aqueous solution is preferably used.

Examples of suitable strong bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, europium hydroxide (II) ), Guanidine, and the like.

Further, in order to increase the crystallinity of the transparent conductive layer and lower the resistivity, it is preferable to perform an annealing process and perform a predetermined annealing process.

That is, the obtained transparent conductive film is preferably exposed at a temperature of 130 to 180 캜 for 0.5 to 2 hours.

[Example]

Hereinafter, the laminate for forming a transparent conductive layer and the like of the present invention will be described in more detail with reference to examples.

[Example 1]

1. Preparation of a composition for forming a hard coat layer

60 parts by weight of an amorphous silica-containing ultraviolet ray-curable resin (BINILOL FC-1000, manufactured by Showa Denko K.K.) (pure fractions from which a diluting solvent was removed, hereinafter the same) and silica of an amorphous silica dispersion , 0.03 part by weight of a crosslinked acrylic copolymer resin (TECH POLYMER XX-27LA, manufactured by Sekisui Chemical Co., Ltd.), and 0.5 part by weight of a silicone leveling agent (BKY-3550, And 0.03 part by weight of a polyvinyl alcohol solution were mixed and uniformly mixed to prepare a composition for forming a hard coat layer having a solid content concentration of 22% by weight.

2. Preparation of composition for forming a high refractive index layer

100 parts by weight of an ultraviolet curable resin (Seika Beam EXF-01L (NS), manufactured by Daiichi Seika Kogyo Co., Ltd.) and a zirconium oxide dispersion (ZRMIBK15WT% -F85, manufactured by CIK Nanotech Co., Ltd.) , 0.05 part by weight of an acrylic leveling agent (BYK-355, manufactured by Big Chem Japan Co., Ltd.) and 3 parts by weight of a photopolymerization initiator (Irgacure 907, BASF Japan) And a solvent was added thereto to prepare a composition for forming a high refractive index layer having a solid content concentration of 1% by weight.

3. Preparation of composition for forming a low refractive index layer

(B), a leveling agent as the component (C), and a photopolymerization initiator as the component (D) in the following composition in an amount of 1 to 10 parts by weight, After that, a solvent was added and uniformly mixed to prepare a composition for forming a low refractive index layer having a solid content concentration of 1% by weight.

Incidentally, the blending amount in the composition shown in the following composition and in Table 1 represents pure fractions obtained by removing the diluting solvent.

Component (A): 100 parts by weight of an ultraviolet-curable acrylic resin containing a fluororesin

(Type of fluororesin: reactive fluorine acrylic resin, content of fluorine resin: 80% by weight, surface free energy of cured resin coating of single fluorine resin: 25 mN / m)

Component (B): 100 parts by weight of reactive hollow silica fine particles

(Volume average particle diameter (D50) 45 nm)

(C) Component: silicone leveling agent 0.03 part by weight

(BYK-3550, manufactured by Big Chemie Japan Co., Ltd.)

Component (D): 10 parts by weight of photopolymerization initiator

(Irgacure 184, manufactured by BASF Japan Co., Ltd.)

The volume average particle diameter (D50) of the component (B) was measured by a laser diffraction scattering type particle size distribution measuring apparatus.

In the following, the photopolymerization initiator as the above-mentioned component (D) may be referred to as " Irgacure 184 ".

4. Formation of hard coat layer

As the base film, a polyester film (PET125KEL86W, manufactured by Teijin Dupont Co., Ltd.) having an adhesive layer (easy adhesion layer) having a thickness of 125 mu m was prepared.

Subsequently, on the surface of the prepared base film, a composition for forming a hard coat layer was coated with a wire bar # 8.

Subsequently, the substrate was dried at 70 DEG C for 1 minute, and then irradiated with ultraviolet rays under the following conditions using an ultraviolet ray irradiation apparatus (manufactured by GSI Yuasa Corporation) under a nitrogen atmosphere to form a hard coat layer .

A hard coat layer was formed on the opposite side of the base film in the same manner.

Light source: High-pressure mercury lamp

Illuminance: 150 mW / cm 2

Light quantity: 150 mJ / cm 2

5. Formation of high refractive index layer

Then, on one of the formed hard coat layers, a composition for forming a high refractive index was coated with a wire bar # 4.

Subsequently, the substrate was dried at 50 DEG C for 1 minute, and then irradiated with ultraviolet rays under the same irradiation condition as the hard coat layer using an ultraviolet ray irradiation apparatus (manufactured by GASUUUSA CO., LTD.) Under a nitrogen atmosphere to form a film thickness of 35 nm , And a high refractive index layer having a refractive index n _D = 1.65.

6. Formation of low refractive index layer

Subsequently, on the formed high refractive index layer, a composition for forming a low refractive index layer was coated with a wire bar # 4.

Subsequently, the substrate was dried at 50 DEG C for 1 minute, and then irradiated with ultraviolet rays under the same irradiation condition as the hard coat layer using an ultraviolet ray irradiation apparatus (manufactured by GSI Yuasa Corporation) under a nitrogen atmosphere to form a film thickness of 50 Nm and a refractive index n _D = 1.37 were formed to obtain a laminate for forming a transparent conductive layer as shown in Fig. 1 (a).

