JP2016187909A - Transparent conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate for forming a transparent conductive layer, which has excellent etching resistance in a hard coat layer, which can make a pattern shape of a transparent conductive layer stably invisible, and which shows excellent antiblocking property in a transparent conductive film to be obtained therefrom, and a transparent conductive film using the laminate.SOLUTION: The laminate for forming a transparent conductive layer comprises a hard coat layer, a substrate film, and an optical adjustment layer, laminated in this order. The hard coat layer is formed by photocuring a composition for forming a hard coat layer containing the following components (A) and (B). The components are: (A) 100 pts.wt. of an active energy ray-curable resin; and (B) 15-100 pts.wt. of silica fine particles.SELECTED DRAWING: Figure 1

Description

The present invention relates to a laminate for forming a transparent conductive layer and a transparent conductive film.
In particular, the laminate for forming a transparent conductive layer is excellent in etching resistance in the hard coat layer, can stably invisible the pattern shape of the transparent conductive layer, and has excellent anti-blocking properties in the obtained transparent conductive film. The present invention relates to a body 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 (for example, see Patent Document 1).

That is, Patent Document 1 discloses a hard coat substrate that includes a transparent substrate, an easy-adhesion layer, and a refractive index adjustment layer in this order, and the refractive index at a wavelength of 550 nm of the refractive index adjustment layer is 1.60. -1.90, the thickness of the refractive index adjustment layer is 0.3-5 μm, and the refractive index of the easy-adhesion layer at a wavelength of 550 nm is 1.56-1.70. A coated substrate is disclosed.
Further, it is described that a function-imparting layer having a filler and containing an antiblocking property is further laminated on the side of the transparent substrate opposite to the side where the refractive index adjusting layer is formed.

JP 2013-202844 A (Claims)

However, in the hard coat substrate disclosed in Patent Document 1, when the transparent conductive layer is patterned by etching, the function-imparting layer containing the filler is easily eroded by the etching solution, thereby the pattern of the transparent conductive layer. There was a problem that it became difficult to make the shape invisible stably.
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 severe alkali treatment is performed, the filler in the function-imparting layer is likely to melt or drop off in the hard coat substrate disclosed in Patent Document 1, and as a result, the transparent conductive layer is stably formed. There was a problem that it was difficult to make the pattern shape invisible.

Therefore, the present inventors made extensive efforts in view of the circumstances as described above, and when forming the hard coat layer that is the outermost back surface of the transparent conductive layer forming laminate, The inventors have found that the problems described above can be solved by using a composition for forming a hard coat layer obtained by blending silica fine particles in a predetermined range, and have completed the present invention.
That is, the object of the present invention is excellent in etching resistance in the hard coat layer, can stably make the pattern shape of the transparent conductive layer invisible, and excellent in anti-blocking property in the obtained transparent conductive film. It is providing the laminated body for transparent conductive layer formation, and a transparent conductive film using the same.

According to this invention, it is the laminated body for transparent conductive layer formation formed by laminating | stacking a hard-coat layer, a base film, and an optical adjustment layer in order, Comprising: A hard-coat layer is following (A)-(B ) A layered product for forming a transparent conductive layer, which is obtained by photocuring a composition for forming a hard coat layer containing a component, can solve the above-mentioned problems.
(A) Active energy ray-curable resin 100 parts by weight (B) Silica fine particles 15 to 100 parts by weight In other words, in the case of the laminate for forming a transparent conductive layer of the present invention, when forming the hard coat layer as the backmost surface. Since the composition for forming a hard coat layer used in the invention contains silica fine particles in a relatively small range with respect to the active energy ray-curable resin, the hard coat layer-forming composition is hard even when subjected to etching treatment including severe alkali treatment. It is possible to effectively prevent the silica fine particles in the coat layer from melting or dropping off (hereinafter, such an effect may be referred to as “etching resistance”).
As a result, it is possible to suppress changes in the film thickness and refractive index of the hard coat layer, and in turn, it is possible to suppress changes in the optical characteristics of the hard coat layer. Can be visualized.
In addition, since the silica fine particles in the hard coat layer can be effectively prevented from melting or falling off, the fine surface irregularities formed due to the silica fine particles on the surface of the hard coat layer are effectively retained. The
As a result, when the obtained transparent conductive film is wound up in a roll shape, it is possible to effectively suppress blocking of the front and back surfaces of the directly contacting film (hereinafter referred to as “anti-blocking property”). May be called).

