JP5651259B2 - LAMINATED FILM, FILM ROLL THEREOF, LIGHT TRANSMITTING CONDUCTIVE FILM OBTAINED FROM THE SAME, AND TOUCH PANEL USING THE SAME - Google Patents

Description

  The present invention relates to a laminated film, a film roll thereof, a light-transmitting conductive film obtainable therefrom, and a touch panel using the same.

  Light transmissive conductive film obtained by laminating a light transmissive conductive layer made of indium tin oxide (ITO) or the like on a light transmissive support layer made of PET or the like as a light transmissive conductive film mounted on a touch panel. Many films are used. In this light-transmitting conductive film, the light-transmitting conductive layer is usually disposed so as to be the outermost layer. This light-transmitting conductive film is once wound up as a film roll after being manufactured and then transported from the manufacturing site to the next destination, where it is rewound at the destination to obtain a film state for further processing. Usually made or used.

  For the purpose of protecting the light-transmitting conductive film when wound up as a film roll in this way, a so-called protective film is stuck on the surface of the light-transmitting conductive film opposite to the light-transmitting conductive layer, and a laminated film (Patent Document 1). When this laminated film is wound up as a film roll, the surfaces of the light-transmitting conductive layer and the protective film are adjacent to each other.

  The light transmissive conductive film may be used after forming a light transmissive conductive layer as a grid-like electrode (so-called patterning). The patterning of the light-transmitting conductive layer is a so-called etching process in which a region that is not desired to be removed is protected by a protective film called an etching resist and then chemical treatment is performed, and only the unprotected region is removed from the light-transmitting conductive layer. Is done.

  This etching process is performed after the film roll formed by winding the above-described laminated film is rewound into a film state. Specifically, the treatment with an etching resist and the treatment with an etching solution are sequentially performed in a film state.

  This laminated film is finally used for applications such as mounting on a touch panel as a light-transmitting conductive film after peeling off the protective film.

JP 2001-332132 A

  After performing the etching treatment by sequentially performing the treatment with the etching resist and the treatment with the etching liquid on the above-described laminated film, when the etching resist is further removed by the chemical treatment, the etching resist film is on the protective film side. The present inventors have found that there is a problem of adhering to the surface. If such an etching resist film adheres to the protective film side, problems such as difficulty in finding appearance defects and the like occur in subsequent processes, which is not preferable.

  An object of the present invention is to provide a laminated film in which an etching resist film is difficult to adhere to the surface on the protective film side after the etching resist is removed.

The inventors of the present invention have intensively studied to solve the above problems and have completed the present invention. Specifically, the present inventors have found that the above problem can be solved by using a protective film having a surface with a contact angle with water in a predetermined range, and have completed the present invention. That is, the present invention is as follows.
Item 1.
(A) a light transmissive conductive film; and (B) a protective film
The light-transmitting conductive film (A) is
(A-1) a light transmissive support layer; and (A-2) one or more light transmissive conductive layers, and at least one outermost layer is one light transmissive conductive layer (A-2). A light transmissive conductive film comprising:
At least one of the light transmissive conductive layers (A-2) of the outermost layer of the light transmissive conductive film (A) is disposed on one surface of the laminated film,
The protective film (B) is disposed on the other surface of the laminated film, and the contact angle with respect to water of the surface on the protective film (B) side is 70 ° or more, and the laminated film .
Item 2.
Item 2. The laminated film according to Item 1, wherein the Haze value is 5% or less.
Item 3.
Item 3. The laminated film according to Item 1 or 2, wherein the light transmissive conductive layer (A-2) contains indium tin oxide.
Item 4.
The film roll formed by winding up the laminated | multilayer film in any one of claim | item 1-3.
Item 5.
The light transmissive conductive film which can be obtained by the method containing the process of obtaining a light transmissive conductive film (A) by peeling a protective film (B) from the laminated | multilayer film in any one of claim | item 1-3. .
Item 6.
Item 6. A touch panel comprising the light transmissive conductive film according to Item 5.

  According to the present invention, it is possible to reduce the amount of the etching resist film adhering to the surface on the protective film side after performing the etching treatment.

