JP6791647B2 - Laminate and protective film - Google Patents

Description

The present invention is a film for laminating a transparent conductive film, a laminate in which a protective film is attached to a surface of the film opposite to the surface on the laminating side of the transparent conductive film, and transparent on the laminating side of the transparent conductive film of the laminate. The present invention relates to a laminate formed by laminating conductive films, and a protective film for forming these laminates.

Conventionally, transparent conductive films have been widely used as materials for products such as touch panels, liquid crystal display devices, organic electroluminescence (organic EL) devices, plasma display panels (PDPs), and solar cells.
As such a transparent conductive film, a film in which a transparent conductive film of ITO (Indium Tin Oxide) is provided on one side of a film base material such as polyester is generally used.

Further, when producing a transparent conductive film, a step of manufacturing a film for laminating a transparent conductive film, a sputtering treatment step for laminating a transparent conductive film on a film for laminating a transparent conductive film, and crystallizing the transparent conductive film. An annealing step for this purpose, a step of patterning a transparent conductive film, a step of forming an electrode on a transparent conductive film, and the like are carried out.

Here, there are various modes in the implementation pattern of each step. For example, due to the limitation of the annealing treatment equipment, it is necessary to perform the steps after the annealing treatment step on each cut sheet (short sheet). May occur.
In this case, first, the manufacturing process and the sputtering process of the transparent conductive film laminating film are performed by roll-to-roll, and one long sheet obtained at this point is cut into a plurality of short sheets, and then these are performed. Are stacked and stored in a laminated state.
Next, the required number of sheets are taken out one by one from the laminated product, and the subsequent steps after the annealing process are performed.
In both the sputtering treatment and the annealing treatment, heating is performed at about 150 ° C., in the sputtering treatment, it is generally exposed to a heating environment for about 1 to several minutes, and in the annealing treatment, it is exposed to a heating environment. It is generally exposed for about 1 hour.

On the other hand, the transparent conductive film is required to be further thinned from the viewpoint of further improving the image sharpness.
Therefore, the transparent conductive film laminated film constituting the film is also required to be thinner than ever.

However, when the transparent conductive film laminated film is made thinner than ever, the film is easily deformed by a slight change in tension or vibration in a heating environment.
Therefore, when each step is carried out in the illustrated manner, there is a problem that it becomes difficult to adjust the tension of the sheet during the roll-to-roll sputtering process.
In addition, if the transparent conductive film for laminating film is made thinner than before, the handleability is excessively lowered, and it becomes difficult to take out the sheets one by one from the state of being stored as a laminated product, and the next annealing There was a problem that it became difficult to use for processing.

On the other hand, Patent Document 1 is a film capable of protecting and peeling off the surface of the transparent conductive film opposite to the conductive thin film, and the surface protective film has an adhesive layer on one side of the base film. Is provided, and the tensile speed at which the surface protective film is peeled off between the adhesive layer and the adherend surface after heating at 150 ° C. for 1 hour with the adhesive layer bonded to the adherend surface. A surface protective film for a transparent conductive film, characterized in that the adhesive strength measured under the condition of 0.3 m / min and the adhesive strength measured under the condition of a tensile speed of 10 m / min are both 2.8 N / 20 mm or less. Is disclosed.

Japanese Patent No. 4151821 (Claims)

The side of the transparent conductive film for laminating film is opposite to the surface on which the transparent conductive film is laminated, in order to deal with the problems during the sputtering treatment and the problem of film take-out after cutting due to the thinning of the transparent conductive film for laminating film. By attaching a protective film to the surface of the film, an attempt was made to improve the film take-out property by increasing the film thickness while reinforcing the film strength during the sputtering treatment.
However, when this aspect is attempted with a conventional protective film, vibration and tension due to transportation are applied in a heating environment when the sputtering treatment is performed, so that peeling occurs between the transparent conductive film lamination film and the protective film. New problems such as uneven thickness of the transparent conductive film of the transparent conductive film and wrinkles on the film have occurred.

On the other hand, in order to solve this, when a protective film having high adhesive strength is used, the protective film can be peeled off after undergoing a sputtering treatment step, an annealing treatment step, and a step of patterning the transparent conductive film. Even if it becomes difficult or can be peeled off, a new problem has arisen in which the pattern of the transparent conductive film is distorted due to the combined effects of the increase in adhesive strength and the thinning.
It should be noted that these new problems could not be solved even by using the protective film as shown in the examples of Patent Document 1.
That is, the present invention is a laminate capable of obtaining a thin transparent conductive film formed by forming a patterned transparent conductive film according to dimensions in a low cost and simple process, and the transparent conductive film laminate side of the laminate. It is an object of the present invention to provide a laminate formed by laminating a transparent conductive film on the surface and a protective film for forming the laminate.

According to the present invention, the laminate includes a transparent conductive film for laminating and a protective film laminated on the side opposite to the side on which the transparent conductive film is laminated. The protective film has a protective film base material and an adhesive layer laminated on one surface of the protective film base material, and is transparently conductive when the laminate is heated in an environment of 150 ° C. for 10 minutes. The adhesive strength P ₁ (peeling angle 180 °, peeling speed 0.3 m / min) of the protective film to the film for film lamination is set to a value within the range of 20 to 400 mN / 25 mm, and the laminate is placed in an environment of 150 ° C. After heating for 60 minutes, the adhesive strength P ₂ (peeling angle 180 °, peeling speed 0.3 m / min) of the protective film to the transparent conductive film for laminating when left to stand in an environment of 25 ° C for 24 hours is 250 to 250. The value is set within the range of 400 mN / 25 mm , and the adhesive force P ₀ (peeling angle 180 °, peeling speed 0.3 m / min) of the protective film to the transparent conductive film for laminating before heating the laminated body is determined. Provided is a laminate characterized in that the difference from the adhesive force P ₁ is a value of 80 mN / 25 mm or less, and the above-mentioned problems can be solved.
That is, in the case of the laminate of the present invention, the adhesive strength when the protective film is peeled from the laminate in a heating environment and the adhesive strength when the protective film is peeled from the laminate after heating are predetermined respectively. Since the range is specified, it is possible to obtain a laminate having excellent adhesion of the protective film during the sputtering treatment and excellent peelability of the protective film when the protective film is finally peeled off after the annealing treatment. Can be done.
Therefore, while effectively suppressing wrinkles and peeling of the transparent conductive film for laminating during the sputtering treatment, the patterned transparent conductive film is distorted when the protective film is finally peeled off after the annealing treatment. Can be effectively suppressed from occurring.

Further, in constructing the laminated body of the present invention, it is preferable that the adhesive strengths P ₁ and P ₂ satisfy the following relational expression (1).
P _2- P ₁ ≤ 300mN / 25mm (1)
With this configuration, it is possible to more stably achieve both the adhesion of the protective film during the sputtering treatment and the peelability of the protective film when the protective film is finally peeled off after the annealing treatment. it can.

Further, in constructing the laminate of the present invention, it is preferable that the thickness of the protective film base material is set to a value within the range of 23 to 250 μm.
With this configuration, it is possible to more stably achieve both the adhesion of the protective film during the sputtering treatment and the peelability of the protective film when the protective film is finally peeled off after the annealing treatment. it can.

Further, in constructing the laminate of the present invention, it is preferable that the surface free energy of the surface of the transparent conductive film laminate film on the side to which the protective film is bonded is set to a value within the range of 30 to 60 mJ / m ^2. ..
With this configuration, it is possible to more stably achieve both the adhesion of the protective film during the sputtering treatment and the peelability of the protective film when the protective film is finally peeled off after the annealing treatment. it can.

Further, in constructing the laminate of the present invention, it is preferable to have a hard coat layer on the side of the transparent conductive film laminate film to which the protective film is bonded.
With such a configuration, the durability and dimensional stability of the transparent conductive film laminated film can be improved, the adhesion of the protective film during the sputtering treatment, and the final protective film after the annealing treatment. It is possible to more stably achieve both the peelability of the protective film at the time of peeling.

Further, in constructing the laminated body of the present invention, it is preferable that the transparent conductive film is laminated on the side where the transparent conductive film is laminated in the transparent conductive film laminating film.

In addition, another aspect of the present invention is a protective film used for forming the above-mentioned laminate.
That is, in the case of the protective film of the present invention, the adhesion to the transparent conductive film laminated film during the sputtering treatment and the peelability to the transparent conductive film laminated film when the protective film is finally peeled off after the annealing treatment. And can be effectively compatible.

1 (a) to 1 (b) are views provided for explaining the laminated body of the present invention. FIG. 2 is a diagram provided for explaining the adhesive strength defined in the present invention.