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 10-100 nm.
By comprising in this way, predetermined | prescribed antiblocking property can be obtained, without reducing the transparency in a hard-coat layer.

Moreover, when comprising the laminated body for transparent conductive layer formation of this invention, it is preferable that the silica particle as (B) component is a solid silica particle.
By comprising in this way, since a particle diameter can be made small compared with a hollow silica fine particle, in spite of having mix | blended the quantity required in order to acquire antiblocking property, a hard-coat layer The transparency can be effectively maintained.

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 a silica particle can be firmly fixed with respect to a hard-coat layer, etching resistance can be improved more effectively.

Moreover, in comprising the laminated body for transparent conductive layer formation of this invention, while the composition for hard-coat layer formation contains a fluorine-type leveling agent as (C) component, the compounding quantity of the said fluorine-type leveling agent is (A ) It is preferable to set the value within the range of 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin as a component.
By comprising in this way, since the silica particle in a hard-coat layer can be protected more effectively, etching resistance can be improved more effectively.

Moreover, when comprising the laminated body for transparent conductive layer formation of this invention, it is preferable to make the film thickness of a hard-coat layer into the value within the range of 0.5-5 micrometers.
With this configuration, sufficient etching resistance can be obtained, and at the same time, the occurrence of curling in the transparent conductive layer forming laminate can be effectively suppressed when annealing is performed.
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.

Further, in constituting the transparent conductive layer forming laminate of the present invention, when the hard coat layer is the first hard coat layer, the second hard coat is interposed between the base film and the optical adjustment layer. It is preferable to have a layer.
By comprising in this way, it can suppress effectively that an optical adjustment layer is contaminated by the oligomer component which bleeds from a base film, and when an annealing process is performed, for transparent conductive layer formation Generation of curl in the laminate can be effectively suppressed.

In constructing the transparent conductive layer forming laminate of the present invention, the second hard coat layer is obtained by photocuring the same hard coat layer forming composition as the first hard coat layer, It is preferable to have the same film thickness as the hard coat layer.
With this configuration, the first and second hard coat layers can be easily formed, and curling in the transparent conductive layer forming laminate can be more effectively suppressed when annealing is performed. can do.

Another aspect of the present invention is a transparent conductive film in which a hard coat layer, a base film, an optical adjustment layer, and a transparent conductive layer are sequentially laminated, and the hard coat layer is A transparent conductive film obtained by photocuring a composition for forming a hard coat layer containing the components (A) to (B).
(A) Active energy ray-curable resin 100 parts by weight (B) Silica fine particles 15 to 100 parts by weight That is, if the transparent conductive film of the present invention is used, a predetermined laminate for forming a transparent conductive layer is used. It is excellent in etching resistance in the coating layer, the pattern shape of the transparent conductive layer can be stably invisible, and excellent antiblocking properties can be obtained.

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 hard coat 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 for explaining the relationship between the compounding amount of silica fine particles and the etching resistance and anti-blocking property in the hard coat layer. FIG. 3 is a diagram provided for explaining the configuration of the transparent conductive film of the present invention.

