JP6587405B2 - Transparent conductive film - Google Patents

Description

The present invention relates to a laminate for forming a transparent conductive layer and a transparent conductive film.
Especially for forming a transparent conductive layer that has excellent etching resistance in a low refractive index layer, can stably invisible the pattern shape of the transparent conductive layer, and has excellent adhesion to the transparent conductive layer, etc. The present invention relates to a laminate and a transparent conductive film using the same.

2. Description of the Related Art Conventionally, a touch panel that can input information by directly touching an image display unit has a light transmissive input device arranged on a display.
As a typical form of such a touch panel, a resistive film type touch panel in which two transparent electrode substrates are arranged with a gap so that the transparent electrode layers face each other, or between a transparent electrode film and a finger is generated. There is a capacitive touch panel that utilizes a change in capacitance.

Among these, in the capacitive touch panel, as a sensor for detecting a finger touch position, a glass sensor in which a transparent conductive layer is roughly laminated on a glass substrate and a transparent conductive layer is a transparent plastic film substrate. There is a film sensor laminated on top.
Particularly in the film sensor, a lattice-like pattern is formed by arranging two transparent conductive films each having a transparent conductive layer patterned in a line so that the patterns cross each other. There are many.

However, when the transparent conductive layer is patterned in this way, a boundary portion between the pattern portion and the non-pattern portion becomes easy to be visually recognized, and there is a problem that the appearance of the capacitive touch panel is deteriorated.
Therefore, a technique for solving such a problem has been disclosed (see, for example, Patent Documents 1 and 2).

  That is, Patent Document 1 discloses a laminated film in which a resin layer is provided on at least one side of a polyester film, and the resin layer contains at least silica particles (B) and an acrylic resin (D). Are hollow particles and / or particles having pores, and the number average particle diameter of the silica particles is 30 nm or more and 120 nm or less, and the acrylic resin (D) is represented by the following general formula (1) ( It is a resin comprising a (meth) acrylate monomer (d-1) and a (meth) acrylate monomer (d-2) represented by the following general formula (2), and has a minimum reflectance on the resin layer side of the laminated film. An optical laminated film characterized by being 2.0% or less is disclosed.

(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 carbocycles.)

Patent Document 2 includes a transparent conductor layer on at least one undercoat layer on one or both sides of a transparent film substrate, and the transparent conductor layer is patterned, and A method for producing a transparent conductive film having at least one undercoat layer in a non-pattern portion having no transparent conductor layer, wherein the transparent film substrate is formed on one or both sides of a transparent film substrate. A step of forming the formed undercoat layer with an organic material, a step of forming a transparent conductor layer on the undercoat layer by a sputtering method, and a step of etching and patterning the transparent conductor layer. A method for producing a transparent conductive film is disclosed.
Further, it is described that the above-described undercoat layer is composed of two layers, and the outermost undercoat layer is an SiO ₂ film formed by applying silica sol.

JP 2013-52676 A (Claims) JP 2011-142089 A (Claims)

However, the optical laminated film disclosed in Patent Document 1 is such that when the transparent conductive layer is patterned by etching, the resin layer on which the transparent conductive layer is formed is easily eroded by the etching solution. There was a problem that it was difficult to stably invisible the pattern shape.
More specifically, in recent years, with the increase in production of smartphones and the like, speeding up of the etching process is required, and in particular, in the alkali treatment for removing the remaining photoresist that is the final step of the etching process, For example, a 5 wt% aqueous sodium hydroxide solution heated to 40 ° C. may be used.
When such a severe alkali treatment is performed, in the optical laminated film disclosed in Patent Document 1, the silica particles in the resin layer are easily dissolved or dropped off, and as a result, the transparent conductive layer can be stably stabilized. There was a problem that it was difficult to make the pattern shape of the above invisible.

Moreover, also in the case of the transparent conductive film obtained by the manufacturing method disclosed in Patent Document 2, when severe alkali treatment is performed, the silica particles in the SiO ₂ film are easily dissolved or dropped off. There has been a problem that it is difficult to stably invisible the pattern shape of the transparent conductive layer.

Therefore, the present inventors made extensive efforts in view of the above circumstances, and when forming the low refractive index layer that is the outermost surface layer of the transparent conductive layer forming laminate, it contains a water-repellent resin. The present inventors have found that the above-mentioned problems can be solved by using a composition for forming a low refractive index layer in which silica fine particles are blended in a predetermined range with respect to the active energy ray curable resin to be completed, and the present invention has been completed. It is.
That is, the object of the present invention is excellent in etching resistance in the low refractive index layer, can stably make the pattern shape of the transparent conductive layer invisible, and has excellent adhesion between the transparent conductive layer and the like. Another object is to provide a laminate for forming a transparent conductive layer and a transparent conductive film using the same.

According to the present invention, it is a laminate for forming a transparent conductive layer in which a hard coat layer and an optical adjustment layer are sequentially laminated on at least one surface of a base film, and the optical adjustment layer is a base film. From the side, 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 are sequentially laminated. , look including the following (a) ~ (B) component, a transparent conductive, characterized in that formed by photocuring the following (B) silica fine particles as the component is a hollow silica fine particle composition for forming a low refractive index layer A laminate for forming a layer is provided, and the above-described problems can be solved.
(A) Active energy ray-curable resin containing water-repellent resin 100 parts by weight (B) Silica fine particles 2 to 120 parts by weight That is, if it is a laminate for forming a transparent conductive layer of the present invention, it is the outermost surface layer. The composition for forming a low refractive index layer used for forming the low refractive index layer includes an active energy ray curable resin containing a water repellent resin, and the active energy ray curable resin containing the water repellent resin. On the other hand, since silica fine particles are contained in a relatively small range, it is effective that silica fine particles in the low refractive index layer melt or fall off even when etching processing including severe alkali treatment is performed. (Hereinafter, this effect may be referred to as “etching resistance”).
In addition, the refractive index of the low refractive index layer, which will increase when the amount of silica fine particles is set in a relatively small range, is lowered to a predetermined range by a water-repellent resin having a relatively low refractive index, thereby reducing the refractive index. A predetermined refractive index required for the refractive index layer can be obtained.
Moreover, since the refractive index of silica fine particles is further reduced by making the silica fine particles into hollow silica fine particles, the refractive index of the low refractive index layer is more efficiently adjusted to a predetermined refractive index even with a small amount of compounding. can do.
As a result, the pattern shape of the transparent conductive layer can be stably invisible.
In addition, the surface free energy of the low refractive index layer, which is lowered by including the water repellent resin, is increased to a predetermined range by the fine surface irregularities formed by the silica fine particles, and is required for the low refractive index layer. The predetermined adhesiveness to the transparent conductive layer or the like can be obtained.
In addition, by providing a hard coat layer, in the production process of the laminate for forming a transparent conductive layer, it is possible to impart scratch resistance to the base film and prevent optical characteristics from being deteriorated. It is possible to suppress the occurrence of a phenomenon in which the substrate films stick to each other when the film is wound into a roll.