In the embodiment of the present invention, as shown in FIG. 1A, the transparent conductive film laminating film 10 and the transparent conductive film 1 shown in FIG. 1B in the transparent conductive film laminating film 10 are laminated. A laminate 100 including a protective film 20 bonded to the side opposite to the side, wherein the protective film 20 is laminated on one surface of the protective film base material 22 and the protective film base material 22. As shown in FIG. 2, it has an adhesive layer 24, and as shown in FIG. 2, the adhesive force P ₁ of the protective film 20 to the transparent conductive film lamination film 10 when the laminate 100 is heated in an environment of 150 ° C. for 10 minutes. The peeling angle (180 °, peeling speed: 0.3 m / min) is set to a value within the range of 20 to 400 mN / 25 mm, and the laminate 100 is heated in an environment of 150 ° C. for 60 minutes and then in an environment of 25 ° C. The adhesive force P ₂ (peeling angle 180 °, peeling speed 0.3 m / min) of the protective film 20 to the transparent conductive film laminated film 10 when allowed to stand for 24 hours shall be a value within the range of 100 to 400 mN / 25 mm. It is a laminated body 100 characterized by the above.
The transparent conductive film laminating film 10 in FIGS. 1 (a) to 1 (b) has a hard coat layer 3 (3a, 3b) and an optical adjustment layer 2 (2a, 2b). It is not an essential configuration in the invention, and it suffices to have at least the transparent conductive film lamination film base material 4.
Hereinafter, embodiments of the present invention will be specifically described with reference to the drawings as appropriate.

1. 1. Adhesive strength (1) Adhesive strength when heated P ₁
As shown in FIG. 2, in the present invention, the adhesive force of the protective film to the transparent conductive film for laminating when the laminate is heated in an environment of 150 ° C. for 10 minutes P ₁ (peeling angle 180 °, peeling speed 0). .3 m / min) is set to a value in the range of 20 to 400 mN / 25 mm.
The reason for this is that when the adhesive force P ₁ during heating is less than 20 mN / 25 mm, the adhesive force of the protective film is excessively lowered during the sputtering treatment step, and the transparent conductive film lamination film This is because wrinkles and peeling may occur in the film, and it may be difficult to stably protect the surface of the transparent conductive film laminating film in a later step. On the other hand, if the adhesive force P ₁ during heating exceeds 400 mN / 25 mm, the adhesive force P ₂ after heating increases excessively, and when the protective film is finally peeled off after the annealing treatment. This is because the patterned transparent conductive film may be distorted.
Therefore, it is more preferable that the lower limit of the adhesive force P ₁ of the protective film to the transparent conductive film laminating film when the laminate is heated in an environment of 150 ° C. for 10 minutes is 50 mN / 25 mm or more, more preferably 100 mN /. It is more preferable to set the value to 25 mm or more.
Further, it is more preferable that the upper limit value of the adhesive force P ₁ of the protective film to the transparent conductive film lamination film when the laminate is heated in an environment of 150 ° C. for 10 minutes is 200 mN / 25 mm or less, more preferably 150 mN /. It is more preferable to set the value to 25 mm or less.
It was confirmed that when the laminate was heated in an environment of 150 ° C. for 10 minutes, the adhesive strength of the protective film was sufficiently reduced, and no significant change was observed even if the laminate was continuously heated. Has been done.
In addition, by measuring the adhesive strength under the condition that the heating time is longer than the sputtering treatment, the pressure-sensitive adhesive layer in a state slightly harsher than the sputtering treatment condition is used as a criterion, and the reproducibility of the effect is ensured. be able to.
Further, it is presumed that the decrease in the adhesive force during heating is caused by the decrease in the elastic modulus of the pressure-sensitive adhesive layer.

(2) Adhesive strength after heating P ₂
Further, as shown in FIG. 2, in the present invention, protection against the transparent conductive film for laminating when the laminate is heated in an environment of 150 ° C. for 60 minutes and then allowed to stand in an environment of 25 ° C. for 24 hours. The film's adhesive strength P ₂ (peeling angle 180 °, peeling speed 0.3 m / min) is set to a value within the range of 100 to 400 mN / 25 mm.
The reason for this is that if the adhesive force P ₂ after heating is less than 100 mN / 25 mm, the adhesive force P ₁ at the time of heating is excessively lowered, and after the sputtering treatment, the transparent conductive film for laminating film is wrinkled. This is because peeling may occur. On the other hand, if the adhesive force P ₂ after heating exceeds 400 mN / 25 mm, the patterned transparent conductive film may be distorted when the protective film is finally peeled off after the annealing treatment. Is.
Therefore, the lower limit of the adhesive strength P ₂ of the protective film to the transparent conductive film laminated film when the laminate is heated in an environment of 150 ° C. for 60 minutes and then allowed to stand in an environment of 25 ° C. for 24 hours is 150 mN /. A value of 25 mm or more is more preferable, and a value of 250 mN / 25 mm or more is further preferable.
Further, the upper limit of the adhesive strength P ₂ of the protective film to the transparent conductive film laminated film when the laminate is heated in an environment of 150 ° C. for 60 minutes and then allowed to stand in an environment of 25 ° C. for 24 hours is 350 mN /. The value is more preferably 25 mm or less, and further preferably 300 mN / 25 mm or less.
When the laminate was heated in an environment of 150 ° C. for 60 minutes and then allowed to stand in an environment of 25 ° C. for 24 hours, the adhesive strength of the protective film was sufficiently increased, and the layer was kept still. It has been confirmed that there is no significant change even if it is placed.
Further, it is presumed that the increase in the adhesive force after heating is caused by the improvement of the adhesive force at the interface between the pressure-sensitive adhesive and the base material by cooling from a high temperature to about room temperature.

(3) Relational expression Further, it is preferable that the adhesive strengths P ₁ and P ₂ described above satisfy the following relational expression (1).
P _2- P ₁ ≤ 300mN / 25mm (1)
The reason for this is that when the value of P _2- P ₁ exceeds 300 mN / 25 mm, the fluctuation of the adhesive force between heating and after heating becomes excessively large, and the protective film adheres during the sputtering treatment. This is because it may be difficult to stably achieve both the property and the peelability of the protective film when the protective film is finally peeled off after the annealing treatment. On the other hand, if the value of P _2- P ₁ becomes too small, manufacturing may become difficult.
Therefore, it is more preferable that the upper limit value of P _2- P ₁ is 250 mN / 25 mm or less, and further preferably 200 mN / 25 mm or less.
Further, the lower limit value of P _2- P ₁ is more preferably set to a value of 50 mN / 25 mm or more, and further preferably set to a value of 100 mN / 25 mm or more.

(4) Adhesive strength before heating P ₀
The adhesive force P ₀ (peeling angle 180 °, peeling speed 0.3 m / min) of the protective film to the transparent conductive film laminated film in the stage before heating the laminated body of the present invention is within the range of 100 to 250 mN / 25 mm. It is preferably a value.
The reason for this is that if the adhesive force P ₀ before heating is less than 100 mN / 25 mm, the adhesiveness to the transparent conductive film laminating film during roll feeding and transport becomes insufficient in the step before the sputtering treatment. This is because not only the adhesive force P ₁ at the time of heating tends to be excessively lowered, and the film for laminating the transparent conductive film may be wrinkled or peeled off by the sputtering treatment accompanied by the transfer. On the other hand, when the adhesive force P ₀ before heating exceeds 250 mN / 25 mm, the adhesive force P ₂ after heating tends to increase excessively, and the protective film is finally peeled off after the annealing treatment. This is because the patterned transparent conductive film may be distorted at that time.
Therefore, it is more preferable that the lower limit of the adhesive force P ₀ of the protective film to the transparent conductive film laminated film before heating the laminated body is 130 mN / 25 mm or more, and 150 mN / 25 mm or more. Is even more preferable.
Further, it is more preferable that the upper limit value of the adhesive force P ₀ of the protective film to the transparent conductive film laminating film before heating the laminated body is 230 mN / 25 mm or less, and 220 mN / 25 mm or less. Is even more preferable.

2. 2. Film for laminating transparent conductive film (1) Film substrate for laminating transparent conductive film (1) -1 type The type of film substrate for laminating transparent conductive film is not particularly limited and is known as an optical substrate. Base film can be used.
For example, polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate (PEN), polyethylene films, polypropylene films, cellophane, diacetyl cellulose films, triacetyl cellulose films, acetyl cellulose butyrate films, and polyvinyl chloride films. , Polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, polyether sulfone film, polyetherimide film, polyimide Plastic films such as films, fluororesin films, polyamide films, acrylic resin films, norbornene-based resin films, and cycloolefin resin films can be preferably mentioned.