[First Embodiment]
As shown in FIG. 1 (a), the first embodiment of the present invention is a laminate for forming a transparent conductive layer, in which a hard coat layer 3a, a base film 4 and an optical adjustment layer 2 are sequentially laminated. In the laminate 10 for forming a transparent conductive layer, wherein the hard coat layer 3a is formed by photocuring a hard coat layer forming composition containing the following components (A) to (B): is there.
(A) Active energy ray-curable resin 100 parts by weight (B) Silica fine particles 15 to 100 parts by weight In addition, in FIG. 1 (a), the form having the hard coat 3 (3a, 3b) on both surfaces of the base film 4 The transparent conductive layer forming laminate 10 is shown as an example, but the hard coat layer 3b between the base film 4 and the optical adjustment layer 2 can be omitted.
In addition, as for the optical adjustment layer 2, an aspect composed of two layers of a high refractive index layer 2 b and a low refractive index layer 2 a is shown as an example, but optical adjustment of an aspect composed of one layer or an aspect composed of three or more layers. Layer 2 may be used.
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), in constructing the transparent conductive layer forming laminate 10 of the present invention, at least the surface of the base film 4 opposite to the side on which the optical adjustment layer 2 is laminated. In addition, a hard coat layer 3a is provided.
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”). .

In addition, as shown in FIG. 1A, when the hard coat layer 3a is the first hard coat layer, the second hard coat layer 3b is interposed between the base film 4 and the optical adjustment layer 2. It is preferable to have.
The reason for this is that, by having such a second hard coat layer, it is possible not only to effectively prevent the optical adjustment layer from being contaminated by the oligomer component that bleeds from the base film, but also for forming a transparent conductive layer. This is because the occurrence of curling in the laminate can be effectively suppressed.
The second hard coat layer is preferably formed by photocuring the same hard coat layer-forming composition as the first hard coat layer and has the same film thickness as the first hard coat layer.
The reason for this is that by forming the second hard coat layer in this way, the formation of the first and second hard coat layers can be facilitated, and the laminate for forming a transparent conductive layer when annealed is applied. This is because the occurrence of curling can be more effectively suppressed.
Accordingly, the following description is common to both the first hard coat layer and the second hard coat layer.

(1) Material substance Moreover, the hard-coat layer in this invention is formed by photocuring the composition for hard-coat layer formation containing the following (A)-(B) component as a material substance.
(A) Active energy ray curable resin 100 parts by weight (B) Silica fine particles 15 to 100 parts by weight The reason for this is that the hard coat layer forming composition used when forming the hard coat layer is an active energy ray curable resin. On the other hand, by including silica fine particles in a relatively small range, it is effective that the silica fine particles in the hard coat layer dissolve or fall off even when etching processing including severe alkali treatment is performed. This is because it can be suppressed.
More specifically, as shown in FIG. 1 (a), when the amount of silica fine particles in the hard coat layer 3a is small, the presence of the matrix portion made of resin is increased, so that severe alkali treatment was performed. Even in this case, the silica fine particles are effectively protected by the matrix portion, and it is possible to effectively suppress melting or falling off.
As a result, changes in the film thickness and refractive index of the hard coat layer can be suppressed, and as a result, changes in the optical properties of the hard coat layer can be suppressed.
On the other hand, as shown in FIG. 1B, when the amount of silica fine particles in the hard coat layer 3a ′ is large, the presence ratio of the matrix portion made of resin is reduced. The silica fine particles are not sufficiently protected by the matrix portion, and are likely to melt or fall off.
Therefore, as shown in FIG. 1 (a), the transparent conductive layer forming laminate 10 of the present invention having a small amount of silica fine particles in the hard coat layer 3a can be formed on the optical adjustment layer 2. The pattern shape of the conductive layer can be made invisible stably.

In addition, since the silica fine particles in the hard coat layer are effectively suppressed from melting or falling off, the fine surface irregularities formed due to the silica fine particles on the surface of the hard coat layer are effective. Retained.
Therefore, when the transparent conductive film obtained is wound up in a roll shape, blocking of the front and back surfaces of the directly contacting film can be effectively suppressed.
Hereinafter, each component will be described.

(1) -1 (A) component: active energy ray curable resin (A) component is an active energy ray curable resin.
The active energy ray-curable resin as the component (A) is a polymerizable compound that has energy quanta in an electromagnetic wave or a charged particle beam, that is, is crosslinked and cured by irradiation with ultraviolet rays or electron beams. For example, a photopolymerizable prepolymer and a photopolymerizable monomer can be mentioned.