Moreover, when comprising the laminated body for transparent conductive layer formation of this invention, it is preferable to make the volume average particle diameter (D50) of the silica fine particle as (B) component into the value within the range of 20-70 nm.
By comprising in this way, a predetermined refractive index can be obtained, without reducing the transparency in a low refractive index layer.

Moreover, when comprising the laminated body for transparent conductive layer formation of this invention, it is preferable that the silica fine particle as (B) component is a reactive silica fine particle.
By comprising in this way, since silica fine particles can be firmly fixed with respect to a low refractive index layer, etching resistance can be improved more effectively.

In constituting 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 a fluororesin. It is preferable.
By configuring in this way, the silica fine particles in the low refractive index layer can be more effectively protected, so that the etching resistance can be improved more effectively and the refractive index of the low refractive index layer can be increased. It can be more effectively reduced to a predetermined range.

Further, in constituting the laminate for forming a transparent conductive layer of the present invention, it is preferable that the surface free energy in the low refractive index layer is 37 mN / m or more.
By comprising in this way, the predetermined adhesiveness with respect to the transparent conductive layer etc. which are requested | required of a low refractive index layer can be obtained more effectively, improving etching resistance.

Moreover, when comprising the laminated body for transparent conductive layer formation of this invention, it is preferable to make the film thickness of a low refractive index layer into the value within the range of 20-150 nm.
By comprising in this way, sufficient etching resistance can be obtained, and, thereby, the pattern shape of a transparent conductive layer can be more stably invisible even under severe etching conditions.

Another embodiment of the present invention is a transparent conductive film in which a hard coat layer, an optical adjustment layer, and a transparent conductive layer are sequentially laminated on at least one surface of a base film, and the optical adjustment The layer is formed by sequentially 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 from the base film side. , the low refractive index layer, see contains the following (a) ~ (B) component, (B) below the silica fine particles as the component obtained by photocuring a certain low refractive index layer-forming composition in the hollow silica fine particles It is a transparent conductive film characterized by these.
(A) Active energy ray-curable resin containing water-repellent resin 100 parts by weight (B) Silica fine particles 2 to 120 parts by weight That is, if it is the transparent conductive film of the present invention, a predetermined laminate for forming a transparent conductive layer Therefore, it is excellent in etching resistance in the low refractive index layer, and even after harsh etching treatment, the pattern shape of the transparent conductive layer can be stably invisible, and excellent for the transparent conductive layer etc. Adhesion can be obtained.
Moreover, since the refractive index of silica fine particles is further reduced by making the silica fine particles into hollow silica fine particles, the refractive index of the low refractive index layer is more efficiently adjusted to a predetermined refractive index even with a small amount of compounding. can do.
In addition, by providing a hard coat layer, in the production process of the laminate for forming a transparent conductive layer, it is possible to impart scratch resistance to the base film and prevent optical characteristics from being deteriorated. It is possible to suppress the occurrence of a phenomenon in which the substrate films stick to each other when the film is wound into a roll.

Moreover, when comprising the transparent conductive film of this invention, it is preferable that the transparent conductive layer is patterned by the etching.
Even in this case, the pattern shape of the transparent conductive layer can be stably invisible due to excellent etching resistance in the low refractive index layer.

FIG. 1A to FIG. 1B are views provided to explain the configuration of the transparent conductive layer forming laminate of the present invention. FIG. 2 is a diagram provided to explain the relationship between the compounding amount of silica fine particles and the etching resistance and surface free energy in the low refractive index layer. FIG. 3 is a diagram provided for explaining the configuration of the transparent conductive film of the present invention.

[First Embodiment]
The first embodiment of the present invention is a laminate 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. From the base film 4 side, the layer 2 has 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 order. A laminate for forming a transparent conductive layer, characterized in that the laminate is formed and the low refractive index layer 2a is obtained by photocuring a composition for forming a low refractive index layer containing the following components (A) to (B). 10.
(A) Active energy ray-curable resin containing a water-repellent resin 100 parts by weight (B) Silica fine particles 2 to 120 parts by weight In addition, in FIG. Although the laminate 10 for forming a transparent conductive layer having an embodiment is shown as an example , the hard coat layer 3 can be omitted as a reference invention .
In FIG. 1A, the particles in each layer are silica fine particles and metal oxide particles.
Hereinafter, a first embodiment of the present invention will be specifically described with reference to the drawings as appropriate.

1. Type of base film (1) The type of base film is not particularly limited, and a known base film can be used as an optical base.
For example, polyester film such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film , Polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide Film, fluororesin film, polyamide film, Lil resin film, norbornene resin film, can be exemplified preferably a plastic film such as a cycloolefin resin film.

Of these, polyester films, polycarbonate films, polyimide films, norbornene resin films, and cycloolefin resin films are more preferable from the viewpoint of heat resistance.
Moreover, it is preferable that it is a PET film especially from a viewpoint of coexistence of transparency, film strength, and a softness | flexibility.

(2) Film thickness Moreover, it is preferable to make the film thickness of a base film into the value within the range of 20-200 micrometers.
The reason for this is that when the film thickness of the base film is less than 20 μm, the strength of the base film is reduced, so that during the annealing process in the existing part and the non-existing part of the transparent conductive layer in the optical adjustment layer This is because the occurrence of distortion may not be effectively suppressed. On the other hand, when the film thickness of the substrate film exceeds 200 μm, optical properties such as transparency in the substrate film may be deteriorated.
Therefore, the thickness of the base film is more preferably set to a value within the range of 30 to 180 μm, and further preferably set to a value within the range of 50 to 150 μm.
Note that “annealing” refers to crystallizing a transparent conductive layer laminated on a transparent conductive layer-forming laminate by heat treatment in order to improve the electrical conductivity of the transparent conductive layer in the transparent conductive film. It means processing to do.

2. Hard Coat Layer As shown in FIG. 1 (a), it is preferable to provide the hard coat layer 3 on both sides or one side of the base film 4 in constituting the transparent conductive layer forming laminate 10 of the present invention.
The reason for this is that by providing such a hard coat layer, in the production process of the laminate for forming a transparent conductive layer, it is possible to impart scratch resistance to the base film and prevent optical properties from being deteriorated, This is because it is possible to suppress the occurrence of a phenomenon in which the base films adhere to each other when the base films are wound into a roll (hereinafter, this effect may be referred to as “anti-blocking”). .

(1) Material substance Moreover, it is preferable that a hard-coat layer consists of hardened | cured material of the composition containing a silica particle and active energy ray-curable resin as a material substance.
The reason for this is that by including silica fine particles and an active energy ray-curable resin, anti-blocking properties can be imparted, so that not only an improvement in winding property can be expected, but also a high refractive index layer that is an upper layer of the hard coat layer. This is because the adhesion can be improved and the layers can be firmly laminated.