Further, among these, from the viewpoint of heat resistance, a polyester film, a polycarbonate film, a polyimide film, a norbornene-based resin film, and a cycloolefin resin film are more preferable.
Further, from the viewpoint of achieving both transparency, film strength and flexibility, a PET film is particularly preferable.

(1) -2 Thickness Further, it is preferable that the thickness of the transparent conductive film laminating film base material is in the range of 20 to 200 μm.
The reason for this is that when the thickness of the transparent conductive film laminating film base material is less than 20 μm, the strength of the transparent conductive film laminating film base material decreases, so that the transparent conductive film on the surface of the optical adjustment layer described later This is because distortion may easily occur in the existing portion and the non-existing portion during the annealing treatment. On the other hand, if the thickness of the transparent conductive film lamination film base material exceeds 200 μm, the optical characteristics such as the image sharpness of the obtained transparent conductive film may deteriorate.
Therefore, the thickness of the transparent conductive film laminating film base material is more preferably set to a value in the range of 30 to 100 μm, and further preferably set to a value in the range of 40 to 80 μm.

(2) Hard Coat Layer As shown in FIG. 1A, when the transparent conductive film lamination film 10 in the present embodiment is formed, at least the side to which the protective film 20 of the transparent conductive film lamination film 10 is bonded is attached. That is, it is preferable to provide the hard coat layer 3a on the side opposite to the side on which the transparent conductive film 1 shown in FIG. 1B is laminated.
The reason for this is that by providing the hard coat layer in this way, the durability and dimensional stability of the transparent conductive film laminating film can be improved, and the adhesion of the protective film during the sputtering treatment and the annealing treatment can be performed. This is because it is possible to more stably achieve both the peelability of the protective film when the protective film is finally peeled off.

Further, as shown in FIG. 1A, when the hardcoat layer 3a is the first hardcoat layer 3a, the transparent conductive film 1 shown in FIG. 1B in the transparent conductive film lamination film base material 4 It is preferable to have a second hard coat layer 3b on the side on which the two are laminated.
The reason for this is that by having such a second hard coat layer, it is possible not only to suppress the migration of the oligomer component bleeding from the transparent conductive film laminating film base material to the transparent conductive film side, but also to prevent the transparent conductive film from bleeding. This is because the generation of curl in the film for laminating the film can be effectively suppressed.
Further, it is preferable that the second hard coat layer is made of the same material as the first hard coat layer and has the same thickness as the first hard coat layer.
The reason for this is that by constructing the second hard coat layer in this way, the formation of the first and second hard coat layers becomes easy, and in the transparent conductive film laminated film when the annealing treatment is performed. This is because the occurrence of curl can be suppressed more effectively.
Therefore, the following description is common to both the first hard coat layer and the second hard coat layer.

(2) -1 Material substance The material substance of the hard coat layer in the present embodiment is not particularly limited, but a composition for forming a hard coat layer containing the following components (A) to (B) as the material substance is used. It is preferably photocured.
(A) 100 parts by weight of active energy ray-curable resin (B) 5 to 30 parts by weight of silica fine particles The reason is that the composition for forming a hard coat layer used when forming a hard coat layer is an active energy ray-curable resin. On the other hand, by containing silica fine particles in a relatively small range, it is effective that the silica fine particles in the hard coat layer are melted or fall off even when an etching treatment including a severe alkali treatment is performed. This is because it can be suppressed.
Further, by controlling the surface characteristics of the hard coat layer within a suitable range, the adhesion of the protective film during the sputtering treatment and the peelability of the protective film when the protective film is finally peeled off after the annealing treatment are determined. This is because it is possible to achieve both in a more stable manner.

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

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, neopentyl glycol di (meth) acrylate of hydroxypivalate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified di (meth) acrylate Meta) acrylate, allylated cyclohexyldi (meth) acrylate, isocyanurate di (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropanthry (meth) ) Polyfunctional acrylates such as acrylate, tris (acryloxyethyl) isocyanurate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Be done.
In addition, these photopolymerizable monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

(Ii) Component (B): Silica fine particles The component (B) is silica fine particles.
The type of the silica fine particles is not particularly limited, but it is preferable to use solid silica fine particles.
The reason for this is that the solid silica fine particles can improve the hard coat property while minimizing the influence on the optical performance.

Further, it is preferable that the silica fine particles are reactive silica fine particles.
The reason for this is that reactive silica fine particles have excellent compatibility with the above-mentioned active energy ray-curable resin and form chemical bonds with the resin, so that the silica fine particles are firmly fixed to the hard coat layer. can do. This is because, in addition to the above-mentioned hard coat property, the etching resistance can be improved more effectively.
The "reactive silica fine particles" are silica fine particles to which an organic compound containing a polymerizable unsaturated group is bonded, and the silanol groups on the surface of the silica fine particles have a functional group capable of reacting with the silanol groups. It can be obtained by reacting a saturated group-containing organic compound.
Further, examples of the above-mentioned polymerizable unsaturated group include a radically polymerizable acryloyl group and a methacryloyl group.

Further, it is preferable that the volume average particle diameter (D50) of the silica fine particles is set to a value in the range of 10 to 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 such a range, a predetermined hard coat property can be obtained without lowering the transparency in the hard coat layer. ..

Further, it is preferable that the blending amount of the silica fine particles is in the range of 5 to 30 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin as the component (A).
The reason for this is that if the blending amount of the silica fine particles is less than 5 parts by weight, the hardness of the hard coat layer may be insufficient. On the other hand, when the blending amount of the silica fine particles exceeds 30 parts by weight, the silica fine particles in the hard coat layer may easily melt or fall off when an etching treatment including a harsh alkali treatment is performed. Because there is.

(Iii) Component (C): Fluorine-based leveling agent Further, it is preferable that the component (C) further contains a fluorine-based leveling agent.
The reason for this is that the etching resistance can be effectively improved by containing the fluorine-based leveling agent.
Further, by controlling the surface characteristics of the hard coat layer within a suitable range, the adhesion of the protective film during the sputtering treatment and the peelability of the protective film when the protective film is finally peeled off after the annealing treatment are determined. This is because it is possible to achieve both in a more stable manner.
As the type of the fluorine-based leveling agent, conventionally known ones can be used.
For example, Futergent 7602A manufactured by Neos Co., Ltd. can be mentioned.

Further, from the viewpoint of improving the etching resistance while keeping the surface free energy of the hard coat layer within a predetermined range, the blending amount of the fluorine-based leveling agent is 100 parts by weight of the active energy ray-curable resin as the component (A). The value is preferably in the range of 0.01 to 0.2 parts by weight.

Component (iv) (D): Photopolymerization initiator Further, since the active energy ray-curable resin can be efficiently cured by active energy rays, particularly ultraviolet rays, a photopolymerization initiator as the component (D) is optionally used in combination. It is also preferable.
Examples of such photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, and 2,2-dimethoxy-2-phenylacetophenone. , 2,2-Diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-Propyl-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2 -Methylanthraquinone, 2-ethylanthraquinone, 2-tershaly butyl anthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, Examples thereof include benzyl dimethyl ketal, acetphenone dimethyl ketal, p-dimethylamine benzoic acid ester and the like.
In addition, these may be used individually by 1 type, and may be used in combination of 2 or more types.
The amount of the photopolymerization initiator blended is preferably in 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. , It is more preferable that the value is in the range of 1 to 5 parts by weight.

(2) -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 and drying it as described later, and curing it.
In the composition, if necessary, an active energy ray-curable resin, a photopolymerization initiator, silica fine particles, and various additive components used as desired are added in a suitable solvent at a predetermined ratio to dissolve or disperse them. Can be prepared by
Examples of various additive components include antioxidants, ultraviolet absorbers, (near) infrared absorbers, silane coupling agents, light stabilizers, leveling agents, antistatic agents, defoaming agents, and the like.

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 cellosolve solvents such as ethyl cellosolve.
The concentration and viscosity of the composition for forming a hard coat layer prepared in this manner are not particularly limited as long as they can be coated, and can be appropriately selected depending on the situation.

(2) -3 Thickness The thickness of the hard coat layer is preferably 0.5 μm or more from the viewpoint of making the etching resistance and the heat resistance more excellent. Further, from the viewpoint of increasing the efficiency of sputtering treatment by lowering the outgas during heating, it is preferable to set the value to 5 μm or less.
Therefore, the lower limit of the thickness of the hard coat layer is more preferably 0.8 μm or more, and further preferably 1 μm or more.
Further, the upper limit of the thickness of the hard coat layer is more preferably set to a value of 4 μm or less, and further preferably set to a value of 3 μm or less.