  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 Component (B): Silica fine particles The component (B) is silica fine particles.
The type of silica fine particles is not particularly limited, but solid silica fine particles are preferably used.
This is because the solid silica fine particles can have a smaller particle diameter than hollow silica fine particles having a volume average particle diameter of 20 nm or more. This is because the transparency of the hard coat layer can be effectively maintained in spite of the incorporation of.
Further, it is economically advantageous as compared with expensive hollow silica fine particles.
The “solid silica fine particles” mean silica fine particles that do not have 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 hard coat layer, and thus can improve the etching resistance 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 a silica fine particle into the value within the range of 10-100 nm.
The reason for this is that by setting the volume average particle diameter (D50) of the silica fine particles to a value within this range, a predetermined antiblocking property can be obtained without reducing the transparency in the hard coat layer. .
That is, when the volume average particle diameter (D50) of the silica fine particles is less than 10 nm, the surface irregularities on the surface of the hard coat layer become excessively small, and it is difficult to effectively exhibit antiblocking properties. Because there is. On the other hand, when the volume average particle diameter (D50) of the silica fine particles exceeds 100 nm, light scattering is likely to occur and the transparency in the hard coat 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 12 to 60 nm, and further preferably set to a value within the range of 14 to 30 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.

Moreover, the compounding quantity of a silica fine particle shall be a value within the range of 15-100 weight part with respect to 100 weight part of active energy ray-curable resins as (A) component.
The reason for this is that when the amount of silica fine particles is less than 15 parts by weight, the hardness of the hard coat layer becomes insufficient, or it becomes difficult to form sufficient surface irregularities on the surface of the hard coat layer, This is because it may be difficult to obtain anti-blocking properties and adhesion to the pressure-sensitive adhesive layer. On the other hand, when the compounding amount of the silica fine particles exceeds 100 parts by weight, the silica fine particles in the hard coat layer may be easily dissolved or dropped off when an etching process including a severe alkali treatment is performed. Because there is.
Therefore, the blending amount of the silica fine particles is more preferably set to a value in the range of 20 to 70 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin as the component (A), and 30 to 50 parts by weight. It is more preferable to set the value within the range.

Next, the relationship between the compounding amount of the silica fine particles and the etching resistance and antiblocking property in the hard coat layer will be described with reference to FIG.
That is, in FIG. 2, the horizontal axis represents the amount (parts by weight) of silica fine particles, and the left vertical axis represents the change in reflectance (%) before and after alkali treatment in the laminate for forming a transparent conductive layer. A curve A and a characteristic curve B taking anti-blocking property (relative value) are shown on the right vertical axis.
In addition, about the specific measurement method of the reflectance variation | change_quantity before and behind alkali treatment in a laminated body for transparent conductive layer formation, and antiblocking property, it describes in an Example.
Further, the reflectance change amount (%) before and after the alkali treatment in the laminate for forming a transparent conductive layer is the reflectivity of the hard coat layer by changing the film thickness and / or the refractive index of the hard coat layer by the alkali treatment. Change, it becomes an index of etching resistance of the hard coat layer, and the smaller the change in reflectance, the better the etching resistance. In addition, it can be determined that the film has excellent etching resistance.

The relative value of the anti-blocking property is a value obtained by converting the anti-blocking property evaluated as described in the examples into a relative value according to the following criteria.
4: Layer surfaces do not adhere to each other 1: Layer surfaces adhere to each other and do not move

First, as understood from the characteristic curve A, the reflectance change amount tends to increase rapidly as the blending amount of the silica fine particles increases.
More specifically, in the range where the amount of silica fine particles is 100 parts by weight or less, the amount of change in reflectance can be stably set to a value of 0.5% or less, but the amount of silica fine particles is 100% by weight. It is understood that the amount of change in reflectivity suddenly increases beyond 0.5% and exceeds 0.5%.
This sudden increase in reflectance change is presumed to be due to the surface of the hard coat layer or the layer itself being destroyed by the alkali treatment.