(1) -1 Active energy ray curable resin The active energy ray curable resin used for the formation of the hard coat layer is one having an energy quantum in electromagnetic waves or charged particle beams, that is, ultraviolet rays or electron beams. It means a polymerizable compound that crosslinks and cures when irradiated with, for example, a photopolymerizable prepolymer and a photopolymerizable monomer.

  Further, the above-mentioned photopolymerizable prepolymer includes a radical polymerization type and a cationic polymerization type. Examples of the radical polymerization type photopolymerizable prepolymer include polyester acrylate, epoxy acrylate, urethane acrylate, polyol acrylate, and the like. Is mentioned.

Moreover, as a polyester acrylate type prepolymer, for example, by esterifying the hydroxyl group of a polyester oligomer having a hydroxyl group at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or The compound obtained by esterifying the terminal hydroxyl group of the oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth) acrylic acid.
Examples of the epoxy acrylate prepolymer include compounds obtained by esterifying an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin with (meth) acrylic acid.
Moreover, as a urethane acrylate type prepolymer, the compound obtained by esterifying the polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol, and polyisocyanate with (meth) acrylic acid is mentioned, for example.
Furthermore, as a polyol acrylate type prepolymer, the compound obtained by esterifying the hydroxyl group of polyether polyol with (meth) acrylic acid is mentioned.
In addition, these polymeric prepolymers may be used individually by 1 type, and may be used in combination of 2 or more type.

On the other hand, as a cationic polymerization type photopolymerizable prepolymer, an epoxy resin is usually used.
Examples of such epoxy resins are compounds obtained by epoxidizing polyhydric phenols such as bisphenol resins and novolak resins with epichlorohydrin, etc., and by oxidizing a linear olefin compound or a cyclic olefin compound with a peroxide or the like. Compounds and 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, and polyethylene glycol di (meth). Acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified phosphoric acid Di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified Polyfunctional acrylates such as dipentaerythritol hexa (meth) acrylate are exemplified.
In addition, these photopolymerizable monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

(1) -2 Photopolymerization initiator Since the active energy ray-curable resin can be efficiently cured with active energy rays, particularly ultraviolet rays, it is also preferable to use a photopolymerization initiator in combination as desired.
Examples of such photopolymerization initiators include radical polymerization type 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-2-methyl-1-phenylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) keto Benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoate, and the like.

Examples of the photopolymerization initiator for the cationic polymerization type photopolymerizable prepolymer include oniums such as aromatic sulfonium ions, aromatic oxosulfonium ions, aromatic iodonium ions, tetrafluoroborate, hexafluorophosphate, hexa Examples thereof include compounds composed of anions such as fluoroantimonate and hexafluoroarsenate.
In addition, these may be used individually by 1 type and may be used in combination of 2 or more type.
Moreover, as a compounding quantity of a photoinitiator, it is preferable to set it as the value within the range of 0.2-10 weight part with respect to 100 weight part of active energy ray-curable resins mentioned above, 1-5 weight part It is more preferable to set the value within the range.

(1) -3 Silica fine particles Further, as the silica fine particles, silica fine particles to which a polymerizable unsaturated group-containing organic compound is bonded, or normal colloidal silica fine particles having no such polymerizable unsaturated group-containing organic compound are used. Can be used.
Further, the silica fine particles to which the polymerizable unsaturated group-containing organic compound is bonded include a functional group capable of reacting with the silanol groups on the surface of the silica fine particles having a volume average particle diameter (D50) of about 0.005 to 1 μm. Examples thereof include those obtained by reacting a polymerizable unsaturated group-containing organic compound having a group.
In addition, as a polymerizable unsaturated group mentioned above, radical polymerizable acryloyl group, a methacryloyl group, etc. are mentioned, for example.
Moreover, as a normal colloidal silica fine particle which does not have a polymerizable unsaturated group containing organic compound, the silica fine particle whose volume average particle diameter is about 0.005-1 micrometer, Preferably about 0.01-0.2 micrometer is alcohol. Colloidal silica suspended in a colloidal state in an organic solvent or cellosolve organic solvent can be preferably used.
The average particle size of the silica fine particles can be obtained by, for example, a zeta potential measurement method, can be obtained by using a laser diffraction scattering type particle size distribution measuring device, and can be obtained based on an SEM image. .
Moreover, as a compounding quantity of a silica particle, it is preferable that it is 5-400 weight part with respect to 100 weight part of active energy ray-curable resins, It is more preferable that it is 20-150 weight part, 30-100 weight More preferably, it is a part.

(2) Composition for forming a hard coat layer The hard coat layer is preferably formed by preparing a composition for forming a hard coat layer in advance, applying, drying and curing as described below.
The composition is dissolved or dispersed in an appropriate solvent by adding an active energy ray curable resin, a photopolymerization initiator, silica fine particles, and various additive components used as required in a predetermined ratio. Can be prepared.
Examples of various additive components include antioxidants, ultraviolet absorbers, (near) infrared absorbers, silane coupling agents, light stabilizers, leveling agents, antistatic agents, and antifoaming agents.

Examples of the solvent 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, methanol, ethanol, propanol, and butanol. Examples thereof include ketones such as alcohol, acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate, and cellosolv solvents such as ethyl cellosolve.
The concentration and viscosity of the hard coat layer-forming composition thus prepared are not particularly limited as long as they can be coated, and can be appropriately selected according to the situation.
Therefore, it is usually preferable to dilute to a solid content concentration of 0.05 to 10% by weight from the viewpoint of easily adjusting the film thickness of the resulting hard coat layer forming composition to a predetermined range. It is more preferable to dilute to ˜8% by weight.

(3) Film thickness Moreover, it is preferable to make the film thickness of a hard-coat layer into the value within the range of 1-15 micrometers.
The reason for this is that when the thickness of the hard coat layer is less than 1 μm, the holding function against the thermal shrinkage of the base film due to the annealing treatment becomes insufficient and curling may not be suppressed. On the other hand, when the film thickness of the hard coat layer exceeds 15 μm, outgas may be easily generated from the hard coat layer by annealing.
Therefore, the thickness of the hard coat layer is more preferably set to a value within the range of 1.5 to 10 μm, and further preferably set to a value within the range of 2 to 5 μm.

3. Optical adjustment layer (1) High refractive index layer (1) -1 Refractive index The refractive index of the high refractive index layer is 1.6 or more.
The reason for this is that when the refractive index of the high refractive index layer is less than 1.6, a significant refractive index difference from the low refractive index layer cannot be obtained, and the pattern shape of the transparent conductive layer is likely to be visually recognized. Because there is. On the other hand, if the refractive index of the high refractive index layer becomes an excessively large value, the film of the high refractive index layer may become fragile.
Therefore, the refractive index of the high refractive index layer is more preferably set to a value within the range of 1.61 to 2, and further preferably set to a value within the range of 1.63 to 1.8.