Lamination of the present invention comprising a light transmissive conductive film (A) having a light transmissive conductive layer (A-2) disposed on one side of a light transmissive support layer (A-1) and a protective film (B). It is sectional drawing which shows a film. The laminate of the present invention comprising a light-transmitting conductive film (A) having a light-transmitting conductive layer (A-2) disposed on both surfaces of the light-transmitting support layer (A-1), and a protective film (B). It is sectional drawing which shows a film. A light transmissive conductive film (A) in which a light transmissive conductive layer (A-2) and a light transmissive underlayer (A-3) are disposed on one side of the light transmissive support layer (A-1); and It is sectional drawing which shows the laminated | multilayer film of this invention which consists of a protective film (B) by which the adhesion layer (B-2) is arrange | positioned at the single side | surface of a protective layer (B-1). A light transmissive conductive layer (A-2), a light transmissive underlayer (A-3), and a hard coat layer (A-4) are further light transmissive on one surface of the light transmissive support layer (A-1). A light-transmitting conductive film (A) in which another hard coat layer (A-4) is disposed on the other surface of the conductive support layer (A-1); It is sectional drawing which shows the laminated | multilayer film of this invention which consists of a protective film (B) by which the adhesion layer (B-2) is arrange | positioned. Light transmissive conductive film (A-2) having light transmissive conductive layer (A-2) disposed on one side of light transmissive support layer (A-1); and adhesive on one side of protective layer (B-1) It is sectional drawing which shows the laminated | multilayer film of this invention which consists of a protective film (B) in which the layer (B-2) is arrange | positioned. Light transmissive conductive film (A-2) having light transmissive conductive layer (A-2) disposed on one side of light transmissive support layer (A-1); and oligomer on one side of protective layer (B-1) It is sectional drawing which shows the laminated | multilayer film of this invention which consists of a protective film (B) with which the block layer (B-3) is arrange | positioned.

1. Laminated film The laminated film of the present invention is a film having a configuration in which two or more films are laminated,
(A) a light transmissive conductive film;
(B) Contains a protective film.

In the laminated film of the present invention, the light transmissive conductive film (A) is:
(A-1) a light transmissive support layer; and (A-2) a light transmissive conductive layer;
Each containing one or more
At least one outermost layer is configured to be one light transmissive conductive layer (A-2). That is, the light transmissive conductive film (A) may contain two or more light transmissive conductive layers (A-2). In this case, the light transmissive conductive film (A) One light transmissive conductive layer (A-2) may be disposed on one surface of the light transmissive support layer (A-1) so as to be the outermost layer, and another light transmissive conductive layer ( A-2) may be disposed on the other surface of the light-transmissive support layer (A-1). In the latter case, the other light transmissive conductive layer (A-2) may be disposed on the other surface of the light transmissive support layer (A-1) so as to be the outermost layer.

  In the laminated film of the present invention, at least one of the light transmissive conductive layers (A-2) arranged in the outermost layer of the light transmissive conductive film (A) is one surface of the laminated film (“light transmissive”). The protective film (B) is disposed on the conductive conductive layer (A-2) side) and the protective film (B) is the other surface of the laminated film (the “protective film (B) side surface”) Is located). In the laminated film of the present invention, the light-transmitting conductive layer (A-2) and the protective film (B) may be disposed on the surface, and the light-transmitting conductive film (A) and the protective film (B). Other structures such as another film may be interposed therebetween. Further, as described above, when the light-transmitting conductive layer (A-2) is disposed on both sides of the light-transmitting support layer (A-1) so as to be the outermost layer, any light transmission is possible. Conductive layer (A-2) may be disposed on the surface of the laminated film.

  Furthermore, the surface on the protective film (B) side of the laminated film of the present invention has a contact angle with water of 70 ° or more. As a result, the laminated film of the present invention has an amount that the etching resist film adheres to the surface on the protective film side when the etching resist is removed after the etching treatment of the light transmissive conductive layer (A-2). Has been reduced.

  In FIG. 1, the one aspect | mode of the laminated | multilayer film of this invention is shown. In this aspect, first, the light-transmitting conductive film is directly (that is, adjacent) to one surface of the light-transmitting support layer (A-1), and the light-transmitting conductive layer (A-2) is provided. The arrangement is arranged. At this time, the light transmissive conductive layer (A-2) is the outermost layer on the surface of the light transmissive support layer (A-1). And this light transmissive conductive layer (A-2) is arrange | positioned at the one surface of a laminated | multilayer film, and the protective film (B) is each arrange | positioned at the other surface of a laminated | multilayer film.

  FIG. 2 shows another embodiment of the laminated film of the present invention. In this aspect, first, the light transmissive conductive film has a configuration in which the light transmissive conductive layer (A-2) is directly disposed on both surfaces of the light transmissive support layer (A-1). Prepare. At this time, the two light-transmissive conductive layers (A-2) are outermost layers on both surfaces of the light-transmissive support layer (A-1). Furthermore, arbitrary one light transmissive conductive layer (A-2) is arrange | positioned at the one surface of a laminated | multilayer film, and the protective film (B) is each arrange | positioned at the other surface of a laminated | multilayer film.

1.1 Light transmissive conductive film (A)
In the present invention, “light-transmitting” means having a property of transmitting light (translucent). “Light transmissivity” includes transparency. “Light transmissivity” means, for example, the property that the total light transmittance is 80% or more, preferably 85% or more, more preferably 88% or more. In the present invention, the total light transmittance is measured based on JIS-K-7105 using a haze meter (trade name: NDH-2000 manufactured by Nippon Denshoku Co., Ltd. or equivalent).