7. Evaluation

(1) Evaluation of etchability

The etching resistance in the obtained transparent conductive layer-forming laminate was evaluated.

That is, the reflectance (%) (on the side of the low refractive index layer) of the resultant laminate for forming a transparent conductive layer was measured with a UV-vis-NIR spectrophotometer (UV-3600 manufactured by Shimadzu Seisakusho Co., Ltd.) At a reflection angle of 8 DEG, a sampling pitch of 1 nm, and a measurement mode: single.

Subsequently, the laminate for forming a transparent conductive layer was immersed in a 5 wt% aqueous solution of sodium hydroxide heated at 40 캜 for 5 minutes, subjected to alkali treatment, and then the reflectance (%) was measured under the same conditions as those described above.

Subsequently, the reflectance (%) after the alkali treatment was subtracted from the reflectance (%) before the alkali treatment to calculate the reflectance change amount (%). The obtained results are shown in Table 1.

The reason why the etching resistance can be evaluated by the reflectance change amount (%) is that the reflectance of the low refractive index layer changes when the film thickness, the refractive index, or both of the low refractive index layer is changed by the etching treatment.

&Amp; cir &: The value of the reflectance change amount is 0.5% or less

X: Value at which the change in reflectance exceeds 0.5%

(2) Evaluation of pattern visibility

A patterned transparent conductive layer was formed on the surface of the obtained low refractive index layer of the laminate for forming a transparent conductive layer, and the visibility was evaluated.

That is, the thus obtained laminate for forming a transparent conductive layer was cut into a piece of 90 mm long × 90 mm wide, and then sputtering was performed using an ITO target (10% by weight tin oxide and 90% by weight indium oxide) A transparent conductive layer having a square shape with a length of 60 mm and a width of 60 mm and a film thickness of 30 nm was formed.

Then, a lattice-patterned photoresist film was formed on the surface of the obtained transparent conductive layer.

Subsequently, the substrate was immersed in 10% by weight hydrochloric acid for 1 minute at room temperature to perform etching treatment to pattern the transparent conductive layer in a lattice pattern.

Subsequently, the substrate was immersed in a 5 wt% aqueous solution of sodium hydroxide heated to 40 DEG C for 5 minutes to conduct an alkali treatment to remove the photoresist film on the transparent conductive layer to obtain a transparent conductive film having a patterned transparent conductive layer.

The transparent conductive film had a transparent conductive layer of 30 nm having a pattern shape in which square pores of 2 mm in each side were partitioned into a lattice by a line portion made of ITO having a line width of 2 mm.

Subsequently, the obtained transparent conductive film was placed at a position of 1 m from the white fluorescent lamp, and a white fluorescent lamp was irradiated to the transparent conductive film. The white fluorescent lamp was irradiated from a position of 30 cm from the transparent conductive film on the same side as the white fluorescent lamp , And the pattern shape of the transparent conductive layer was observed at the time of visual observation and evaluated according to the following criteria. The obtained results are shown in Table 1.

?: The pattern shape of the transparent conductive layer is not recognized

?: The pattern shape of the transparent conductive layer was slightly visually observed

X: The pattern shape of the transparent conductive layer is observed.

(3) Evaluation of surface free energy

The surface free energy (mN / m) measured under the condition of 23 캜 according to JIS K 6768 in the obtained transparent conductive layer-forming laminate was evaluated.

Namely, on the obtained transparent conductive layer-forming laminate, a wet tensile test liquid having a predetermined surface tension was applied on the upper surface of the outermost layer of the low refractive index layer so as to have a width of 10 mm and a length of 60 mm using a cotton swab.

If the coating film of the wet tension test liquid is not cut off for 2 seconds, it is judged that the surface free energy is acceptable, and the same operation is continued by using a wet tensile test liquid having a higher surface tension successively, The test was repeated until it was broken within a second, and the highest surface free energy passed was the measurement result. The obtained results are shown in Table 1.

In addition, since the thermodynamic, wet tension and surface free energy are the same, in the present invention, wet tension is described as surface free energy.

[Example 2]

In Example 2, a composition for forming a low refractive index layer was prepared in the same manner as in Example 1 except that the amount of the reactive hollow silica fine particles (volume average particle diameter (D50) 45 nm) was changed to 60 parts by weight, A laminate was prepared and evaluated. The obtained results are shown in Table 1.

[Example 3]

In Example 3, the composition for forming a low refractive index layer was prepared in the same manner as in Example 1, except that the amount of the reactive hollow silica fine particles (volume average particle diameter (D50) 45 nm) A laminate was prepared and evaluated. The obtained results are shown in Table 1.

[Example 4]

In Example 4, a composition for forming a low refractive index layer was prepared in the same manner as in Example 1 except that the amount of the reactive hollow silica fine particles (volume average particle diameter (D50) 45 nm) was 20 parts by weight, A laminate was prepared and evaluated. The obtained results are shown in Table 1.