(1) -2 Material substance Moreover, it is preferable that a high refractive index layer consists of hardened | cured material of the composition containing the metal oxide microparticles | fine-particles and active energy ray-curable resin as a material substance.
This is because the refractive index in the high refractive index layer can be easily adjusted by including the metal oxide fine particles and the active energy ray-curable resin.

In addition, the type of metal oxide is preferably tantalum oxide, zinc oxide, indium oxide, hafnium oxide, cerium oxide, tin oxide, niobium oxide, indium tin oxide (ITO), antimony tin oxide (ATO), or the like. .
Further, from the viewpoint of realizing a high refractive index without lowering transparency, it is particularly preferable that at least one selected from titanium oxide and zirconium oxide is used.
In addition, these metal oxides may be used individually by 1 type, and may use 2 or more types together.
The volume average particle diameter (D50) of the metal oxide fine particles is preferably set to a value within the range of 0.005 μm to 1 μm.
In addition, the volume average particle diameter (D50) of the metal oxide fine particles can be obtained, for example, by a measurement method using a zeta potential measurement method, or can be obtained using a laser diffraction scattering type particle size distribution measuring device, Further, it can be obtained based on the SEM image.
In addition, as the active energy ray-curable resin and the photopolymerization initiator used for the high refractive index layer, those mentioned in the description of the hard coat layer can be appropriately used.
Moreover, as a compounding quantity of metal oxide microparticles | fine-particles, it is preferable that it is 20-2000 weight part with respect to 100 weight part of active energy ray-curable resins, It is more preferable that it is 80-1000 weight part, 150- More preferably, it is 400 parts by weight.

(1) -3 Composition for forming a high refractive index layer The high refractive index layer is formed by preparing a composition for forming a high refractive index layer in advance, applying, drying and curing as described later. It is preferable.
If necessary, the composition may be dissolved or dissolved in an appropriate solvent by adding an active energy ray-curable resin, a photopolymerization initiator, metal oxide fine particles, and various additive components used as required in a predetermined ratio. It can be prepared by dispersing.
The various additive components, the solvent, the concentration of the composition for forming the high refractive index layer, and the like are the same as in the description of the hard coat layer.

(1) -4 Film thickness It is preferable that the film thickness of the high refractive index layer is 20 to 130 nm.
This is because if the film thickness of the high refractive index layer is less than 20 nm, the film of the high refractive index layer becomes brittle and the shape of the layer may not be maintained. On the other hand, when the thickness of the high refractive index layer exceeds 130 nm, the pattern shape of the transparent conductive layer is likely to be visually recognized.
Therefore, the film thickness of the high refractive index layer is more preferably 23 to 120 nm, and further preferably 30 to 110 nm.

(2) Low refractive index layer (2) -1 Refractive index The low refractive index layer has a refractive index of 1.45 or less.
The reason for this is that when the refractive index of the low refractive index layer exceeds 1.45, a significant refractive index difference from the high refractive index layer cannot be obtained, and the pattern shape of the transparent conductive layer is easily visible. Because there is. On the other hand, if the refractive index of the low refractive index layer becomes too small, the film of the low refractive index layer may become brittle.
Therefore, the refractive index of the low refractive index layer is more preferably set to a value within the range of 1.3 to 1.44, and further preferably set to a value within the range of 1.35 to 1.43.

(2) -2 Material Substance The low refractive index layer in the present invention is obtained by photocuring a composition for forming a low refractive index layer containing the following components (A) to (B) as a material substance. To do.
(A) Active energy ray-curable resin containing a water-repellent resin 100 parts by weight (B) 2 to 120 parts by weight of silica fine particles This is because the composition for forming a low refractive index layer used when forming a low refractive index layer However, the active energy ray-curable resin containing a water-repellent resin contains a relatively small amount of silica fine particles, so that even when an etching treatment including a severe alkali treatment is performed, the low refractive index layer This is because it is possible to effectively suppress the silica fine particles from being melted or falling off.
More specifically, as shown in FIG. 1 (a), when the amount of silica fine particles in the low refractive index layer 2a is small, the existence ratio of the matrix portion made of resin increases, so that severe alkali treatment is performed. Even in such a case, the silica fine particles are effectively protected by the matrix portion, and it is possible to effectively suppress melting or dropping off.
On the other hand, as shown in FIG. 1B, when the amount of silica fine particles in the low refractive index layer 2a ′ is large, the presence rate of the matrix portion made of resin is reduced, and thus when severe alkali treatment is performed. In this case, the silica fine particles are not sufficiently protected by the matrix portion, and are likely to melt or fall off.

In addition, the refractive index of the low refractive index layer, which will increase when the amount of silica fine particles is set in a relatively small range, is lowered to a predetermined range by a water-repellent resin having a relatively low refractive index, thereby reducing the refractive index. A predetermined refractive index required for the refractive index layer can be obtained.
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 will be lowered by including the water repellent resin, is increased to a predetermined range by the fine surface irregularities formed by the silica fine particles, and is required for the refractive index layer. Predetermined adhesion to the transparent conductive layer or the like can be obtained.
Hereinafter, each component will be described.

(I) Component (A): 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 and the photopolymerizable monomer mentioned in the description of the hard coat layer can be used as appropriate.

The water-repellent resin constituting the component (A) is not particularly limited as long as it is a resin having water repellency, and a conventionally known water-repellent resin can be used.
More specifically, if the surface free energy in the resin film formed of a single water-repellent resin is a value within the range of 10 to 30 mN / m, it can be suitably used as the water-repellent resin in the present invention.

Specific examples of the water-repellent resin include, for example, a silicone resin and a fluorine resin such as polyvinylidene fluoride, a fluorine-based acrylic resin, and polyfluoroethylene.
Among them, it is preferable to use a fluororesin, and particularly a reactive fluoroacrylic resin.
This is because the fluororesin can more effectively protect the silica fine particles in the low refractive index layer, so that the etching resistance can be improved more effectively.

Moreover, it is preferable to make content of water-repellent resin into the value within the range of 50 to 90 weight%, when (A) whole component is 100 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 silica fine particles in the low refractive index layer, and thus it is difficult to improve the etching resistance. This is because there may be cases. Further, this is because it may be difficult to set the refractive index of the low refractive index layer to a sufficiently low value. 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, which is a predetermined value for the transparent conductive layer and the like required for the refractive index layer. This is because it may be difficult to obtain the adhesion.
Therefore, the content of the water-repellent resin is more preferably set to a value within the range of 60 to 85% by weight, with the whole component (A) being 100% by weight, and within the range of 70 to 80% by weight. More preferably, it is a value.

(Ii) Component (B): Silica fine particles The component (B) is silica fine particles.
The type of silica fine particles is not particularly limited, but it is preferable to use hollow silica fine particles.
The reason for this is that if the hollow silica fine particles contain air in the hollow portion inside, the refractive index of the silica fine particles as a whole will be further lowered, and even if the amount is small, the refractive index is more efficiently reduced. This is because the refractive index of the refractive index layer can be adjusted to a predetermined refractive index.
The “hollow silica fine particles” mean silica fine particles having cavities inside the particles.