  In the present invention, the thickness of each layer is determined using a commercially available reflection spectral film thickness meter (Otsuka Electronics, FE-3000 (product name), or equivalent). Alternatively, it may be obtained by observation using a commercially available transmission electron microscope. Specifically, a film to be measured is thinly cut in a direction perpendicular to the film surface using a microtome or a focused ion beam, and the cross section is observed.

  In this specification, when mentioning the relative positional relationship between two layers among a plurality of layers arranged on one surface of the light transmissive support layer (A-1), the light transmissive support layer (A- On the basis of 1), one layer having a large distance from the light transmissive support layer (A-1) may be referred to as an “upper” layer or the like.

1.1.1 Light transmissive support layer (A-1)
In the present invention, the light-transmitting support layer refers to a light-transmitting conductive film containing a light-transmitting conductive layer that plays a role of supporting a layer including the light-transmitting conductive layer. Although it does not specifically limit as a light transmissive support layer (A-1), For example, in the conductive film for touch panels, what is normally used as a light transmissive support layer can be used.

  Although the raw material of a light-transmissive support layer (A-1) is not specifically limited, For example, various organic polymers etc. can be mentioned. The organic polymer is not particularly limited. For example, polyester resin, acetate resin, polyether resin, polycarbonate resin, polyacrylic resin, polymethacrylic resin, polystyrene resin, polyolefin resin, polyimide resin, etc. Examples thereof include resins, polyamide resins, polyvinyl chloride resins, polyacetal resins, polyvinylidene chloride resins, and polyphenylene sulfide resins. Although it does not specifically limit as polyester-type resin, For example, a polyethylene terephthalate (PET), a polyethylene naphthalate (PEN), etc. are mentioned. The material of the light transmissive support layer (A-1) is preferably a polyester resin, and particularly preferably PET. The light transmissive support layer (A-1) may be composed of any one of these, or may be composed of a plurality of types. Further, a plurality of light-transmitting support layers may be bonded with an adhesive or the like. When a plurality of light-transmitting support layers are used, a plurality of the same types may be used, or a plurality of types may be used.

  Although the thickness of a light-transmissive support layer (A-1) is not specifically limited, For example, the range of 2-300 micrometers is mentioned.

1.1.2 Light transmissive conductive layer (A-2)
In the laminated film of the present invention, at least one light transmissive conductive layer (A-2) is directly or at least one other layer on at least one surface of the light transmissive support layer (A-1). Are arranged to be the outermost layer.

  The light transmissive conductive layer (A-2) may be disposed at least one layer on each of both surfaces of the light transmissive support layer (A-1).

  In the present invention, the light-transmitting conductive layer means a layer containing a conductive substance, conducting electricity and transmitting visible light. Although it does not specifically limit as a light transmissive conductive layer (A-2), For example, what is normally used as a light transmissive conductive layer in the conductive film for touch panels can be used.

  The material for the light transmissive conductive layer (A-2) is not particularly limited, and examples thereof include indium oxide, zinc oxide, tin oxide, and titanium oxide. The light transmissive conductive layer (A-2) is preferably a light transmissive conductive layer containing indium oxide doped with a dopant in terms of achieving both transparency and conductivity. The light transmissive conductive layer (A-2) may be a light transmissive conductive layer made of indium oxide doped with a dopant. Although it does not specifically limit as a dopant, For example, a tin oxide, a zinc oxide, those mixtures, etc. are mentioned.

In the case of using indium oxide doped with tin oxide as the material of the light transmissive conductive layer (A-2), indium oxide (III) (In ₂ O ₃ ) is doped with tin (IV) oxide (SnO ₂ ). (Tin-doped indium oxide; ITO) is preferable. In this case, the addition amount of SnO ₂ is not particularly limited, and examples thereof include 1 to 15% by weight, preferably 2 to 10% by weight, and more preferably 3 to 8% by weight. Moreover, you may use as a raw material of a transparent conductive layer (A-2) what added the other dopant to indium tin oxide in the range which the total amount of a dopant does not exceed the numerical range of the left. Although it does not specifically limit as another dopant in the left, For example, selenium etc. are mentioned.

  The light transmissive conductive layer (A-2) may be composed of any one of the various materials described above, or may be composed of a plurality of types.

  The light transmissive conductive layer (A-2) is not particularly limited, but may be a crystalline or amorphous body, or a mixture thereof.

  Although the thickness of a light transmissive conductive layer (A-2) is not specifically limited, Usually, it is 5-50 nm. The thickness of the light transmissive conductive layer (A-2) is preferably 10 to 40 nm, more preferably 12 to 35 nm, and still more preferably 15 to 30 nm.

  The method of disposing the light transmissive conductive layer (A-2) may be either wet or dry, and is not particularly limited. Specific examples of the method for disposing the light transmissive conductive layer (A-2) include a sputtering method, a vacuum deposition method, an ion plating method, a CVD method, and a pulse laser deposition method.