(3) Optical Adjustment Layer As shown in FIG. 1 (a), in constructing the transparent conductive film laminating film 10 in the present embodiment, optical is applied to the side on which the transparent conductive film 1 shown in FIG. 1 (b) is laminated. It is preferable to provide the adjusting layer 2.
More specifically, the high refractive index layer 2b having a relatively high refractive index and the low refractive index layer 2a having a relatively low refractive index are laminated in this order from the side of the transparent conductive film lamination film base material 4. It is preferable to do so.
The reason for this is that by forming the optical adjustment layer in such a laminated structure, the pattern shape of the transparent conductive film is caused by the difference between the refractive index of the transparent conductive film and the refractive index of the film substrate for laminating the transparent conductive film. This is because it is possible to effectively suppress that the image is easily visible.

(3) -1 High-refractive index layer (i) Refractive index The refractive index of the high-refractive index layer is preferably 1.6 or more.
The reason for this is that if the refractive index of the high refractive index layer is less than 1.6, a significant difference in refractive index from the low refractive index layer cannot be obtained, and the pattern shape of the transparent conductive film may be easily visible. 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 brittle.
Therefore, the refractive index of the high refractive index layer is more preferably set to a value in the range of 1.61 to 2, and further preferably set to a value in the range of 1.63 to 1.8.

(Ii) Material Material Further, it is preferable that the high refractive index layer is made of a cured product of a composition containing metal oxide fine particles and an active energy ray-curable resin.
The reason for this is that the inclusion of the metal oxide fine particles and the active energy ray-curable resin facilitates the adjustment of the refractive index in the high refractive index layer.

The types of metal oxides are preferably tantalum oxide, zinc oxide, indium oxide, hafnium oxide, cerium oxide, tin oxide, niobium oxide, indium tin oxide (ITO), antimony tin oxide (ATO) and the like. ..
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 a value within the range of 0.005 to 1 μm.
The volume average particle diameter (D50) of the metal oxide fine particles can be determined by using, for example, a laser diffraction / scattering type particle size distribution measuring device.
Further, 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.
The amount of the metal oxide fine particles to be blended is preferably 20 to 2000 parts by weight, more preferably 80 to 1000 parts by weight, and 150 to 1000 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin. It is more preferably 400 parts by weight.

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

(Iv) Thickness Further, it is preferable that the thickness of the high refractive index layer is 20 to 130 nm.

(3) -2 Low refractive index layer (i) Refractive index The refractive index of the low refractive index layer is preferably 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 difference in refractive index from the high refractive index layer cannot be obtained, and the pattern shape of the transparent conductive film becomes easily visible. Because there is. On the other hand, if the refractive index of the low refractive index layer becomes an excessively small value, 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 in the range of 1.3 to 1.44, and further preferably set to a value in the range of 1.35 to 1.43.

(Ii) Material Material It is preferable that the low refractive index layer is formed by photocuring a composition for forming a low refractive index layer containing the following components (a) to (b).
(A) 100 parts by weight of active energy ray-curable resin (b) 2 to 120 parts by weight of silica fine particles The reason is that the composition for forming a low refractive index layer used for forming a low refractive index layer is activated energy ray curable. By containing silica fine particles in a relatively small range with respect to the sex resin, the silica fine particles in the low refractive index layer may be melted or fall off even when an etching treatment including a harsh alkaline treatment is performed. This is because can be effectively suppressed.
Further, the active energy ray-curable resin can form a matrix portion in the low refractive index layer by curing, more effectively protect the silica fine particles in the low refractive index layer, and further effectively improve the etching resistance. it can.
Hereinafter, each component will be described.

(Ii) -1 (a) component: 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 appropriately used.

Further, it is preferable that the active energy ray-curable resin contains a water-repellent resin.
The reason for this is that by containing the water-repellent resin, 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.
Further, the water-repellent resin is not particularly limited as long as it is a water-repellent resin, and a conventionally known water-repellent resin can be used.
More specifically, if the surface free energy of the resin film formed of the water-repellent resin alone is in the range of 10 to 30 mJ / m ² , it can be suitably used as the water-repellent resin in the present invention.

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

Further, from the viewpoint of obtaining the surface free energy described above while improving the etching resistance, the content of the water-repellent resin is 50 to 90% by weight when the entire component (a) is 100% by weight. It is preferable that the value is within the range.

(Ii) -2 (b) component: silica fine particles The type of the silica fine particles is not particularly limited, but it is preferable to use hollow silica fine particles from the viewpoint of further lowering the refractive index.
The "hollow silica fine particles" mean silica fine particles having cavities inside the particles.

Further, it is preferable that the silica fine particles are reactive silica fine particles.
The reason for this is that if the reactive silica fine particles are used, the silica fine particles can be firmly fixed 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 an organic compound containing a polymerizable unsaturated group is bonded, and have a functional group capable of reacting the silanol group on the surface of the silica fine particles. It can be obtained by reacting a saturated group-containing organic compound.
Further, examples of the above-mentioned polymerizable unsaturated group include a radically polymerizable acryloyl group and a methacryloyl group.

Further, it is preferable that the volume average particle diameter (D50) of the silica fine particles is set to a value in the range of 20 to 70 nm.
The reason for this is that by setting the volume average particle diameter (D50) of the silica fine particles to a value within such a range, a predetermined refractive index can be obtained without lowering the transparency in the low refractive index layer. ..
The volume average particle diameter (D50) of the silica fine particles can be determined by using, for example, a laser diffraction / scattering type particle size distribution measuring device.

Further, from the viewpoint of etching resistance and refractive index adjustment, the blending amount of the 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 as the component (a). It is preferable to do so.

(Iii) Composition for forming a low refractive index layer The low refractive index layer is formed by preparing a composition for forming a low refractive index layer in advance, applying, drying, and curing as described later.
If necessary, the composition comprises the above-mentioned active energy ray-curable resin as the component (a), silica fine particles as the component (b), a photopolymerization initiator and other various additive components in an appropriate solvent. Can be prepared by adding each of them in a predetermined ratio and dissolving or dispersing them.
The various additive components, the solvent, the concentration, the viscosity, etc. of the composition for forming the low refractive index layer are the same as those in the description of the hard coat layer.

(Iv) Thickness Further, it is preferable that the thickness of the low refractive index layer is set to a value in the range of 20 to 150 nm.
The reason for this is that by setting the thickness of the low refractive index layer to a value within such a range, the pattern shape of the transparent conductive film can be made invisible more stably, and at the same time, sufficient etching resistance can be obtained. Because it can be done.

(4) Surface free energy Further, it is preferable that the surface free energy of the surface of the transparent conductive film laminating film on the side to which the protective film is bonded is set to a value in the range of 30 to 60 mJ / m ² .
The reason for this is that when the surface free energy is less than 30 mJ / m ² , the adhesive force P ₁ at the time of heating is excessively lowered, and the transparent conductive film lamination film is wrinkled or peeled by the sputtering treatment. Because there is. On the other hand, when the surface free energy exceeds 60 mJ / m ² , the adhesive force P ₂ after heating tends to increase excessively, and when the protective film is finally peeled off after the annealing treatment, This is because the patterned transparent conductive film may be distorted.
Therefore, it is more preferable that the lower limit of the surface free energy of the surface of the transparent conductive film laminated film on the side to which the protective film is bonded is 35 mJ / m ² or more, and 40 mJ / m ² or more. It is more preferable to do so.
The upper limit of the surface free energy of the surface of the protective side which the film is stuck in the transparent conductive film laminated film, more preferably, to 55 mJ / m ² or less of the value, and 50 mJ / m ² or less of the value It is more preferable to do so.
The above-mentioned surface free energy means the surface free energy of the hard coat layer surface when the hard coat layer is provided, and when the hard coat layer is not provided, the surface of the transparent conductive film lamination film base material. Means the surface free energy of.