The silica fine particles are preferably reactive silica fine particles.
This is because the reactive silica fine particles can firmly fix the silica fine particles to the low refractive index layer, so that the etching resistance can be improved more effectively.
The “reactive silica fine particles” are silica fine particles to which a polymerizable unsaturated group-containing organic compound is bonded. The polymerizable fine particles having a functional group capable of reacting with the silanol groups on the silanol groups on the surface of the silica fine particles. It can be obtained by reacting a saturated group-containing organic compound.
Moreover, as a polymerizable unsaturated group mentioned above, radical polymerizable acryloyl group, a methacryloyl group, etc. are mentioned, for example.

Moreover, it is preferable to make the volume average particle diameter (D50) of silica fine particles into a value within the range of 20 to 70 nm.
This is because by setting the volume average particle diameter (D50) of the silica fine particles to a value within this range, a predetermined refractive index can be obtained without reducing the transparency in the low refractive index layer. .
That is, when the volume average particle diameter (D50) of the silica fine particles is less than 20 nm, particularly in the case of hollow silica fine particles, it is difficult to secure a sufficient cavity inside the particles due to the structure, and the low refractive index. This is because the effect of lowering the refractive index of the layer may be insufficient. On the other hand, when the volume average particle diameter (D50) of the silica fine particles is a value exceeding 70 nm, light scattering is likely to occur, and the transparency in the low refractive index layer may be easily lowered.
Therefore, the volume average particle diameter (D50) of the silica fine particles is more preferably set to a value within the range of 30 to 60 nm, and further preferably set to a value within the range of 40 to 50 nm.
In addition, the volume average particle diameter (D50) of the silica fine particles can be obtained by, for example, a zeta potential measurement method, or can be obtained by using a laser diffraction scattering type particle size distribution measuring apparatus, and further based on an SEM image. You can ask for it.

Further, the amount of silica fine particles is set to a value within the range of 2 to 120 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin containing the water repellent resin as the component (A). To do.
The reason for this is that when the amount of silica fine particles is less than 2 parts by weight, it becomes difficult to sufficiently reduce the refractive index of the low refractive index layer, or sufficient surface irregularities are formed on the surface of the low refractive index layer. This is because it may be difficult to form, and it may be difficult to obtain predetermined adhesion to the transparent conductive layer or the like. On the other hand, when the amount of silica fine particles exceeds 120 parts by weight, the silica fine particles in the low refractive index layer are likely to melt or fall off when etching processing including severe alkali treatment is performed. Because there is.
Therefore, the amount of silica fine particles is more preferably set to a value in the range of 30 to 110 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin containing the water repellent resin as the component (A). More preferably, the value is in the range of 50 to 100 parts by weight.

Next, the relationship between the compounding amount of the silica fine particles and the etching resistance and surface free energy in the low refractive index layer will be described with reference to FIG.
That is, in FIG. 2, characteristic curves A and A ′ in which the horizontal axis represents the compounding amount (parts by weight) of silica fine particles, and the left vertical axis represents etching resistance (relative value) in the low refractive index layer, A characteristic curve B in which the surface free energy (mN / m) in the low refractive index layer is taken on the right vertical axis is shown.
The characteristic curves A and B are characteristic curves when an active energy ray-curable resin containing a water repellent resin as the component (A) is used, and the characteristic curve A ′ is a water repellent resin as the component (A). It is a characteristic curve at the time of using the active energy ray hardening resin which does not contain.
A specific method for measuring the etching resistance and surface free energy in the low refractive index layer will be described in Examples.

In addition, the relative value of the etching resistance is obtained by changing the reflectance change amount (%) before and after the alkali treatment in the laminate for forming a transparent conductive layer measured as described in the examples according to the following criteria. It is the value.
4: Reflectance change is a value of 0.5% or less 1: Reflectance change is a value exceeding 0.5%

First, as understood from the characteristic curve A, the etching resistance value tends to rapidly decrease as the amount of silica fine particles increases.
More specifically, when the blending amount of the silica fine particles is 120 parts by weight or less, excellent etching resistance can be stably maintained, but when the blending amount of the silica fine particles exceeds 120 parts by weight, the etching resistance is rapidly increased. It is understood that the performance is reduced.
On the other hand, as understood from the characteristic curve A ′, when the component (A) forming the matrix does not contain a water-repellent resin, the etching resistance is already obtained when the amount of silica fine particles is 20 parts by weight. It is understood that it will decline.

Further, as understood from the characteristic curve B, the value of the surface free energy tends to increase gradually as the amount of silica fine particles is increased.
Therefore, from the characteristic curves A, A ′ and B, in order to obtain a predetermined etching resistance, an ultraviolet curable resin containing a water repellent resin is used as the component (A) for forming the matrix, and the silica fine particles are used. It is understood that the blending amount should be 120 parts by weight or less.
Further, in order to obtain surface free energy (for example, 37 mN / m or more) for obtaining predetermined adhesion to the transparent conductive layer or the like required for the low refractive index layer, the blending amount of silica fine particles is 2 parts by weight or more. It is understood that the value of

(2) -3 Low Refractive Index Layer Forming Composition The low refractive index layer is formed by preparing a low refractive index layer forming composition in advance, applying, drying, and curing as described below.
The composition comprises, if necessary, an active energy ray-curable resin containing the water-repellent resin as the component (A) described above in a suitable solvent, silica fine particles as the component (B), and photopolymerization initiation. It can be prepared by adding various additives such as an agent in a predetermined ratio and dissolving or dispersing them.
In addition, about the concentration of various additive components, a solvent, the composition for low refractive index layer formation, a viscosity, etc., it is the same as the content in description of a hard-coat layer.

(2) -4 Film thickness The film thickness of the low refractive index layer is preferably set to a value in the range of 20 to 150 nm.
The reason for this is that 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 at the same time sufficient etching resistance can be obtained. It is because it can do.
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 brittle and etching resistance may be insufficient. 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 may be easily visually recognized.
Therefore, the thickness of the low refractive index layer is more preferably set to a value in the range of 25 to 120 nm, and further preferably set to a value in the range of 30 to 100 nm.

(2) -5 Surface free energy Moreover, it is preferable to make the surface free energy measured on the conditions of 23 degreeC based on JISK6768 in a low refractive index layer into the value of 37 mN / m or more.
This is because the surface free energy in the low refractive index layer is set to a value within this range, thereby improving the etching resistance while maintaining the predetermined adhesion to the transparent conductive layer or the like required for the low refractive index layer. This is because it can be obtained more effectively.
That is, when the surface free energy is less than 37 mN / m, it may be difficult to obtain predetermined adhesion to the transparent conductive layer or the like. On the other hand, when the surface free energy becomes excessively large, the adhesion with the protective film laminated on the transparent conductive layer forming laminate for surface protection becomes excessively strong, and the work in the peeling process of the protective film This is because the efficiency may be reduced.
Therefore, the surface free energy measured in accordance with JIS K 6768 in the low refractive index layer is more preferably set to a value in the range of 40 to 65 mN / m, and a value in the range of 45 to 60 mN / m. More preferably.