Further, as understood from the characteristic curve B, the anti-blocking value tends to increase rapidly as the amount of silica fine particles increases.
More specifically, when the amount of silica fine particles is less than 15 parts by weight, the anti-blocking value is low, but when it is 15 parts by weight or more, the predetermined anti-blocking property required in practice seems to be obtained. Thus, it is understood that when it is 40 parts by weight or more, excellent anti-blocking properties can be stably obtained.
Therefore, it is understood from the characteristic curves A and B that the blending amount of the silica fine particles should be a value within the range of 15 to 100 parts by weight in order to achieve both the etching resistance and the anti-blocking property. .

(1) -3 Component (C): Fluorine Leveling Agent It is preferable that the component (C) further contains a fluorine leveling agent.
The reason for this is that the inclusion of the fluorine leveling agent can more effectively protect the silica fine particles in the hard coat layer, and therefore the etching resistance can be more effectively improved.
More specifically, the water repellent property of the fluorine-based leveling agent can effectively protect the silica fine particles in the hard coat layer from the alkali component used for the alkali treatment.
As the type of fluorine leveling agent, conventionally known ones can be used. However, compared with a linear fluorine leveling agent, it has low volatility and excellent thermal stability. A fluorine-based leveling agent having a rigid molecular structure containing a heavy bond is preferable, and examples of such a fluorine-based leveling agent include Neos Co., Ltd., “Factent 7602A”.

Moreover, it is preferable to make the compounding quantity of a fluorine-type leveling agent into the value within the range of 0.01-0.2 weight part with respect to 100 weight part of active energy ray-curable resins as (A) component.
The reason for this is that when the amount of the fluorine leveling agent is less than 0.01 parts by weight, it becomes difficult to effectively protect the silica fine particles in the hard coat layer, and thus the etching resistance can be improved. This is because it may be difficult. On the other hand, when the amount of the fluorine-based leveling agent exceeds 0.2 parts by weight, the surface free energy of the hard coat layer becomes excessively low, and the pressure-sensitive adhesive layer required for the hard coat layer, etc. This is because it may be difficult to obtain predetermined adhesion to the film.
Accordingly, the blending amount of the fluorine leveling agent is more preferably set to a value within the range of 0.03 to 0.18 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin as the component (A). More preferably, the value is in the range of 0.05 to 0.15 parts by weight.

(1) -4 (D) Component: Photopolymerization Initiator Moreover, since the active energy ray-curable resin can be efficiently cured with active energy rays, particularly ultraviolet rays, a photopolymerization initiator as component (D) is optionally added. Use in combination is also preferred.
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.
The blending amount of the photopolymerization initiator is preferably set to a value within the range of 0.2 to 10 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin as the component (A) described above. More preferably, the value is in the range of 1 to 5 parts by weight.

(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 the resulting hard coat layer-forming composition to a solid content concentration of 0.05 to 30% by weight from the viewpoint of easily adjusting the film thickness to a predetermined range. It is more preferable to dilute to ˜25% 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 0.5-5 micrometers.
This is because when the film thickness of the hard coat layer is less than 0.5 μm, the curability of the resin is lowered and it becomes difficult to obtain sufficient etching resistance. This is because the holding function against heat shrinkage becomes insufficient and curling may not be suppressed. On the other hand, when the film thickness of the hard coat layer exceeds 5 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 0.8 to 4 μm, and further preferably set to a value within the range of 1 to 3 μm.

3. Optical Adjustment Layer As shown in FIG. 1A, the optical adjustment layer 2 includes a high refractive index layer 2b having a relatively high refractive index and a low refractive index having a relatively low refractive index from the base film 4 side. The layer 2a is preferably laminated in order.
This is because the optical adjustment layer has such a laminated structure, so that the pattern shape of the transparent conductive layer is easily visually recognized due to the difference between the refractive index of the transparent conductive layer and the refractive index of the base film 4. This is because it can be effectively suppressed.