(5) Method for Producing Transparent Conductive Laminating Film The transparent conductive film for laminating in the present embodiment can be obtained, for example, by a manufacturing method including the following steps (a) to (b).
(A) Step of forming a hard coat layer on both sides of a transparent conductive film laminating film base material (b) Step of forming an optical adjustment layer on one of the hard coat layers

(5) -1 Step (a): Step of forming a hard coat layer The above-mentioned composition for forming a hard coat layer is applied to both surfaces of a transparent conductive film laminating film by a conventionally known method to form a coating film. After that, it is dried, and the coating film is cured by irradiating it with active energy rays to form a hard coat layer.
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 a drying condition, it is preferable to carry out at 60 to 150 ° C. for about 10 seconds to 10 minutes.
Further, examples of the active energy ray include ultraviolet rays and electron beams.
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, and the irradiation amount thereof is usually preferably 100 to 500 mJ / cm ² .
On the other hand, examples of the light source of the electron beam include an electron beam accelerator, and the irradiation amount thereof is usually preferably 150 to 350 kV.
Further, when irradiating the active energy rays, it is more preferable to perform the irradiation in a nitrogen atmosphere.
The reason for this is that by performing the process in a nitrogen atmosphere, the curing reaction on the surface of the hard coat layer proceeds effectively, and the etching resistance of the hard coat layer can be further effectively improved.

(5) -2 Step (b): Step of forming the optical adjustment layer Next, on the formed hard coat layer (when the hard coat layer is not formed, directly on the transparent conductive film lamination film base material), A high refractive index layer is formed.
That is, in the high refractive index layer, the above-mentioned composition for forming the high refractive index layer is applied and dried in the same manner as the hard coat layer is formed on the transparent conductive film laminating film base material, and the active energy ray is applied. It can be formed by irradiating and curing.
Next, a low refractive index layer is further formed on the formed high refractive index layer.
That is, in the low refractive index layer, the above-mentioned composition for forming the low refractive index layer is applied and dried in the same manner as the hard coat layer is formed on the transparent conductive film laminating film base material, and the active energy ray is applied. It can be formed by irradiating and curing.
Further, when irradiating the active energy rays, it is more preferable to perform the irradiation in a nitrogen atmosphere.
The reason for this is that by performing in a nitrogen atmosphere, the curing reaction on the surface of the optical adjustment layer proceeds effectively, and the etching resistance of the optical adjustment layer, particularly the low refractive index layer, which is the outermost surface layer, is further effectively improved. This is because it can be made to.

3. 3. Protective film (1) Protective film base material (1) -1 type The type of protective film base material is not particularly limited, and is, for example, a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate, or polypropylene. Polyolefin-based resin, paper, etc. can be used.
Among these, polyester-based resins and polyolefin-based resins are more preferable.

(1) -2 Thickness The thickness of the protective film base material is preferably set to a value within the range of 23 to 250 μm.
The reason for this is that if the thickness of the protective film base material is less than 23 μm, the effect of holding the thin transparent conductive film laminated film during the sputtering treatment may be insufficient. Further, since the base material is not stiff, it may be difficult to finally peel off after the annealing treatment. On the other hand, when the thickness of the protective film base material exceeds 250 μm, the followability of the protective film base material to the adherend is lowered, and the transparent conductive film corresponding to the portion where the protective film base material cannot follow. Wrinkles and peeling may occur from the part of the laminating film.
Therefore, the lower limit of the thickness of the protective film base material is more preferably set to a value of 50 μm or more, and further preferably set to a value of 100 μm or more.
Further, the upper limit of the thickness of the protective film base material is more preferably set to a value of 188 μm or less, and further preferably set to a value of 135 μm or less.

(2) Adhesive layer (2) -1 Material substance The adhesive used for the adhesive layer is not particularly limited, and conventionally known adhesives can be used.
For example, acrylic adhesives, silicone adhesives, urethane adhesives, ester adhesives, olefin adhesives and the like are preferably mentioned. Among them, from the adjustment easily viewpoint such that the adhesive satisfying the above adhesive strength P ₁ and P _2, acrylic adhesive, or, more preferably silicone adhesive.

The acrylic pressure-sensitive adhesive preferably contains a (meth) acrylic acid ester copolymer having a weight average molecular weight of 300,000 to 2.5 million as a main component. As the monomer constituting such a copolymer, a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms can be preferably mentioned. As the (meth) acrylic acid alkyl ester, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like can be preferably mentioned. These can be used alone or in combination.

Further, the above-mentioned copolymer preferably contains a functional group-containing monomer as a monomer constituting the copolymer. When the above-mentioned copolymer contains a functional group-containing monomer as a constituent component, the above-mentioned copolymers can form a three-dimensional network structure with each other via a cross-linking agent described later. This makes it possible to obtain a pressure-sensitive adhesive more readily to satisfy the adhesion P ₁ and P ₂ described above.
Examples of the functional group-containing monomer include monomers containing a carboxyl group, a hydroxyl group, an epoxy group, an amino acid, and the like. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, fumaric acid, maleic acid, and itaconic acid. Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (meth). Preferred examples of the monomer containing an epoxy group such as hydroxyhexyl acrylate and N-methylol (meth) acrylamide include glycidyl (meth) acrylate. These can be used alone or in combination.

The ratio of the above-mentioned constituent monomers in the (meth) acrylic acid ester copolymer is not particularly limited, but the above-mentioned functional group-containing monomer is added to 100 parts by weight of the above-mentioned (meth) acrylic acid alkyl ester. It is preferably contained in an amount of 1 to 15 parts by weight, more preferably 1 to 10 parts by weight. Incidentally, the monomers constituting the (meth) acrylic acid ester copolymer is not limited to the aforementioned monomers, it may be used as appropriate within a range that satisfies the adhesive force P ₁ and P _2.

Preferred examples of the cross-linking agent include an epoxy-based cross-linking agent, an isocyanate-based cross-linking agent, an imine-based cross-linking agent, and a metal chelate-based cross-linking agent. Of these, an epoxy-based cross-linking agent or an isocyanate-based cross-linking agent is preferable. The mixing ratio of the cross-linking agent to the (meth) acrylic acid ester copolymer is not particularly limited, but usually, the cross-linking agent (solid content) is 0.01 to 10 with respect to 100 parts by weight of the above-mentioned copolymer (solid content). About a part by weight is preferable. In order to carry out high-density cross-linking, it is preferable that the mixing ratio of the cross-linking agent is 3 parts by weight or more.

Further, as the above-mentioned pressure-sensitive adhesive, a tackifier, a plasticizer, a filler, an antioxidant, an ultraviolet absorber, a photocuring agent, a silane coupling agent and the like can be appropriately used as needed. The pressure-sensitive adhesive having an adhesive force P ₁ and P _2, one skilled in the art, fine adjustment proportion of monomers constituting the copolymer described above and, and amount of the crosslinking agent, and adhesive layer thickness below It can be easily obtained by doing so.

Further, as the silicone-based pressure-sensitive adhesive, for example, organopolysiloxane and / or a derivative thereof can be contained as a main component.
In particular, the main component may contain a silicone compound containing an additive organopolysiloxane composed of an organopolysiloxane having an alkenyl group and an organopolysiloxane having a siloxane bond as a main skeleton and an organohydrogenpolysiloxane, and a platinum catalyst as constituent components. preferable.

The organopolysiloxane having this siloxane bond as the main skeleton and having an alkenyl group is specifically a compound represented by the following formula (1) and having at least two alkenyl groups in the molecule. Is preferable.
R1 _a SiO _{(4-a) / 2} (1)
(In the formula (1), R1 is an unsubstituted or substituted monovalent hydrocarbon group having the same or different carbon atoms of 1 to 12, preferably 1 to 8, and a is 1.5 to 2.8, preferably 1.5 to 2.8. Is a positive number in the range of 1.8 to 2.5, more preferably 1.95 to 2.05.)

Examples of the unsubstituted or substituted monovalent hydrocarbon group bonded to the silicon atom represented by R1 described above include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group and a cyclohexenyl group. Alkenyl group such as octenyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group. Alkyl group such as alkyl group, phenyl group, trill group, xylyl group, naphthyl group and other aryl group, benzyl group, phenylethyl group, phenylpropyl group and other aralkyl groups, and some or all of the hydrogen atoms of these groups are fluorine. , Bromine, chlorine and other halogen atoms, those substituted with a cyano group and the like, for example, a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group, a cyanoethyl group and the like.

Further, as the alkenyl group in the organopolysiloxane, if it is a vinyl group, the curing time is short and it is preferable from the viewpoint of productivity.
The organohydrogenpolysiloxane has a SiH group in the molecule and can be cured by an addition reaction with the alkenyl group of the organopolysiloxane having a siloxane bond as a main skeleton and an alkenyl group.

Examples of the platinum catalyst for curing the silicone pressure-sensitive adhesive include platinum black, second platinum chloride, platinum chloride acid, a reaction product of platinum chloride acid and monovalent alcohol, a complex of platinum chloride acid and olephens, and platinum. Bisacetoacetate and the like can be exemplified.
The amount of the platinum catalyst used is preferably in the range of 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the additive organopolysiloxane.