4). The manufacturing method of the laminated body for transparent conductive layer formation The laminated body for transparent conductive layer formation of this invention can be obtained with the manufacturing method containing the following process (a)-(b), for example.
(A) The process of forming a hard coat layer on both surfaces of a base film (b) The process of forming an optical adjustment layer on one hard coat layer Hereafter, the part which overlaps with the previous content is abbreviate | omitted, and a different part Only detailed.
In addition, although the laminated body for transparent conductive layer formation of reference invention does not make a hard-coat layer an essential structural requirement, in the following description, the case where a hard-coat layer is formed is mentioned as an example, and is demonstrated.

(1) Step (a): Step of forming a hard coat layer The above-described hard coat layer forming composition is applied to both surfaces of a base film by a conventionally known method to form a coating film, and then dried. A hard coat layer is formed by irradiating this with active energy rays and curing the coating film.
Examples of the method for applying the composition for forming a hard coat layer include a bar coat method, a knife coat method, a roll coat method, a blade coat method, a die coat method, and a gravure coat method.

Moreover, as drying conditions, it is preferable to carry out at 60-150 degreeC for about 10 seconds-10 minutes.
Furthermore, examples of the active energy rays include ultraviolet rays and electron beams.
In addition, examples of the ultraviolet light source include a high-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, a xenon lamp, and the like. The irradiation amount is usually preferably 100 to 500 mJ / cm ² .
On the other hand, examples of the electron beam light source include an electron beam accelerator, and the irradiation amount is preferably 150 to 350 kV.

(2) Step (b): Step of forming an optical adjustment layer Next, a high refractive index is formed on the formed hard coat layer (directly on the base film when no hard coat layer is formed as a reference invention ). Form a layer.
That is, the high refractive index layer is cured by applying and drying the above-described composition for forming a high refractive index layer and irradiating with an active energy ray in the same manner as forming a hard coat layer on a base film. Can be formed.
Next, a low refractive index layer is further formed on the formed high refractive index layer.
That is, the low refractive index layer is cured by applying and drying the above-described composition for forming a low refractive index layer and irradiating with an active energy ray in the same manner as forming a hard coat layer on a base film. Can be formed.

[Second Embodiment]
In the second embodiment of the present invention, as shown in FIG. 3, a transparent conductive film 100 in which an optical adjustment layer 2 and a transparent conductive layer 1 are sequentially laminated on at least one surface of a base film 4. The optical adjustment layer 2 includes a high refractive index layer 2b having a refractive index of 1.6 or more and a low refractive index of 1.45 or less from the base film 4 side. The layer 2a is laminated in order, and the low refractive index layer 2a is obtained by photocuring a composition for forming a low refractive index layer containing the following components (A) to (B). This is a conductive film 100.
(A) Active energy ray-curable resin containing a water-repellent resin 100 parts by weight (B) Silica fine particles 2 to 120 parts by weight Hereinafter, the second embodiment of the present invention is omitted from the parts that overlap with the previous contents. Only the different parts will be described in detail.

1. Transparent Conductive Layer (1) Material Material In the transparent conductive film of the present invention, the material material of the transparent conductive layer is not particularly limited as long as it has both transparency and conductivity. Examples thereof include indium, zinc oxide, tin oxide, indium tin oxide (ITO), tin antimony oxide, zinc aluminum oxide, and indium zinc oxide.
In particular, it is preferable to use ITO as a material substance.
This is because if ITO is used, a transparent conductive layer excellent in transparency and conductivity can be formed by employing appropriate film forming conditions.

(2) Pattern shape Moreover, it is preferable that a transparent conductive layer is formed in pattern shape like a line form or a grid | lattice form by an etching.
Moreover, it is preferable that the line width of the part in which the transparent conductive layer exists and the line width of the part in which the transparent conductive layer does not exist are substantially equal to the pattern shape mentioned above.
Furthermore, the said line | wire width is 0.1-10 mm normally, Preferably, it is 0.2-5 mm, Most preferably, it is 0.5-2 mm.
Note that the line width in the above-described line shape or lattice shape is not limited to a fixed one, and for example, a line connected to a shape required for a capacitive touch panel can be freely selected.
Specific examples include a pattern shape in which rhombus portions and line portions are repeatedly connected, and such a pattern shape is also included in the category of “line shape”.

(3) Film thickness Moreover, it is preferable that the thickness of a transparent conductive layer is 5-500 nm.
This is because if the thickness of the transparent conductive layer is less than 5 nm, the transparent conductive layer becomes brittle and sufficient conductivity may not be obtained. On the other hand, when the thickness of the transparent conductive layer exceeds 500 nm, the color attributed 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 further preferably 20 to 100 nm.

2. Production method of transparent conductive film For the optical adjustment layer obtained in step (b) in the production method of the laminate for forming a transparent conductive layer described above, vacuum deposition, sputtering, CVD, ion plating, spray A transparent conductive film can be obtained by forming a transparent conductive layer by a known method such as a method or a sol-gel method.
Examples of the sputtering method include a normal 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 a reactive gas, or to use ozone addition or ion assist together.
In addition, after forming the transparent conductive layer as described above, a resist mask having a predetermined pattern is formed by a photolithography method, and then an etching process is performed by a known method to form a line pattern or the like. can do.
As an etchant, an aqueous solution of an acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like is preferably used.
Moreover, as a liquid used for the alkali treatment for removing the remaining photoresist which is the final step of the etching process, from the viewpoint of speeding up the etching process, the liquid temperature is 10 to 50 ° C., the concentration is 1 to 10% by weight, It is preferable to use a strong base aqueous solution having a pH of 13.4 to 14.4.
Suitable strong bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, calcium hydroxide, strontium hydroxide, hydroxide Examples include barium, europium (II) hydroxide, thallium (I) hydroxide, and guanidine.

In order to increase the crystallinity of the transparent conductive layer and reduce the resistivity, it is preferable to perform an annealing process by providing an annealing process.
That is, it is preferable to expose the obtained transparent conductive film to a temperature condition of 130 to 180 ° C. for 0.5 to 2 hours.

  Hereinafter, with reference to an Example, the transparent conductive layer forming laminated body of this invention, etc. are demonstrated in detail.

[Example 1]
1. Preparation of composition for forming hard coat layer In a container, 60 parts by weight of amorphous silica-containing UV curable resin (manufactured by Showa Denko KK, Vinylol FC-1000) (excluding the dilution solvent) is represented. ), 45 parts by weight of silica in the amorphous silica dispersion, 0.03 parts by weight of a cross-linked acrylic copolymer resin (manufactured by Sekisui Plastics Co., Ltd., Techpolymer XX-27LA), and a silicone leveling agent 0.03 parts by weight (Bick Chemie Japan Co., Ltd., BKY-3550) was accommodated, and then a solvent was added and mixed uniformly to obtain a composition for forming a hard coat layer having a solid content concentration of 22% by weight. Prepared.