[Comparative Example 1]

In Comparative Example 1, a laminate for forming a transparent conductive layer was prepared and evaluated in the same manner as in Example 1 except that the composition for forming the low refractive index layer was changed to the following composition. The obtained results are shown in Table 1.

Incidentally, the blending amount in the composition shown in the following composition and in Table 1 represents pure fractions obtained by removing the diluting solvent.

Component (A): 100 parts by weight of an ultraviolet curable acrylic resin

Component (C): Acrylic leveling agent 0.05 part by weight

(BYK-355, manufactured by Big Chemie Japan Co., Ltd.)

Component (D): Photopolymerization initiator 5 parts by weight

(Irgacure 184, manufactured by BASF Japan Co., Ltd.)

[Comparative Example 2]

In Comparative Example 2, in preparing the composition for forming a low refractive index layer, a reactive hollow silica fine particle (volume average particle diameter (D50) of 45 nm) was further added to adjust the amount of the reactive hollow silica fine particles to 20 parts by weight, A laminate for forming a transparent conductive layer was prepared and evaluated in the same manner as in Comparative Example 1. [ The obtained results are shown in Table 1.

[Comparative Example 3]

In Comparative Example 3, in preparing a composition for forming a low refractive index layer, a reactive hollow silica fine particle (volume average particle diameter (D50) 45 nm) was further added to adjust the amount of the reactive hollow silica fine particles to 100 parts by weight, A laminate for forming a transparent conductive layer was prepared and evaluated in the same manner as in Comparative Example 1. [ The obtained results are shown in Table 1.

[Comparative Example 4]

In Comparative Example 4, the composition for forming the low refractive index layer was prepared in the same manner as in Example 1, except that the amount of the reactive hollow silica fine particles (volume average particle diameter (D50) 45 nm) A laminate was prepared and evaluated. The obtained results are shown in Table 1.

[Comparative Example 5]

In Comparative Example 5, the composition for forming the low refractive index layer was prepared in the same manner as in Example 1 except that the amount of the reactive hollow silica fine particles (volume average particle diameter (D50) 45 nm) was 230 parts by weight, A laminate was prepared and evaluated. The obtained results are shown in Table 1.

[Table 1]

As described above, according to the present invention, when forming the low refractive index layer which is the outermost layer of the laminate for forming a transparent conductive layer, the active energy ray curable resin containing the water repellent resin is immersed in the fine particles of silica in a predetermined range , A laminate for forming a transparent conductive layer having excellent resistance to etching in the low refractive index layer can be obtained.

As a result, the pattern shape of the transparent conductive layer can be stably invisible, and a laminate for forming a transparent conductive layer having excellent adhesion between the transparent conductive layer and the like can be obtained.

Therefore, it is expected that the laminate for forming a transparent conductive layer of the present invention and the transparent conductive film using the same will remarkably contribute to a high quality of the touch panel.

1: transparent conductive layer, 2: optical adjusting layer, 2a: low refractive index layer, 2b: high refractive index layer, 3: hard coat layer, 4: base film, 10: laminate for forming a transparent conductive layer,

Claims (9)

A laminate for forming a transparent conductive layer having an optical adjustment layer on at least one surface of a base film,
Wherein the optical adjustment layer is formed by laminating a high refractive index layer having a refractive index of 1.6 or more and a low refractive index layer having a refractive index of 1.45 or less in this order from the base film side,
Wherein the low refractive index layer is formed by photocuring a composition for forming a low refractive index layer containing the following components (A) to (B).
(A) 100 parts by weight of an active energy ray-curable resin containing a water-repellent resin
(B) 2 to 120 parts by weight of fine silica particles The method according to claim 1,
Wherein the volume average particle diameter (D50) of the fine silica particles as the component (B) is set to a value within a range of 20 to 70 nm. The method according to claim 1,
Wherein the fine silica particles as the component (B) are hollow silica fine particles. The method according to claim 1,
Wherein the fine silica particles as the component (B) are reactive silica fine particles. The method according to claim 1,
Wherein the water-repellent resin constituting a part of the active energy ray-curable resin containing the water-repellent resin as the component (A) is a fluororesin. The method according to claim 1,
Wherein the surface free energy in the low refractive index layer is set to a value of 37 mN / m or more. The method according to claim 1,
Wherein the film thickness of the low refractive index layer is within a range of 20 to 150 nm. A transparent conductive film comprising an optical adjustment layer and a transparent conductive layer laminated in order on at least one surface of a base film,
Wherein the optical adjustment layer is formed by laminating a high refractive index layer having a refractive index of 1.6 or more and a low refractive index layer having a refractive index of 1.45 or less in this order from the base film side,
Wherein the low refractive index layer is formed by photo-curing a composition for forming a low refractive index layer containing the following components (A) to (B).
(A) 100 parts by weight of an active energy ray-curable resin containing a water-repellent resin
(B) 2 to 120 parts by weight of fine silica particles 9. The method of claim 8,
Wherein the transparent conductive layer is patterned by etching.

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