Further, in the addition type organopolysiloxane of the main component, in order to further enhance the adhesive strength, various silicone resins used for silicone-based pressure-sensitive adhesives, that is, trifunctional or tetrafunctional siloxane units are contained in the molecule. It is also preferable to blend the containing polyorganosiloxane.
When such polyorganosiloxane is blended, the blending amount is preferably 50 parts by weight or less with respect to 100 parts by weight of the addition type organopolysiloxane.
A person skilled in the art can easily adjust the adhesive strengths P ₁ and P ₂ described above by finely adjusting the blending amount of each component and the thickness of the pressure-sensitive adhesive described above.

(2) -2 Thickness The thickness of the pressure-sensitive adhesive layer is preferably set to a value within the range of 2 to 100 μm.
The reason for this is that if the thickness of the pressure-sensitive adhesive layer is less than 2 μm, the adhesive strength may be insufficient. On the other hand, if the thickness of the pressure-sensitive adhesive layer exceeds 100 μm, the outgas of the pressure-sensitive adhesive layer may become a problem.
Therefore, the lower limit of the thickness of the pressure-sensitive adhesive layer is more preferably 5 μm or more, and further preferably 10 μm or more.
Further, the upper limit of the thickness of the pressure-sensitive adhesive layer is more preferably set to a value of 50 μm or less, and further preferably set to a value of 30 μm or less.

(3) Method for Producing Protective Film The protective film can be obtained by applying an adhesive composition to a protective film base material and curing it with heat or light to form an adhesive layer by a conventionally known method. Can be done.
For example, a coating liquid is prepared by mixing the above-mentioned pressure-sensitive adhesive components while diluting them with a solvent such as toluene or ethyl acetate.
The coating liquid is applied to one surface of the protective film using a coating device such as a comma coater, a knife coater, an applicator, and a roll coater.
Then, heat drying is performed at 80 to 160 ° C. for about 30 seconds to 10 minutes. When a photo-curing agent is added to the pressure-sensitive adhesive, the active energy rays of the amount of light required for curing are irradiated before or after the above-mentioned drying. Then, if necessary, a curing period of about several days to two weeks is provided at about room temperature.
Thereby, a protective film having a predetermined pressure-sensitive adhesive layer on the protective film base material can be obtained.
Further, the laminate of the present invention can be obtained by laminating the obtained protective film on the side of the transparent conductive film for laminating film opposite to the side on which the transparent conductive film is laminated by a conventionally known method. Can be done.

4. Laminated body provided with a transparent conductive film In another embodiment of the present invention, as shown in FIG. 1 (b), the transparent conductive film 1 is laminated on one surface of the transparent conductive film laminating film 10, and the transparent conductive film 1 is laminated. The laminated body 100'in which the protective film 20 is attached to the other surface of the film laminating film 10.
Hereinafter, the present embodiment will be described in detail only in different parts, omitting parts that overlap with the contents so far.

(1) Transparent Conductive Material (1) -1 Material Material The material material of the transparent conductive film is not particularly limited as long as it has both transparency and conductivity, but for example, indium oxide and zinc oxide. , Tin oxide, indium tin oxide (ITO), tin antimony oxide, zinc aluminum oxide, indium zinc oxide and the like.
Further, it is particularly preferable to use ITO as a material material.
The reason for this is that with ITO, a transparent conductive film having excellent transparency and conductivity can be formed by adopting appropriate film forming conditions.

(1) -2 Pattern shape The transparent conductive film may be uniformly formed on the entire surface or may be partially formed, regardless of the type. Above all, the transparent conductive film is preferably formed in a pattern shape such as a mesh shape, a line shape, or a lattice shape.
Further, in the above-mentioned pattern shape, it is preferable that the line width of the portion where the transparent conductive film is present and the line width of the portion where the transparent conductive film is not present are substantially equal.
Further, the line width is usually 0.1 to 10 mm, preferably 0.2 to 5 mm, and particularly preferably 0.5 to 2 mm.
The line width in the line shape or the grid shape described above is not limited to a constant case, and for example, a touch panel having a shape required for a capacitance type touch panel can be freely selected.
Specific examples thereof include a pattern shape in which a rhombus portion and a line portion are repeatedly connected, and such a pattern shape is also included in the category of "line shape".

(1) -3 Thickness The thickness of the transparent conductive film is preferably 5 to 500 nm.
The reason for this is that if the thickness of the transparent conductive film is less than 5 nm, not only the transparent conductive film becomes brittle, but also sufficient conductivity may not be obtained. On the other hand, when the thickness of the transparent conductive film exceeds 500 nm, the color tint due to the transparent conductive film becomes strong, and the pattern shape may be easily recognized.
Therefore, the thickness of the transparent conductive film is more preferably 15 to 250 nm, further preferably 20 to 100 nm.

(2) Method for Forming Transparent Conductive Film (2) -1 Lamination of Transparent Conductive Film The protective film 20 of the transparent conductive film lamination film 10 is attached to the laminate 100 composed of the transparent conductive film lamination film 10 and the protective film 20. The transparent conductive film 1 can be laminated on the surface opposite to the one formed by a known method such as a vacuum deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, or a sol-gel method. it can.
Above all, in the laminate 100 composed of the transparent conductive film laminating film 10 and the protective film 20 of the first embodiment described above, it is particularly preferable to laminate the transparent conductive film 1 by a roll-to-roll method by a sputtering method due to its characteristics. preferable.
In addition, examples of the sputtering method include a normal sputtering method using a compound, a reactive sputtering method using a metal target, and the like.
At this time, it is also preferable to introduce oxygen, nitrogen, water vapor or the like as the reactive gas, or to add ozone, ion assist or the like in combination.

(2) -2 Storage after laminating the transparent conductive film As described above, it is preferable to perform the transparent conductive film laminating step (preferably the sputtering treatment step) by roll-to-roll from the viewpoint of productivity. However, since the annealing treatment in the next step has a long heating time, it is preferable to perform the annealing treatment for each lot from the viewpoint of equipment. The order of the annealing process and the patterning process described later can be changed as needed. However, even if the patterning process comes first, it is preferable to process each lot.
For this reason, it is preferable that the laminate composed of the transparent conductive film and the protective film is cut from a long sheet unwound from a roll into a short sheet of a predetermined size after sputtering treatment. It should be noted that the cut short sheets are usually stored by stacking predetermined quantities with each other until the next process.

(2) -3 Annealing Treatment It is preferable that the transparent conductive film obtained in the previous step is subjected to a predetermined annealing treatment by providing an annealing step in order to increase the crystallinity and reduce the resistivity.
That is, it is preferable that the obtained laminate composed of the transparent conductive film and the protective film is heated under a temperature condition of 130 to 180 ° C. for 0.5 to 2 hours.

(2) -4 Patterning treatment The transparent conductive film is formed by forming a film as described above, annealing treatment, forming a resist mask having a predetermined pattern by a photolithography method, and then etching treatment by a known method. , A line-shaped pattern or the like can be formed.
As the etching solution, an aqueous solution of an acid such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid is preferably used.
The liquid used for the alkali treatment for removing the residual photoresist, which is the final step of the etching treatment, has a liquid temperature of 10 to 50 ° C. and a concentration of 1 to 10% by weight from the viewpoint of speeding up the etching treatment. 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, and hydroxide. Examples thereof include barium, europium hydroxide (II), talium hydroxide (I), and guanidine.

(2) -5 Isolation of Transparent Conductive Film By going through each of the above steps, a laminate composed of a transparent conductive film and a protective film on which a patterned transparent conductive film is laminated can be obtained. By peeling the protective film from the obtained laminate, a thin transparent conductive film on which the patterned transparent conductive film is laminated can be isolated. According to the laminated body of the present embodiment, it is possible to obtain a transparent conductive film formed by laminating a patterned transparent conductive film which is thin and has no distortion or the like with a high probability.
In the above, the present invention has been described in detail in each embodiment so that the present invention can be understood, but the present invention is not limited thereto. In addition, examples are shown below and described in more detail, but similarly, the present invention is not limited thereto.

Hereinafter, the laminate and the like of the present invention will be described in more detail with reference to Examples.