  As a method for forming the light transmissive conductive layer (B), a method including a step of baking a conductive material is preferable. Although it does not specifically limit as a baking method, For example, the drum heating at the time of performing sputtering etc., a hot-air-type baking furnace, a far-infrared baking furnace, etc. can be mentioned as an example. Although a calcination temperature is not specifically limited, Usually, it is 30-250 degreeC, Preferably it is 50-200 degreeC, More preferably, it is 80-180 degreeC, More preferably, it is 100-160 degreeC. The firing time is preferably 3 minutes to 180 minutes, more preferably 5 minutes to 120 minutes, and even more preferably 10 minutes to 90 minutes. As an atmosphere for performing the firing, an atmosphere, an inert gas such as nitrogen or argon, oxygen, hydrogenated nitrogen, or a combination of two or more of these can be given under vacuum. By firing the conductive material, crystallization of the conductive material is promoted.

1.1.3 Light transmissive underlayer (A-3)
The light transmissive conductive film (A) further contains a light transmissive underlayer (A-3), and at least one light transmissive conductive layer (A-2) is at least a light transmissive underlayer (A). -3) may be disposed on the surface of the light transmissive support layer (A-1).

  The light transmissive conductive layer (A-2) may be disposed adjacent to the light transmissive underlayer (A-3).

  In FIG. 3, the one aspect | mode of the laminated | multilayer film of this invention is shown. In this embodiment, in the light transmissive conductive film (A), the light transmissive underlayer (A-3) is directly disposed on one surface of the light transmissive support layer (A-1). The light transmissive underlayer (A-3) is disposed via the transmissive underlayer (A-3). Other configurations are the same as those in FIG. 5 described later.

The material for the light-transmitting underlayer (A-3) is not particularly limited, but may be, for example, a dielectric material. The material for the light-transmitting underlayer (A-3) is not particularly limited. For example, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon alkoxide, alkylsiloxane and its condensate, polysiloxane, silsesquiskies. Examples include oxane, polysilazane, and acrylic silica hybrid. The light transmissive underlayer (A-3) may be composed of any one of them, or may be composed of a plurality of types. The light-transmitting underlayer (A-3) is preferably a light-transmitting underlayer including one selected from the group consisting of polysilazane, acrylic silica hybrid, and SiO _x (x = 1.0 to 2.0). . The light transmissive underlayer (A-3) is a light transmissive underlayer made of one selected from the group consisting of polysilazane, acrylic silica hybrid, and SiO _x (x = 1.0 to 2.0). Also good. The light transmissive underlayer (A-3) is preferably a light transmissive underlayer containing SiO _x (x = 1.0 to 2.0). The light transmissive underlayer (A-3) may be a light transmissive underlayer made of SiO _x (x = 1.0 to 2.0). Hereinafter, for example, a light-transmitting underlayer made of SiO _x (x = 1.0 to 2.0) may be abbreviated as an SiO _x layer.

One layer of the light transmissive underlayer (A-3) may be disposed. Alternatively, two or more layers may be arranged adjacent to each other or separated from each other via other layers. Two or more light-transmitting underlayers (A-3) are preferably disposed adjacent to each other. Examples of such embodiments include, for example, stacking composed of adjacent SiO ₂ layers and SiO _x layers, and stacking composed of adjacent SiO ₂ layers and SiO _x N _y layers. For example, when two layers are arranged adjacent to each other, the order of the SiO ₂ layer and the SiO _x layer is arbitrary, but the light transmissive underlayer made of SiO ₂ on the light transmissive support layer (A-1) side. (B-2) It is preferable to dispose a light-transmitting underlayer (C-2) made of SiO _x (x = 1.0 to 2.0) on the light-transmitting conductive layer (A-2) side.

  Although it does not specifically limit as thickness per layer of a light transmissive base layer (A-3), For example, 15-25 nm etc. are mentioned. When two or more layers are disposed adjacent to each other, the total thickness of all the light-transmitting underlayers (A-3) adjacent to each other may be within the above range.

  The refractive index of the light-transmitting underlayer (A-3) is not particularly limited as long as the light-transmitting conductive film (A) can be used as a touch panel application. For example, 1.4 to 1.5 is preferable.

  As a method of disposing the light-transmitting underlayer (A-3), as a dry method, for example, a method of laminating on an adjacent layer by a sputtering method, an ion plating method, a vacuum deposition method, or a pulsed laser deposition method, or the like. Can be mentioned.

1.1.4 Hard coat layer (A-4)
The light transmissive conductive film (A) has a hard coat layer (A-4) in place of the light transmissive underlayer (A-3) or in addition to the light transmissive underlayer (A-3). And at least one light transmissive conductive layer (A-2) may be disposed on the surface of the light transmissive support layer (A-1) via at least the hard coat layer (A-4). .

  When the light transmissive conductive film (A) includes both the light transmissive underlayer (A-3) and the hard coat layer (A-4) on the same surface of the light transmissive support layer (A-1), The light transmissive underlayer (A-3) is disposed on the surface of the light transmissive support layer (A-1) via at least the hard coat layer (A-4). In this case, the light transmissive underlayer (A-3) is preferably disposed adjacent to the hard coat layer (A-4).