(1) High refractive index layer (1) -1 Refractive index The refractive index of the high refractive index layer is preferably 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, the viscosity, 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 refractive index of the low refractive index layer is preferably set to a value 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 preferably formed by photocuring a low refractive index layer forming composition containing the following components (a) to (b) as a material substance.
(A) Active energy ray curable resin 100 parts by weight (b) Silica fine particles 2 to 120 parts by weight This is because the composition for forming a low refractive index layer used when forming a low refractive index layer is active energy ray curable. The silica fine particles in the low-refractive index layer can be dissolved or dropped even when etching processing including severe alkali treatment is performed by containing silica fine particles in a relatively small range with respect to the functional resin. It is because it can suppress effectively.
In addition, the active energy ray-curable resin forms a matrix portion in the low refractive index layer by curing, more effectively protects the silica fine particles in the low refractive index layer, and further effectively improves the etching resistance. it can.
Hereinafter, each component will be described.

(I) Component (a): Active energy ray curable resin The component (a) is an active energy ray curable resin.
As the active energy ray-curable resin as 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 active energy ray-curable resin preferably contains a water repellent resin.
This is because the silica fine particles in the low refractive index layer can be more effectively protected by containing the water-repellent resin, so that the etching resistance can be improved more effectively.
In addition, the water repellent resin has a lower refractive index than the (meth) acrylic UV curable resin, which is the main active energy ray curable resin, so that the refractive index of the low refractive index layer can be determined more easily. This is because it can be reduced to a range of.
Further, the water-repellent resin 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 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.

Moreover, it is preferable to make the compounding quantity of a silica fine particle into the value within the range of 2-120 weight part with respect to 100 weight part of active energy ray-curable resins containing the water repellent resin as (A) component.
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 compounding amount of the silica fine particles exceeds 120 parts by weight, the silica fine particles in the low refractive index layer are likely to be dissolved or dropped off when an etching treatment including a severe alkali treatment is performed. It is because there is a case to do.
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.

(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 an active energy ray-curable resin as component (A) described above and silica fine particles as component (B), and a photopolymerization initiator and other various additive components in an appropriate solvent as necessary. Can be prepared by adding them at 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.

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 this invention does not make the hard-coat layer an essential structural requirement on both surfaces of a base film, in the following description, the hard-coat layer was formed on both surfaces of the base film. A case will be described as an example.

(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.
Moreover, when irradiating an active energy ray, it is more preferable to carry out in a nitrogen atmosphere.
This is because the curing reaction on the surface of the hard coat layer effectively proceeds by performing in a nitrogen atmosphere, and the etching resistance in the hard coat layer can be further effectively improved.

(2) Step (b): Step of forming an optical adjustment layer Next, a high refractive index layer is formed on the formed hard coat layer (in the case of not forming the hard coat layer, directly on the base film). .
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.
Moreover, when irradiating an active energy ray, it is more preferable to carry out in a nitrogen atmosphere.
The reason for this is that when the reaction is carried out in a nitrogen atmosphere, the curing reaction on the surface of the optical adjustment layer effectively proceeds, and the etching resistance in the optical adjustment layer, particularly the low refractive index layer, which is the outermost surface layer, is further effectively improved. It is because it can be made.

[Second Embodiment]
As shown in FIG. 3, the second embodiment of the present invention is a transparent conductive film in which a hard coat layer, a base film, an optical adjustment layer, and a transparent conductive layer are sequentially laminated. The hard coat layer is a transparent conductive film obtained by photocuring a composition for forming a hard coat layer containing the following components (A) to (B).
(A) Active energy ray-curable resin 100 parts by weight (B) Silica fine particles 15 to 100 parts by weight Hereinafter, in the second embodiment of the present invention, parts overlapping with the previous contents are omitted, and only different parts are included. Detailed description.