[Example 1]
1. 1. Production of film for laminating transparent conductive film (1) Preparation of composition for forming hard coat layer In a container, an active energy ray-curable resin as a component (A), silica fine particles as a component (B), and (C). ) A leveling agent as a component and a photopolymerization initiator as a component (D) are contained in the following composition, and then a solvent is added and mixed uniformly to form a hard coat layer having a solid content concentration of 16% by weight. The composition was prepared.
The blending amounts in the following composition and the composition shown in Table 1 represent the pure content excluding the diluting solvent.
Component (A): Dipentaerythritol hexaacrylate 100 parts by weight (B) Component: Reactive solid silica fine particles 20 parts by weight (volume average particle diameter (D50) 15 nm)
Ingredient (C): Fluorine-based leveling agent 0.05 parts by weight (manufactured by Neos Co., Ltd., Footgent 7602A)
Ingredient (D): Photopolymerization initiator 3 parts by weight (BASF Japan Ltd., Irgacure 184)
The volume average particle diameter (D50) of the component (B) described above was measured by a laser diffraction / scattering type particle size distribution measuring device.
Further, in the following, the photoinitiator as the component (D) described above may be referred to as "Irgacure 184".

(2) Preparation of composition for forming a high refractive index layer 100 parts by weight (pure excluding diluent) of ultraviolet curable resin (Seikabeam EXF-01L (NS) manufactured by Dainichi Seika Kogyo Co., Ltd.) is placed in a container. (The same applies hereinafter), 200 parts by weight of a zirconium oxide dispersion (manufactured by CIK Nanotech Co., Ltd., ZRMIBK15WT% -F85), and an acrylic leveling agent (manufactured by Big Chemie Japan Co., Ltd., BYK-355). , And 3 parts by weight of a photopolymerization initiator (Irgacure 907, manufactured by BASF Japan Co., Ltd.), and then a solvent was added to mix them uniformly to obtain a solid content concentration of 1% by weight. A composition for forming a high refractive index layer was prepared.

(3) Preparation of composition for forming a low refractive index layer In a container, an active energy ray-curable resin containing a water-repellent resin as a component (a), silica fine particles as a component (b), and (c). A leveling agent as a component and a photopolymerization initiator as a component (d) are contained in the following composition, and then a solvent is added and mixed uniformly to form a low refractive index layer having a solid content concentration of 1% by weight. The composition was prepared.
The blending amount in the composition shown below represents the pure content excluding the diluting solvent.
(A) Component: Ultraviolet curable acrylic resin containing fluororesin
100 parts by weight (type of fluororesin: reactive fluoroacrylic resin, content of fluororesin: 80% by weight, surface free energy of cured resin coating film of fluororesin alone: 25 mN / m)
(B) Component: 100 parts by weight of reactive hollow silica fine particles (volume average particle diameter (D50) 45 nm)
(C) Ingredient: Acrylic leveling agent 0.05 parts by weight (manufactured by Big Chemie Japan Co., Ltd., BYK-355)
(D) Ingredient: 5 parts by weight of photopolymerization initiator (BASF Japan Ltd., Irgacure 184)
The volume average particle diameter (D50) of the component (b) described above was measured by a laser diffraction / scattering type particle size distribution measuring device.

(4) Formation of hard coat layer As a film base material for laminating a transparent conductive film, a polyester film with an easy-adhesion layer having a thickness of 50 μm, a heat shrinkage rate of 0.7% in the MD direction, and a heat shrinkage rate of 0.4 in the TD direction (Toray). A roll (long sheet) of UH33 manufactured by Co., Ltd. was prepared.
Next, the composition for forming a hard coat layer was applied to the surface of the prepared film base material for laminating a transparent conductive film with a gravure coater.
Then, after drying at 70 ° C. for 1 minute, ultraviolet rays are irradiated under the following conditions using an ultraviolet irradiation device (manufactured by GS Yuasa Corporation) in a nitrogen atmosphere, and the surface of the transparent conductive film lamination film base material is irradiated. A hard coat layer having a thickness of 2 μm was formed on the surface.
In addition, a hard coat layer was similarly formed on the opposite surface of the transparent conductive film laminating film base material.
Light source: High-pressure mercury lamp Illuminance: 150 mW / cm ²
Light intensity: 150mJ / cm ²

Further, the surface free energy on the surface of the obtained hard coat layer was determined by the Kitazaki-Hata theory based on the contact angles (measurement temperature: 25 ° C.) of various droplets.
That is, using diiodomethane as a "dispersion component", 1-bromonaphthalene as a "dipole component", and distilled water as a "hydrogen bond component" as droplets, DM-70 manufactured by Kyowa Interface Science Co., Ltd. The contact angle (measurement temperature: 25 ° C.) was measured according to JIS R3257 by the static drip method, and the surface free energy (mJ / m ² ) was obtained by Kitazaki-Hata theory based on the value. ..
As a result, the surface free energy on the surface of the hard coat layer was 42 mJ / m ² .

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

(6) Formation of Low Refractive Index Layer Next, a composition for forming a low refractive index layer was applied on the formed high refractive index layer with a gravure coater.
Next, after drying at 50 ° C. for 1 minute, ultraviolet rays are irradiated under the same irradiation conditions as the hard coat layer using an ultraviolet irradiation device (manufactured by GSS Yoursa Corporation) in a nitrogen atmosphere, and the surface is on the high refractive index layer. A low refractive index layer having a thickness of 50 nm and a refractive index of n _D = 1.37 was formed on the surface, and a roll (long sheet) of a laminated body for forming a transparent conductive film as shown in FIG. 1 (a) was obtained.

2. 2. Manufacture of Protective Film As a protective film base material, a roll of PET film (Toray Industries, Inc., Lumirror U48) having a thickness of 125 μm, a heat shrinkage rate of 0.7% in the MD direction, and a heat shrinkage rate of 0.4% in the TD direction. A long sheet) was prepared.
Next, the following acrylic pressure-sensitive adhesive composition is applied to the surface of the prepared protective film base material, dried and seasoned, and a roll (long sheet) of the protective film having a pressure-sensitive adhesive layer having a thickness of 15 μm is applied. Obtained. The exposed surface side of the obtained adhesive layer was protected by attaching a release film (long sheet) until use.

<Acrylic adhesive composition>
By normal solution polymerization, a (meth) acrylic acid ester copolymer having a weight average molecular weight of 700,000 was obtained at 2-ethylhexyl acrylate / butyl acrylate / acrylic acid = 15/85/5 (weight ratio). An acrylic pressure-sensitive adhesive composition was obtained by adding 6 parts by weight of N, N, N', N'-tetraglycidyl-m-xylylenediamine as an epoxy-based cross-linking agent to 100 parts by weight of this copolymer. It was.

3. 3. Adhesion of Protective Film Next, the film is pulled out from the roll of the transparent conductive film laminated film, the film is pulled out from the roll of the protective film in the same manner, the release film is peeled off, and the hard coat layer in the transparent conductive film laminated film is protected. The pressure-sensitive adhesive layer of the film is bonded to each other using a laminator, and the transparent conductive film laminated film and the protective film bonded to the side of the transparent conductive film laminated film opposite to the side on which the transparent conductive film is laminated. , A roll (long sheet) of a laminated body was obtained.

4. Measurement of adhesive strength (1) Adhesive strength before heating P ₀
In the stage before heating the obtained laminate, the adhesive force when the protective film was peeled from the transparent conductive film laminate film was measured.
That is, a sample having a width of 50 mm and a length of 150 mm was cut out from the roll (long sheet) of the obtained laminate. The adhesive strength (mN / 25 mm) when the protective film was peeled from the transparent conductive film laminating film was measured under the conditions of a peeling angle of 180 ° and a peeling speed of 0.3 m / min in an environment of 25 ° C. The results obtained are shown in Table 1.

(2) Adhesive strength during heating P ₁
At the stage of heating the obtained laminate, the adhesive force when the protective film was peeled from the transparent conductive film laminate film was measured.
That is, the above-mentioned sample is heated in a furnace at 150 ° C. for 10 minutes, and the protective film is peeled off from the transparent conductive film laminating film under the conditions of a peeling angle of 180 ° and a peeling speed of 0.3 m / min under such a heating environment. The adhesive strength (mN / 25 mm) was measured. The results obtained are shown in Table 1.

(3) Adhesive strength after heating P ₂
In the stage after heating the obtained laminate, the adhesive force when peeling the protective film from the transparent conductive film laminate film was measured.
That is, the above-mentioned sample was allowed to stand in an environment of 25 ° C. for 24 hours, and then heated in a furnace at 150 ° C. for 60 minutes.
Then, after standing for 24 hours in an environment of 25 ° C., the adhesive force (mN / 25 mm) when the protective film is peeled off from the transparent conductive film laminating film under the conditions of a peeling speed of 180 ° and a peeling speed of 0.3 m / min. ) Was measured. The results obtained are shown in Table 1.