  The hard coat layer (A-4) is preferably disposed adjacent to at least one surface of the light transmissive support layer (A-1).

  One layer of the hard coat layer (A-4) may be disposed. Alternatively, two or more layers may be arranged adjacent to each other or separated from each other via other layers.

  The hard coat layer (A-4) may be disposed on both surfaces of the light transmissive support layer (A-1).

  In FIG. 6, the one aspect | mode of the laminated | multilayer film of this invention is shown. In this embodiment, in the light transmissive conductive film (A), one hard coat layer (A-4) is directly disposed on one surface of the light transmissive support layer (A-1). A light-transmitting underlayer (A-3) is further disposed through the coat layer (A-4), and the light-transmitting conductive layer (A-2) is disposed through the light-transmitting underlayer (A-3). It is further arranged. Moreover, the other hard-coat layer (A-4) is directly arrange | positioned also at the other surface of the transparent support layer (A-1). Other configurations are the same as those in FIG. 5 described later.

  In the present invention, the hard coat layer means a layer that prevents the plastic surface from being damaged. Although it does not specifically limit as a hard-coat layer (A-4), For example, what is normally used as a hard-coat layer in the transparent conductive film for touchscreens can be used.

  The material of the hard coat layer (A-4) is not particularly limited, and examples thereof include acrylic resins, silicone resins, urethane resins, melamine resins, and alkyd resins. Examples of the material for the hard coat layer (A-4) further include those obtained by dispersing colloidal particles such as silica, zirconia, titania and alumina in the resin. The hard coat layer (A-4) may be composed of any one of these, or may be composed of a plurality of types. As the hard coat layer (A-4), an acrylic resin in which zirconia particles are dispersed is preferable.

  Although the thickness per layer of a hard-coat layer (A-4) is not specifically limited, For example, 0.03-10 micrometers, 0.5-5 micrometers, 1-3 micrometers, etc. are mentioned. When two or more layers are disposed adjacent to each other, the total thickness of all the hard coat layers (A-4) adjacent to each other may be within the above range. In the example list shown on the left, the following are more preferable than the above.

  The refractive index of the hard coat layer (A-4) is not particularly limited as long as the light transmissive conductive film (A) can be used as a touch panel application, and examples thereof include 1.4 to 1.7.

  The hard coat layer (A-4) may have a higher refractive index than the light-transmitting underlayer (A-3). In this case, the light-transmitting underlayer (A-3) is preferably disposed adjacent to one surface of the hard coat layer (A-4). By adopting such a configuration, the transmittance of the light transmissive conductive film (A) is improved by the optical interference action of the light transmissive underlayer (A-3) and the hard coat layer (A-4), which is preferable. . Further, by adopting such a configuration, the pattern appearance of the patterned light-transmitting conductive layer (A-2) is reduced.

  The method of disposing the hard coat layer (A-4) is not particularly limited, and examples thereof include a method of applying to a film and curing with heat, a method of curing with active energy rays such as ultraviolet rays and electron beams, and the like. It is done. From the viewpoint of productivity, a method of curing with ultraviolet rays is preferable.

1.1.5 Other layers (A-5)
In addition to the light-transmitting conductive layer (A-2), the light-transmitting conductive film of the present invention is provided on at least one surface of the light-transmitting support layer (A-1). 3) At least one layer selected from the group consisting of the hard coat layer (A-4) and at least one other layer (A-5) different from them may be further arranged.

  Although it does not specifically limit as another layer (A-5), For example, an adhesive layer etc. are mentioned.

  The adhesive layer is a layer that is disposed between two layers so as to be adjacent to each other and to adhere the two layers to each other. Although it does not specifically limit as a contact bonding layer, For example, what is normally used as a contact bonding layer in the transparent conductive film for touchscreens can be used. The adhesive layer may be composed of any one of these, or may be composed of a plurality of types.

1.2 Protective film (B)
In the present invention, the protective film (B) refers to a film that is used by being attached to a light-transmitting conductive film for the purpose of protecting the light-transmitting conductive film mainly when wound as a film roll. . In the wound state, the surfaces of the light transmissive conductive layer and the protective film are adjacent to each other, thereby protecting the light transmissive conductive layer.

  The protective film (B) is not particularly limited, and can be widely selected from those usually used for this purpose.

  Although the raw material of a protective film (B) is not specifically limited, For example, polyester, a polypropylene, polyethylene, etc. are mentioned. Among these, polyester is preferable in terms of heat resistance.

  The surface of the protective film (B) facing the light transmissive conductive layer (A-2) in a state of being wound as a film roll, that is, the surface of the laminated film on the side of the protective film (B) is the surface. The contact angle with respect to water is 70 ° or more. As a result, in the laminated film of the present invention, the amount of the etching resist film adhering to the surface on the protective film side after the etching treatment of the light transmissive conductive layer (A-2) is reduced. In terms of reducing the adhesion amount of the etching resist soot, it is more preferable that the surface has a water contact angle of 80 ° or more.