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”.
In addition, when the transparent conductive layer is formed in this way, the pattern shape of the transparent conductive layer is usually conspicuous by performing an annealing treatment. However, as shown in FIG. 3, hard coat layers are formed on both sides of the base film. When providing, if it is the transparent conductive film of this invention, the pattern shape of a transparent conductive layer can be made invisible.

(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 container, active energy ray-curable resin as component (A), silica fine particles as component (B), leveling agent as component (C), (D) After containing a photopolymerization initiator as a component in the following composition, a solvent was added and mixed uniformly to prepare a hard coat layer forming composition having a solid content concentration of 22% by weight.
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 dipentaerythritol hexaacrylate (B) Component: 43.2 parts by weight of reactive solid silica fine particles (volume average particle diameter (D50) 15 nm)
Component (C): Fluorine-based leveling agent 0.05 parts by weight (manufactured by Neos Co., Ltd., Footent 7602A)
Component (D): 3 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 photoinitiator as the component (D) may be referred to as “Irgacure 184”.

2. Preparation of composition for forming a high refractive index layer In a container, 100 parts by weight of UV curable resin (manufactured by Dainichi Seika Kogyo Co., Ltd., Seika Beam EXF-01L (NS)) (representing the pure content excluding the dilution solvent) The same shall apply hereinafter), 200 parts by weight of a zirconium oxide dispersion (manufactured by CIK Nanotech Co., Ltd., ZRMIBK15WT% -F85), and an acrylic leveling agent (BYK-355, BYK-355). After containing 05 parts by weight and 3 parts by weight of a photopolymerization initiator (BASF Japan Co., Ltd., Irgacure 907), a solvent is added and mixed uniformly to obtain a high refractive index with a solid content concentration of 1% by weight. A layer forming composition was prepared.

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 After containing 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 composition shown to the following composition represents the pure part except a dilution solvent.
(A) Component: UV curable acrylic resin containing fluororesin
100 parts by weight (type of fluororesin: reactive fluoroacrylic resin, fluororesin content: 80% by weight, surface free energy of cured resin coating film of fluororesin alone: 25 mN / m)
Component (b): Reactive hollow silica fine particles 100 parts by weight (volume average particle diameter (D50) 45 nm)
(C) Ingredient: Acrylic leveling agent 0.05 parts by weight (BYK-355, manufactured by BYK Japan KK)
(D) Component: 5 parts by weight of photopolymerization initiator (manufactured by BASF Japan Ltd., 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.

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 converted into an ultraviolet-visible-near-infrared (UV-vis-NIR) spectrophotometer (manufactured by Shimadzu Corporation, UV). -3600), measurement was performed under the 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.
Next, the reflectance change amount (%) was calculated by subtracting the reflectance (%) after alkali treatment from the reflectance (%) before alkali treatment. The obtained results are shown in Table 1.
In addition, if the reflectance change amount is a value of 0.5% or less, it can be determined that it has practically excellent etching resistance.
The reason why the etching resistance can be evaluated by the reflectance change amount (%) is that the reflectance of the hard coat layer changes when the film thickness and / or the refractive index of the hard coat layer change due to the etching process.

(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 visually recognized.

(3) Evaluation of antiblocking property The antiblocking property in the obtained laminated body for transparent conductive layer formation was evaluated.
That is, the laminate for forming a transparent conductive layer was placed on a flat glass plate so that the hard coat layer faced upward without using an adhesive or the like.
Next, another transparent conductive layer forming laminate is placed on the placed transparent conductive layer forming laminate, and then pressed by hand to rub these two transparent conductive layer forming laminates. Then, the hard coat layers and the hard coat layer and the low refractive index layer were rubbed together, and the anti-blocking property was evaluated according to the following criteria. The obtained results are shown in Table 1.
○: Layer surfaces do not adhere to each other ×: Layer surfaces adhere to each other and do not move