5. Evaluation (1) Appearance of Protective Film at the Time of Sputtering The appearance of the laminated body made of a transparent conductive film / protective film when a transparent conductive film was formed on the obtained laminate by sputtering was evaluated.
That is, the obtained laminated roll (long sheet) is sputtered (temperature 150) using an ITO target (tin oxide 10% by weight, indium oxide 90% by weight) by operating a roll-to-roll sputtering processing apparatus. A transparent conductive film having a thickness of 30 nm was formed on the low refractive index layer by performing (° C., transport speed 1 m / min, roll tension 100 N / 500 mm). Then, it was cut into a sheet shape (short sheet) having a length of 500 mm and a width of 500 mm.
With respect to 10 samples of the obtained sheet-like (short sheet) laminate (transparent conductive film / protective film), the appearance of the laminate (transparent conductive film / protective film) when heated was evaluated according to the following criteria. The results obtained are shown in Table 1.
⊚: No wrinkles or floating of the transparent conductive film was confirmed in all of the 10 samples.
◯: No wrinkles or floating of the transparent conductive film was confirmed in 7 to 9 samples out of 10 samples.
Δ: No wrinkles or floating of the transparent conductive film was confirmed in 4 to 6 samples out of 10 samples. Even if wrinkles and floats were not confirmed, the laminated body having curls that could not be advanced to the next step was not added to the successful sample.
X: No wrinkles or floating of the transparent conductive film was confirmed in 0 to 3 samples out of 10 samples. Even if wrinkles and floats were not confirmed, the laminated body having curls that could not be advanced to the next step was not added to the successful sample.

(2) Appearance of Patterned Conductive Film A sheet-like laminate made of a transparent conductive film / protective film that has undergone the above-mentioned sputtering treatment was annealed by heating at 150 ° C. for 1 hour.
The laminate that had undergone the annealing treatment formed a photoresist film that was patterned in a lattice pattern on the surface of the transparent conductive film.
Then, at room temperature, the transparent conductive film was patterned in a grid pattern by immersing it in 10% by weight hydrochloric acid for 1 minute for etching treatment.
Next, the photoresist film on the transparent conductive film was removed by immersing it in a 5% by weight sodium hydroxide aqueous solution heated to 40 ° C. for 5 minutes for alkaline treatment.
The obtained patterned conductive film had a pattern shape in which square voids having a side of 2 mm were partitioned in a grid pattern by a line portion made of ITO having a line width of 2 mm, and had a thickness of 30 nm.

Next, after the protective film is peeled off from the laminated body in which the patterned conductive film is formed, the patterned conductive film formed on the transparent conductive film lamination film is visually observed, and the patterned conductive film formed on the transparent conductive film is visually observed and in accordance with the following criteria. evaluated. In this evaluation, only 10 sheet-like laminates (short sheets) having no problem in the sputtering treatment were collected and evaluated through a series of steps after the sputtering treatment described above. The results obtained are shown in Table 1.
◯: In 7 to 10 out of 10 sheets, the patterned conductive film was in a good state without any appearance defects such as distortion.
Δ: In 4 to 6 out of 10 sheets, the patterned conductive film was in a good state without any appearance defects such as distortion.
X: In 0 to 3 out of 10 sheets, the patterned conductive film was in a good state without any appearance defects such as distortion.

[Example 2]
In Example 2, a laminate was produced and evaluated in the same manner as in Example 1 except that the pressure-sensitive adhesive composition of the pressure-sensitive adhesive layer was changed when the protective film was produced. Details of the acrylic pressure-sensitive adhesive composition are shown below. The results obtained are shown in Table 1.

<Acrylic adhesive composition>
By ordinary solution polymerization, a (meth) acrylic acid ester copolymer having a weight average molecular weight of 500,000 was obtained at butyl acrylate / acrylic acid = 100/5 (weight ratio). An acrylic pressure-sensitive adhesive composition was obtained by adding 5 parts by weight of N, N, N', N'-tetraglycidyl-m-xylylenediamine as an epoxy-based cross-linking agent to 100 parts by weight of this copolymer. It was.

[Example 3]
In Example 3, a laminate was produced and evaluated in the same manner as in Example 1, except that the pressure-sensitive adhesive layer was changed to a silicone-based pressure-sensitive adhesive layer when the protective film was produced. Details of the silicone pressure-sensitive adhesive composition are shown below. The results obtained are shown in Table 1.

<Silicone adhesive composition>
Additive-type organopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KS-847H) composed of organopolysiloxane having a vinyl group and an organopolysiloxane having a siloxane bond as the main skeleton and a platinum catalyst (Shin-Etsu Chemical Co., Ltd.) Add 0.03 parts by mass of (trade name: PL-50T) and 20 parts by mass of silicone resin component (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KR3700) and dilute with methyl ethyl ketone to a solid content concentration of about 20% by mass. The silicone pressure-sensitive adhesive composition was obtained.

[Comparative Example 1]
In Comparative Example 1, when the protective film was manufactured, the protective film base material was changed from PET film (manufactured by Toray Industries, Inc., Lumirror U48) to PET film (manufactured by Toray Industries, Inc., PET38T-100, thickness 38 μm) and adhered. A laminate was produced and evaluated in the same manner as in Example 1 except that the thickness of the agent layer was changed from 15 μm to 20 μm and the pressure-sensitive adhesive composition was changed as follows. The results obtained are shown in Table 1.

<Acrylic adhesive composition>
By ordinary solution polymerization, a (meth) acrylic acid ester copolymer having a weight average molecular weight of 600,000 was obtained at butyl acrylate / acrylic acid = 100/6 (weight ratio). An acrylic pressure-sensitive adhesive composition was obtained by adding 6 parts by weight of 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane as an epoxy-based cross-linking agent to 100 parts by weight of this copolymer. It was.

[Comparative Example 2]
In Comparative Example 2, a laminate was produced and evaluated in the same manner as in Comparative Example 1, except that the pressure-sensitive adhesive composition was changed as follows when the protective film was produced. The results obtained are shown in Table 1.

<Acrylic adhesive composition>
By ordinary solution polymerization, a (meth) acrylic acid ester copolymer having a weight average molecular weight of 600,000 was obtained at butyl acrylate / acrylic acid = 100/6 (weight ratio). An acrylic pressure-sensitive adhesive composition was obtained by adding 4 parts by weight of 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane as an epoxy-based cross-linking agent to 100 parts by weight of this copolymer. It was.

1: Transparent conductive film 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: Transparent conductive film lamination film base material, 10: Transparent conductive film lamination film, 20: Protective film, 22: Protective film base material, 24: Adhesive layer, 100: Laminated body

Claims (5)

A laminate including a film for laminating a transparent conductive film and a protective film bonded to the side opposite to the side on which the transparent conductive film is laminated in the film for laminating a transparent conductive film.
The protective film has a protective film base material and a pressure-sensitive adhesive layer laminated on one surface of the protective film base material and containing at least an acrylic pressure-sensitive adhesive .
The surface free energy of the surface of the transparent conductive film laminated film on the side to which the protective film is bonded is set to a value in the range of 30 to 60 mJ / m ² .
The adhesive force P ₁ (peeling angle 180 °, peeling speed 0.3 m / min) of the protective film to the transparent conductive film laminating film when the laminated body is heated in an environment of 150 ° C. for 10 minutes is 20 to 400 mN. The value should be within the range of / 25 mm, and
The adhesive force P ₂ (peeling angle 180 °) of the protective film to the transparent conductive film lamination film when the laminate is heated in an environment of 150 ° C. for 60 minutes and then allowed to stand in an environment of 25 ° C. for 24 hours. , Peeling speed 0.3 m / min) is set to a value within the range of 250 to 400 mN / 25 mm.
The difference between the adhesive force P _{0 of the} protective film and the adhesive force P ₁ to the transparent conductive film lamination film in the stage before heating the laminate is set to a value of 80 mN / 25 mm or less. Laminated body. The laminate according to claim 1, wherein the adhesive strengths P ₁ and P ₂ satisfy the following relational expression (1).
P _2- P ₁ ≤ 300mN / 25mm (1) The laminate according to claim 1 or 2, wherein the thickness of the protective film base material is set to a value in the range of 23 to 250 μm. The laminate according to any one of claims 1 to 3 , wherein a hard coat layer is provided on the side of the transparent conductive film laminate film to which the protective film is bonded. The laminate according to any one of claims 1 to 4 , wherein the transparent conductive film is laminated on the side where the transparent conductive film is laminated in the transparent conductive film lamination film.