  In the present invention, the contact angle with respect to water is measured as follows. Measurement is performed using an automatic contact angle meter (DM500) manufactured by Kyowa Interface Science Co., Ltd. or its equivalent. Specifically, the sample is cut out, 1 μL of distilled water is slowly dropped from a height of 5 mm with a syringe, the syringe is quickly separated from the sample, and is further left for 3 seconds. After leaving, the contact angle (angle formed by the tangent line between the hard coat layer surface and the droplet) is observed and measured with a CCD camera. The same operation is repeated 10 times, and the average value is taken as the contact angle with water in the present invention.

  The laminated film of the present invention has no problem as long as the haze value is usually at least 5% or less. Therefore, the Haze value of the protective film (B) can be appropriately set within a range where the Haze value of the entire film is 5% or less. In the left column, the Haze value of the entire laminated film is preferably 3% or less, and more preferably 2.5% or less.

  By setting the thermal shrinkage rates of the protective film (B) and the light-transmitting conductive film (A) to values close to each other, the degree of curling when a laminated film is formed can be suppressed.

  Although the thickness of a protective film (B) is not specifically limited, Usually, it is 25-125 micrometers.

  Although the thickness of a protective film (B) is not specifically limited, If the total thickness is 170 micrometers or more in the state which bonded the transparent conductive film and the protective film, it is preferable. More preferably, the total thickness is 170 to 270 μm.

  By setting the thermal shrinkage rates of the protective film (B) and the light-transmitting conductive film (A) to values close to each other, the degree of curling when a laminated film is formed can be suppressed.

  Although the method of arrange | positioning a protective film (B) is not specifically limited, Usually, it can arrange by sticking to an adjacent surface through the adhesion layer mentioned later.

1.2.1 Adhesive layer (B-2)
The protective film (B) may have a laminated structure, and in this case, the layer having the configuration and characteristics described in 1.2 above is used as a main layer (for convenience, the “protective layer (B-1 ) ") And may further contain, for example, an adhesive layer (B-2).

  The pressure-sensitive adhesive layer (B-2) refers to a layer used for the purpose of disposing the protective film (B) on the surface of the light transmissive conductive film (A).

  The pressure-sensitive adhesive layer (B-2) is not particularly limited, and can be selected widely from those usually used for this purpose. In general, an acrylic pressure-sensitive adhesive or a silicone-based pressure-sensitive adhesive is used for this purpose from the viewpoint of processability. Therefore, for example, these can be selected suitably and an adhesion layer (B-2) can also be formed.

  In the laminated film of the present invention, in this case, the protective film (B) is disposed on the surface of the light-transmitting conductive film via the adhesive layer (B-2). Therefore, the surface of the protective film (B) opposite to the adhesive layer (B-2) has a contact angle with water of 70 ° or more.

  In FIG. 5, the one aspect | mode of the electroconductive film of this invention is shown. In this embodiment, the protective film (B) has the same configuration as that shown in FIG. 1 except that the protective film (B) is composed of a protective layer (B-1) and an adhesive layer (B-2).

1.2.2 Oligomer block layer (B-3)
In addition to the adhesive layer (B-2), the protective film (B) includes the layer having the configuration and characteristics described in 1.2 above as a main layer (protective layer (B-1)) or is adhesive. Instead of the layer (B-2), an oligomer block layer (B-3) may be contained.

  The oligomer block layer (B-3) is used for the purpose of preventing the oligomer from being deposited on the film surface after heat treatment (for example, heat treatment at 150 ° C. for 1 hour) and causing the appearance of the film to become cloudy. It refers to the layer.

  The material of the oligomer block layer (B-3) can be widely selected from materials usually used for this purpose. More specifically, it can be appropriately selected from those capable of forming a transparent film, and may be an inorganic material, an organic material, or a composite material thereof.

  The thickness of the oligomer block layer (B-3) is not particularly limited, but is preferably 0.01 to 2 μm.

  In the laminated film of the present invention, in this case, the protective film (B) is disposed such that the oligomer block layer (B-3) is located on the outermost surface. Therefore, the surface of the oligomer block layer (B-3) needs to have a contact angle with water of 70 ° or more.

  FIG. 6 shows one embodiment of the conductive film of the present invention. In this embodiment, the protective film (B) has the same configuration as that shown in FIG. 1 except that the protective film (B-1) is composed of a protective layer (B-1) and an oligomer block layer (B-3). .

1.3 Use of the laminated film of the present invention The light transmissive conductive film (A) obtained by peeling the protective film (B) from the laminated film of the present invention can be used for the production of touch panels and the like. . Details of the touch panel are as described in 3.

2. Film Roll of the Present Invention The film roll of the present invention is a film roll formed by winding up the laminated film of the present invention.