[Example 2]
In Example 2, a transparent conductive layer-forming laminate was produced and evaluated in the same manner as in Example 1 except that the following composition was used when preparing the hard coat layer-forming composition. 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.
(A1) component: dipentaerythritol hexaacrylate
99.5 parts by weight (A2) component: Cross-linked acrylic copolymer resin 0.5 parts by weight (manufactured by Sekisui Plastics Co., Ltd., Techpolymer XX-27LA)
Component (B): 100 parts by weight of reactive solid silica fine particles (volume average particle diameter (D50) 15 nm)
Component (C): Fluorine-based leveling agent 0.13 parts by weight (manufactured by Neos Co., Ltd., Footgent 7602A)
Component (D): 6.7 parts by weight of 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 cross-linked acrylic copolymer resin as the component (A2) may be referred to as “Techpolymer XX-27LA”.

[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 hard coat 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 dipentaerythritol hexaacrylate (B) Component: 150 parts by weight of reactive solid silica fine particles (volume average particle diameter (D50) 15 nm)
Component (C): Fluorine-based leveling agent 0.05 parts by weight (manufactured by Neos Co., Ltd., Footent 7602A)
Component (D): 5 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.

[Comparative Example 2]
In Comparative Example 2, a transparent conductive layer-forming laminate was produced and evaluated in the same manner as in Example 1 except that the following composition was used when preparing the hard coat layer-forming composition. 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.
Component (A): 100 parts by weight of dipentaerythritol hexaacrylate (C) Component: 0.05 part by weight of a fluorine-based leveling agent (manufactured by Neos Co., Ltd., Footage 7602A)
Component (D): 5 parts by weight of a photopolymerization initiator (BASF Japan, Irgacure 184)

As described above in detail, according to the present invention, when forming the hard coat layer which is the outermost surface of the transparent conductive layer forming laminate, silica fine particles are added to the active energy ray-curable resin in a predetermined range. By using the composition for forming a hard coat layer formed by blending, a transparent conductive layer-forming laminate having excellent etching resistance in the hard coat 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 excellent in antiblocking property in the obtained transparent conductive film can be obtained. 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, 3a: first hard coat layer, 3b: second hard coat layer, 4: base film, 10: laminate for forming transparent conductive layer, 100: transparent conductive film

Claims (10)

A laminate for forming a transparent conductive layer in which a hard coat layer, a base film, and an optical adjustment layer are laminated in order,
A laminate for forming a transparent conductive layer, wherein the hard coat layer is obtained by photocuring a composition for forming a hard coat layer containing the following components (A) to (B).
(A) Active energy ray-curable resin 100 parts by weight (B) Silica fine particles 15 to 100 parts by weight   The laminate 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 10 to 100 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 solid silica fine particles.   The laminate for forming a transparent conductive layer according to any one of claims 1 to 3, wherein the silica fine particles as the component (B) are reactive silica fine particles.   The hard coat layer forming composition contains a fluorine leveling agent as component (C), and the blending amount of the fluorine leveling agent is 100 parts by weight of the active energy ray-curable resin as the component (A). The transparent conductive layer forming laminate according to any one of claims 1 to 4, wherein the value is within a range of 0.01 to 0.2 parts by weight.   The laminate for forming a transparent conductive layer according to claim 1, wherein the hard coat layer has a thickness in a range of 0.5 to 5 μm.   When the hard coat layer is a first hard coat layer, a second hard coat layer is provided between the base film and the optical adjustment layer. The laminated body for transparent conductive layer formation as described in any one.   The second hard coat layer is formed by photocuring the same hard coat layer forming composition as the first hard coat layer, and has the same film thickness as the first hard coat layer. The laminate for forming a transparent conductive layer according to claim 7. A transparent conductive film obtained by laminating a hard coat layer, a base film, an optical adjustment layer, and a transparent conductive layer in order,
The said hard-coat layer photocures the composition for hard-coat layer formation containing the following (A)-(B) component, The transparent conductive film characterized by the above-mentioned.
(A) Active energy ray-curable resin 100 parts by weight (B) Silica fine particles 15 to 100 parts by weight   The transparent conductive film according to claim 9, wherein the transparent conductive layer is patterned by etching.

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