2. Preparation of composition for forming a high refractive index layer In a container, 100 parts by weight of an ultraviolet curable resin (manufactured by Daiichi Seika Kogyo Co., Ltd., Seika Beam EXF-01L (NS)) and a zirconium oxide dispersion (CIK Nanotech ( Co., Ltd., ZRMIBK15WT% -F85) 200 parts by weight, acrylic leveling agent (BIC Chemie Japan Co., Ltd., BYK-355) 0.05 parts by weight, photopolymerization initiator (BASF Japan Co., Ltd.) And 3 parts by weight of Irgacure 907) were added, and then a solvent was added and mixed uniformly 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 low refractive index layer In a container, active energy ray-curable resin containing a water repellent resin as component (A), silica fine particles as component (B), and component (C) as component (C) After storing the leveling agent and the photopolymerization initiator as the component (D) in the following composition, a solvent is added and mixed uniformly to obtain a composition for forming a low refractive index layer having a solid content concentration of 1% by weight. Prepared.
In addition, the compounding quantity in the following composition and the composition shown in Table 1 represents the pure part except a dilution solvent.
Component (A): 100 parts by weight of ultraviolet curable acrylic resin containing fluororesin (type of fluororesin: reactive fluoroacrylic resin, fluororesin content: 80% by weight, surface of cured resin coating film of fluororesin alone Free energy: 25mN / m)
Component (B): 100 parts by weight of reactive hollow silica fine particles (volume average particle diameter (D50) 45 nm)
Component (C): 0.03 part by weight of silicone-based leveling agent (BYK-3550, manufactured by Big Chemie Japan Co., Ltd.)
Component (D): 10 parts by weight of a photopolymerization initiator (BASF Japan, Irgacure 184)
In addition, the volume average particle diameter (D50) of the component (B) described above was measured with a laser diffraction / scattering particle size distribution analyzer.
In the following, the above-mentioned photopolymerization initiator as the component (D) may be referred to as “Irgacure 184”.

4). Formation of Hard Coat Layer A polyester film with an easy-adhesion layer having a film thickness of 125 μm (manufactured by Teijin DuPont Co., Ltd., PET125KEL86W) was prepared as a base film.
Next, the hard coat layer forming composition was applied to the surface of the prepared base film with a wire bar # 8.
Next, after drying at 70 ° C. for 1 minute, ultraviolet rays were irradiated under the following conditions using an ultraviolet irradiation device (manufactured by GS Yuasa Corporation) in a nitrogen atmosphere, and the surface of the base film was 2 μm thick A hard coat layer was formed.
A hard coat layer was also formed on the opposite surface of the base film in the same manner.
Light source: High pressure mercury lamp Illuminance: 150 mW / cm ²
Light intensity: 150 mJ / cm ²

5. Formation of High Refractive Index Layer Next, a composition for forming a high refractive index was applied on one hard coat layer formed with wire bar # 4.
Next, after drying at 50 ° C. for 1 minute, ultraviolet rays were irradiated under the same irradiation conditions as the hard coat layer using an ultraviolet irradiation device (manufactured by GS Yuasa Corporation) in a nitrogen atmosphere. A high refractive index layer having a thickness of 35 nm and a refractive index n _D = 1.65 was formed.

6). Formation of Low Refractive Index Layer Next, a composition for forming a low refractive index layer was coated on the formed high refractive index layer with a wire bar # 4.
Next, after drying at 50 ° C. for 1 minute, ultraviolet rays were irradiated under the same irradiation conditions as the hard coat layer using an ultraviolet irradiation device (manufactured by GS Yuasa Corporation) in a nitrogen atmosphere, and on the high refractive index layer A low refractive index layer having a film thickness of 50 nm and a refractive index n _D = 1.37 was formed to obtain a transparent conductive layer forming laminate as shown in FIG.

7). Evaluation (1) Evaluation of etching resistance The etching resistance of the obtained laminate for forming a transparent conductive layer was evaluated.
That is, the reflectivity (%) (low refractive index layer side) of the obtained laminate for forming a transparent conductive layer was measured with an ultraviolet-visible-near-infrared (UV-vis-NIR) spectrophotometer (manufactured by Shimadzu Corporation) UV-3600), and measurement was performed under conditions of a reflection angle: 8 °, a sampling pitch: 1 nm, and a measurement mode: single.
Next, the transparent conductive layer-forming laminate was immersed in a 5% by weight sodium hydroxide aqueous solution heated to 40 ° C. for 5 minutes and then subjected to alkali treatment, and then the reflectance (%) was measured under the same conditions as described above. It was measured.
Subsequently, the reflectance change amount (%) was calculated by subtracting the reflectance (%) after alkali treatment from the reflectance (%) before alkali treatment, and evaluated according to the following criteria. 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 thickness and / or the refractive index of the low refractive index layer changes due to the etching process. is there.
○: Reflectance change amount is a value of 0.5% or less ×: Reflectance change amount is a value exceeding 0.5%

(2) Evaluation of pattern visibility The patterned transparent conductive layer was formed with respect to the surface of the low refractive index layer of the obtained laminated body for transparent conductive layer formation, and the visibility was evaluated.
That is, after the obtained laminate for forming a transparent conductive layer was cut into a length of 90 mm × width of 90 mm, sputtering was performed using an ITO target (10% by weight of tin oxide, 90% by weight of indium oxide) on the low refractive index layer. A transparent conductive layer having a square shape of 60 mm in length and 60 mm in width and a film thickness of 30 nm was formed at the center of the film.
Next, a photoresist film patterned in a lattice shape was formed on the surface of the obtained transparent conductive layer.
Next, an etching treatment was performed by immersing in 10% by weight hydrochloric acid at room temperature for 1 minute, and the transparent conductive layer was patterned in a lattice shape.
Next, the substrate is immersed in a 5 wt% aqueous sodium hydroxide solution heated to 40 ° C. for 5 minutes for alkali treatment, the photoresist film on the transparent conductive layer is removed, and the transparent conductive layer having a patterned transparent conductive layer A characteristic film was obtained.
The transparent conductive film had a 30 nm transparent conductive layer having a pattern shape in which square gaps each having a side of 2 mm were partitioned in a lattice pattern by a line portion made of ITO having a line width of 2 mm.
Next, the obtained transparent conductive film is installed at a position 1 m from the white fluorescent lamp, and the white fluorescent lamp is reflected on the transparent conductive film on the same side where the white fluorescent lamp is installed. The pattern shape of the transparent conductive layer was visually observed from a position 30 cm from the transparent conductive film in 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 visually recognized ○: The pattern shape of the transparent conductive layer is slightly visually recognized ×: The pattern shape of the transparent conductive layer is visually recognized

(3) Evaluation of surface free energy The surface free energy (mN / m) measured on the conditions of 23 degreeC was evaluated based on JISK6768 in the obtained laminated body for transparent conductive layer formation.
That is, a wet tension test solution having a predetermined surface tension is applied to the top surface of the low refractive index layer, which is the outermost layer, on the obtained transparent conductive layer forming laminate so as to have a width of 10 mm and a length of 60 mm. did.
If the coating film of the wetting tension test solution is not interrupted for 2 seconds, it is determined that the surface free energy is acceptable, and the same operation is successively performed using the wetting tension test solution having a higher surface tension. It was repeated until the coating film was interrupted within 2 seconds, and the highest surface free energy passed was taken as the measurement result. The obtained results are shown in Table 1.
Since wetting tension and surface free energy are synonymous in thermodynamics, wetting tension is described as surface free energy in the present invention.