  Although not particularly limited, the film roll of the present invention is usually formed by winding the laminated film of the present invention having a width of 0.2 to 2 m and a length of 10 to 1000 m.

  Although the film roll of this invention is not specifically limited, For example, it can obtain as follows. On the light-transmitting support layer (A-1), a layer serving as a base of the light-transmitting conductive layer (A-2) and other layers are arranged on the opposite surface as necessary. A protective film (B) is stuck and a film roll is created by winding up this laminated film. At this time, the laminated film may be surface-treated. The film roll of this invention can be obtained by throwing this film roll into a sputtering device in a roll shape and forming the light-transmitting conductive layer (A-1) while winding it into a roll shape.

  After the laminated film wound up in a roll shape is cut into a sheet shape, the protective film (B) is further peeled off from the sheet-like laminated film subjected to various processing as required, thereby translucent conductive. A film (A) is obtained and can be used as a transparent electrode for a touch panel.

3. Touch Panel of the Present Invention The touch panel of the present invention contains a light transmissive conductive film (A) obtained by peeling the protective film (B) from the laminated film of the present invention, and further contains other members as necessary. It contains.

The touch panel of the present invention is not particularly limited, but may be a capacitive touch panel, for example. Specific examples of the configuration of the capacitive touch panel according to the present invention include the following configurations. It should be noted that the protective layer (1) side is used with the operation screen side and the glass (5) side faces the opposite side of the operation screen.
(1) Protective layer (2) Light transmissive conductive film of the present invention (Y-axis direction)
(3) Insulating layer (4) Light transmissive conductive film of the present invention (X-axis direction)
(5) Glass Although the capacitive touch panel of the present invention is not particularly limited, for example, it can be produced by combining the above (1) to (5) and other members as required according to a usual method. it can.

4). The manufacturing method of the laminated | multilayer film of this invention The manufacturing method of the laminated | multilayer film of this invention may contain the process included in the manufacturing method of a transparent electroconductive film (A). The light-transmitting conductive film (A) is produced by adding a light-transmitting underlayer on at least one surface of the light-transmitting support layer (A-1) in addition to the light-transmitting conductive layer (A-2). (A-3), a hard coat layer (A-4), and a step of disposing at least one kind of layer selected from the group consisting of at least one other layer (A-5) different from them, respectively. You may go out.

  The manufacturing method of the laminated | multilayer film of this invention may contain the process included in the manufacturing method of a protective film (B). The manufacturing method of a protective film (B) arrange | positions an oligomer block layer (B-3) on the adhesive layer (B-2) and / or the other surface, respectively on one surface of a protective layer (B-1). Each of the steps may be included.

  In each of the above steps, the step of disposing each layer is as described for each layer. In the case where at least one other layer is disposed in addition to the light transmissive conductive layer (A-2), for example, the light transmissive support layer is provided on at least one surface of the light transmissive support layer (A-1). Although it may be arranged sequentially from the (A-1) side, the arrangement order is not particularly limited. For example, you may arrange | position another layer to one side of the layer (for example, light transmissive conductive layer (A-2)) which is not a light transmissive support layer (A-1) first. Alternatively, one composite layer is obtained by arranging two or more layers adjacent to each other on the one hand, or at the same time, two or more layers are similarly disposed adjacent to each other on the other side. Thus, one type of composite layer may be obtained, and these two types of composite layers may be further arranged adjacent to each other.

  Moreover, the manufacturing method of the laminated | multilayer film of this invention is replaced with the above, or in addition to the above, on one surface of a transparent electroconductive film (A), directly or through another film, a protective film ( A step of arranging B) may be included.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
1. Example 1.1 Preparation of Hard Coat Material 1.1.1 Hard Coat 1 (H1)
A liquid hard coating material (solid content concentration) is added to a photopolymerizer-containing acrylic oligomer by adding a mixed solvent obtained by mixing toluene and methyl isobutyl ketone (MIBK) at a ratio of 5: 5 (weight ratio). : 40% by weight).

1.1.2 Protective film 1 part by weight of an isocyanate-based crosslinking agent is blended with 100 parts by weight of solid content of adhesive SK Dyne 1473H (solid content 30%) manufactured by Soken Chemical Co. A pressure-sensitive adhesive solution adjusted to 10% was prepared. This was applied on a PET film so as to have a thickness of 10 μm, and dried at 100 ° C. for 2 minutes to form an adhesive layer. Further, the film was aged for 72 hours at 40 ° C. to obtain a surface protective film. As a base material for the PET film, a substrate provided with an oligomer block layer on one side was used. The contact angle of the oligomer block layer was measured and found to be 80 °. This protective film is referred to as “protective film R1”.

1.2 Example 1
With a 125 μm thick easily adhesive polyester film (trade name: A4300, manufactured by Toyobo Co., Ltd.) as a light-transmitting support layer, a liquid hard coat material (H1) is applied to one surface thereof with a bar coater, Further, the coated film was heat-dried using a dryer oven under the conditions of 100 ° C. × 1 minute. Next, the coated film after drying was irradiated with ultraviolet rays (irradiation amount: 300 mJ / cm ² ) to dispose a hard coat layer having a thickness of about 2 μm on the light-transmitting support layer.

  A roll of a film (hard coat film) in which a hard coat layer having a thickness of about 2 μm is disposed on both surfaces of the light transmissive support layer by performing the same operation on the other surface of the light transmissive support layer. Got. Before winding up the film roll, a protective film R1 was laminated on one side of the hard coat film.

Using a sintered body material composed of 95% by weight of indium oxide and 5% by weight of tin oxide as a target material on the surface opposite to the surface on which the protective film R1 was laminated of the film thus obtained, A light transmissive conductive layer was formed by magnetron sputtering. Specifically, after the inside of the chamber is evacuated to 5 × 10 ⁻⁴ Pa or less, a mixed gas composed of 95% Ar gas and 5% oxygen gas is introduced into the chamber, and the pressure in the chamber is reduced to 0. 0. Sputtering was performed at 2 to 0.3 Pa. Sputtering was performed so that the film thickness of the finally obtained transparent conductive layer was 20 nm. The sheet resistance value after annealing of the obtained film (150 ° C., 1 hour) was 150Ω / □.

1.3 Examples 2-4
Processing was performed in the same manner as in Example 1 except that the protective film (R2 to R4) having the contact angle shown in Table 1 as the contact angle of the oligomer block layer of the protective film was used.

2. Comparative Examples 1 and 2
Processing was carried out in the same manner as in Example 1 except that protective films (R5, R6) having the contact angles shown in Table 1 as the contact angle of the oligomer block layer of the protective film were used.

3. Various evaluation methods Various evaluation methods were performed as follows.
3.1 Resist soot adhesion confirmation method 3.1.1 Preparation of resist soot As an acid resistant resist, an ultraviolet curable etching resist (TPER-194B-2) manufactured by Kyoyo Chemical Industry was used. After thinly applying the resist agent on the surface of an appropriate film base material, the resist agent was cured by irradiating with an ultraviolet ray having an integrated light quantity of 1,000 mJ / cm ² .

  Subsequently, the resist cured film was swelled and peeled off from the film substrate by dipping in an alkaline solution, specifically 250 ml of a 3% strength by weight sodium hydroxide aqueous solution.

  After recovering the film substrate, the cured resist film was crushed to an appropriate size using an ultrasonic homogenizer to obtain an alkaline liquid in which a fine resist film was dispersed.

3.1.2 Evaluation Method After the alkali solution is lightly stirred to uniformly disperse the fine resist film, the laminated films obtained in Examples and Comparative Examples are immediately immersed, and the surface on the protective film side A resist film was attached to the film.

  Subsequently, the resist film adhering to the surface on the protective film side can be easily removed by gently washing with pure water. ◎, the protective film side can be removed by shaking the laminated film slightly in pure water. The case where the resist film adhering to the surface was removed was marked as ◯, and the case where the resist film could not be removed was marked as x.

  The evaluation results are shown in Table 1. When a protective film having a contact angle of 53.1 to 68.1 ° is used, it is difficult to remove the resist film adhering to the surface of the protective film, while at least a contact angle of 71.0 to 85.0 ° is protected. In the case of using a film, it was found that the resist film adhering to the protective film surface can be easily removed.

1 Laminated film 11 Light transmissive conductive film (A)
111 Light-transmissive support layer (A-1)
112 Light-transmissive conductive layer (A-2)
113 Light transmissive underlayer (A-3)
114 Hard coat layer (A-4)
12 Protective film (B)
121 Protective layer (B-1)
122 Adhesive layer (B-2)
123 Oligomer block layer (B-3)

Claims (5)

(A) a light transmissive conductive film; and (B) a laminated film containing a protective film,
The light-transmitting conductive film (A) is
(A-1) a light transmissive support layer; and (A-2) each containing one or more light transmissive conductive layers, and at least one outermost layer is one light transmissive conductive layer (A-2). A light transmissive conductive film comprising:
At least one of the light transmissive conductive layers (A-2) of the outermost layer of the light transmissive conductive film (A) is disposed on one surface of the laminated film,
The protective film (B) is detachably attached to the other surface of the laminated film, and the contact angle of the surface on the protective film (B) side with respect to water is 70 ° or more. , Laminated film. The laminated film according to claim 1, wherein the light transmissive conductive layer (A-2) contains indium tin oxide. The film roll formed by winding up the laminated | multilayer film of Claim 1 or 2. The light-transmitting electroconductive property which can be obtained by the method containing the process of obtaining a light-transmitting conductive film (A) by peeling a protective film (B) from the laminated | multilayer film in any one of Claims 1-3. the film. A touch panel containing the light transmissive conductive film according to claim 4.

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