[Example 2]
In Example 2, when preparing the composition for forming a low refractive index layer, the amount of the reactive hollow silica fine particles (volume average particle diameter (D50) 45 nm) was changed to 60 parts by weight. Similarly, a laminate for forming a transparent conductive layer was produced and evaluated. The obtained results are shown in Table 1.

[Example 3]
In Example 3, when preparing the composition for forming a low refractive index layer, the amount of the reactive hollow silica fine particles (volume average particle diameter (D50) 45 nm) was set to 40 parts by weight. Similarly, a laminate for forming a transparent conductive layer was produced and evaluated. The obtained results are shown in Table 1.

[Example 4]
In Example 4, when preparing the composition for forming a low refractive index layer, the amount of the reactive hollow silica fine particles (volume average particle diameter (D50) 45 nm) was changed to 20 parts by weight. Similarly, a laminate for forming a transparent conductive layer was produced 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 produced and evaluated in the same manner as in Example 1 except that the following composition was used when preparing the composition for forming a low refractive index layer. The obtained results are shown in Table 1.
In addition, the compounding quantity in the following composition and the composition shown in Table 1 represents the pure part except a dilution solvent.
(A) Component: 100 parts by weight of an ultraviolet curable acrylic resin (C) Component: 0.05 part by weight of an acrylic leveling agent (BYK-355, manufactured by Big Chemie Japan Co., Ltd.)
Component (D): 5 parts by weight of a photopolymerization initiator (BASF Japan, Irgacure 184)

[Comparative Example 2]
In Comparative Example 2, when preparing the composition for forming a low refractive index layer, reactive hollow silica fine particles (volume average particle diameter (D50) 45 nm) are further added, and the amount of the reactive hollow silica fine particles is 20 wt. The laminated body for transparent conductive layer formation was manufactured similarly to the comparative example 1 except having set it as the part, and it evaluated. The obtained results are shown in Table 1.

[Comparative Example 3]
In Comparative Example 3, when preparing the composition for forming a low refractive index layer, reactive hollow silica fine particles (volume average particle diameter (D50) 45 nm) are further added, and the amount of the reactive hollow silica fine particles is 100 wt. The laminated body for transparent conductive layer formation was manufactured similarly to the comparative example 1 except having set it as the part, and it evaluated. The obtained results are shown in Table 1.

[Comparative Example 4]
In Comparative Example 4, when preparing the composition for forming a low refractive index layer, the amount of the reactive hollow silica fine particles (volume average particle diameter (D50) 45 nm) was changed to 130 parts by weight. Similarly, a laminate for forming a transparent conductive layer was produced and evaluated. The obtained results are shown in Table 1.

[Comparative Example 5]
In Comparative Example 5, when preparing the composition for forming a low refractive index layer, the amount of the reactive hollow silica fine particles (volume average particle diameter (D50) 45 nm) was changed to 230 parts by weight. Similarly, a laminate for forming a transparent conductive layer was produced and evaluated. The obtained results are shown in Table 1.

As described above in detail, according to the present invention, when the low refractive index layer, which is the outermost surface layer of the laminate for forming a transparent conductive layer, is formed, the active energy ray-curable resin containing the water repellent resin is used. On the other hand, by using a composition for forming a low refractive index layer in which silica fine particles are blended in a predetermined range, a laminate for forming a transparent conductive layer excellent in etching resistance in the low refractive index layer can be obtained. Became.
As a result, it becomes possible to obtain a laminate for forming a transparent conductive layer that can stably make the pattern shape of the transparent conductive layer invisible and has excellent adhesion to the transparent conductive layer and the like. It was.
Therefore, the laminate for forming a transparent conductive layer of the present invention and the transparent conductive film using the same are expected to significantly contribute to the quality improvement of the touch panel.

1: transparent conductive layer, 2: optical adjustment layer, 2a: low refractive index layer, 2b: high refractive index layer, 3: hard coat layer, 4: base film, 10: laminate for forming transparent conductive layer, 100: Transparent conductive film

Claims (8)

A transparent conductive layer forming laminate in which a hard coat layer and an optical adjustment layer are sequentially laminated on at least one surface of a base film,
The optical adjustment layer is formed by sequentially 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 from the base film side. As well as
The low refractive index layer, see contains the following (A) ~ (B) component, (B) below the silica fine particles as the component obtained by photocuring a certain low refractive index layer-forming composition in the hollow silica fine particles A laminate for forming a transparent conductive layer.
(A) Active energy ray-curable resin containing water-repellent resin 100 parts by weight (B) Silica fine particles 2 to 120 parts by weight   The layered product for forming a transparent conductive layer according to claim 1, wherein the volume average particle diameter (D50) of the silica fine particles as the component (B) is set to a value in the range of 20 to 70 nm.   The laminate for forming a transparent conductive layer according to claim 1 or 2, wherein the silica fine particles as the component (B) are reactive silica fine particles. The water-repellent resin constituting a part of the active energy ray curable resin containing a water repellent resin as component (A), in any one of claims 1-3, characterized in that the fluororesin The laminated body for transparent conductive layer formation of description. The surface-free energy in the said low-refractive-index layer shall be 37 mN / m or more, The transparent conductive layer forming laminated body as described in any one of Claims 1-4 characterized by the above-mentioned. The transparent conductive layer forming laminate according to any one of claims 1 to 5 , wherein the thickness of the low refractive index layer is set to a value within a range of 20 to 150 nm. A transparent conductive film obtained by laminating a hard coat layer, an optical adjustment layer, and a transparent conductive layer in this order on at least one surface of a base film,
The optical adjustment layer is formed by sequentially 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 from the base film side. As well as
The low refractive index layer, see contains the following (A) ~ (B) component, (B) below the silica fine particles as the component obtained by photocuring a certain low refractive index layer-forming composition in the hollow silica fine particles A transparent conductive film characterized by
(A) Active energy ray-curable resin containing water-repellent resin 100 parts by weight (B) Silica fine particles 2 to 120 parts by weight The transparent conductive film according to claim 7 , wherein the transparent conductive layer is patterned by etching.

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