WO2015186549A1

WO2015186549A1 - Laminate, transfer film, method for producing laminate, conductive film laminate, capacitive input device and image display device

Info

Publication number: WO2015186549A1
Application number: PCT/JP2015/064879
Authority: WO
Inventors: 一真両角; 吉成　伸一; 崇一郎長田; 公竹内; 菅▲崎▼　敦司
Original assignee: 富士フイルム株式会社
Priority date: 2014-06-06
Filing date: 2015-05-25
Publication date: 2015-12-10
Also published as: JPWO2015186549A1; TW201545870A

Abstract

This laminate comprises at least two transparent resin layers that are laminated on a part or the whole of a front plate, and an electrode pattern that is arranged above the at least two transparent resin layers. The elastic modulus (E1) of a first transparent resin layer, which is in contact with the electrode pattern, and the elastic modulus (E2) of a second transparent resin layer, which is the second transparent resin layer from the electrode pattern, satisfy formula (1). The elongation at break (φ) of the second transparent resin layer satisfies formula (2). E1 > E2 formula (1) φ ≥ 10% formula (2)

Description

LAMINATE, TRANSFER FILM, LAMINATE MANUFACTURING METHOD, CONDUCTIVE FILM LAMINATE, CAPACITANCE TYPE INPUT DEVICE, AND IMAGE DISPLAY DEVICE

The present invention relates to a laminate, a transfer film, a laminate production method, a conductive film laminate, a capacitance-type input device, and an image display device. More specifically, a laminate that can suppress electrode pattern disconnection even when the front plate is cracked and bent, a transfer film for producing the laminate, a method for producing the laminate, and a conductive film using the laminate The present invention relates to a laminated body, a capacitive input device using the conductive film laminated body, and an image display device using the capacitive input device.

In recent years, electronic devices such as mobile phones, car navigation systems, personal computers, ticket vending machines, and bank terminals have been equipped with tablet-type input devices on the surface of liquid crystal devices and instructions displayed in the image display area of liquid crystal display devices. There is a type in which information corresponding to an instruction image can be input by touching a part where the instruction image is displayed with a finger or a touch pen while referring to the image.

Capacitance type input devices are more resistant to changes in operating temperature range and changes over time than resistance film type input devices that have a two-layer structure of film and glass. Has advantages. In addition, the capacitive input device has an advantage that a light-transmitting conductive film is simply formed on a single substrate. The capacitive touch panel of the cover glass integrated type (OGS: One Glass Solution) touch panel has a front plate integrated with the capacitive input device, and thus can be reduced in thickness and weight.

In Patent Document 1, an image display member and a light-transmitting cover member having a light-shielding layer formed on a peripheral portion are light-transmitted through a light-transmitting cured resin layer formed from a liquid photocurable resin composition. In the manufacturing method of an image display device laminated so that the light shielding layer forming surface of the transmissive cover member is disposed on the image display member side, the manufacturing method of the image display device including the following steps (A) to (D) is provided. Are listed.
(A) A liquid photocurable resin composition is formed on the light shielding layer forming side surface of the light transmissive cover member or the surface of the image display member with the light shielding layer and the light shielding layer forming side surface of the light transmissive cover member. Applying thicker than the light-shielding layer so as to cancel the uneven step;
(B) A step of forming a temporarily-cured resin layer by irradiating the applied photo-curable resin composition with ultraviolet rays and temporarily curing the composition;
(C) A step of bonding the light-transmitting cover member to the image display member so that the light shielding layer and the temporarily cured resin layer are inside;
(D) The temporary curing resin layer sandwiched between the image display member and the light-transmitting cover member is irradiated with ultraviolet rays to be fully cured, thereby allowing the image display member and the light-transmitting cover member to transmit light. Step of obtaining an image display device by laminating through a photocurable resin layer:
In Patent Document 1, an image display device is manufactured by laminating an image display member and a light-transmitting cover member disposed on the surface side of the image display member via a cured resin layer of a photocurable resin composition by the above manufacturing method. In this case, the photocurable resin composition between the light shielding layer and the image display member is sufficiently cured without being excluded from the light shielding layer and the light transmissive property without using a thermal polymerization process. It is described that a step between the surface of the cover member can be canceled and an image display device can be manufactured only by a photopolymerization process.

JP 2014-81642 A

Smartphones and tablet PCs equipped with a capacitive touch panel on a liquid crystal or organic EL display have been developed and announced using a tempered glass typified by Corning's gorilla glass on the front plate (the surface directly touched by a finger) Has been.
Tempered glass is used for the glass substrate for the touch panel, and it is difficult to break even when impact force is applied, but in the unlikely event that the glass substrate breaks, it can also maintain the function as a capacitive input device It was left as a technical issue. In particular, when the glass substrate is broken, it is difficult for the electrode pattern to be disconnected. In other words, when the capacitance type input device includes a device for storing data, it is required that the data can be taken out.

However, Patent Document 1 neither discloses nor suggests that controlling the elastic modulus and elongation at break improves the suppression of disconnection of the electrode pattern when the front plate is cracked and bent.

The problem to be solved by the present invention is to provide means for suppressing the disconnection of the electrode pattern even if the front plate is cracked and bent.

The present inventors have laminated at least two transparent resin layers on a part or all of the front plate (one surface of the front plate), and further on the at least two transparent resin layers (at least two of the above). A transparent resin layer (first transparent resin layer) in contact with the electrode pattern, having a layer structure of a laminate having an electrode pattern on the surface of the transparent resin layer opposite to the surface facing the front plate) And the elastic modulus of the second transparent resin layer (second transparent resin layer) from the electrode pattern side satisfy a specific relationship, and further, the second transparent resin layer ( By increasing the breaking elongation of the second transparent resin layer), it was found that the electrode pattern disconnection can be suppressed even when the front plate is cracked and bent, and the present invention has been achieved.
Here, in Patent Document 1, the liquid photocurable resin composition is applied to the light shielding layer forming side surface of the light transmitting cover member or the surface of the image display member, and the light shielding layer forming side of the light transmitting cover member. The coating is thicker than the thickness of the light shielding layer so that the step formed between the surface and the surface is cancelled. Therefore, as in the laminate of the present invention, at least two transparent resin layers are laminated on a part or all of the front plate, and a layer structure having an electrode pattern on the at least two transparent resin layers. Was never disclosed or suggested. That is, the present invention is completely different from the invention described in Patent Document 1 in the layer configuration.

The present invention, which is a specific means for solving the above problems, is as follows.
[1] A laminate having at least two transparent resin layers laminated on a part or all of the front plate, and further having an electrode pattern on the at least two transparent resin layers,
The elastic modulus E1 of the first transparent resin layer in contact with the electrode pattern and the second transparent resin layer from the electrode pattern side (the side opposite to the surface facing the electrode pattern of the first transparent resin layer) The elastic modulus E2 of the second transparent resin layer that is a transparent resin layer in contact with the surface of
A laminate in which the elongation at break φ of the second transparent resin layer satisfies the following formula 2.
E1> E2 Formula 1
φ ≧ 10% Formula 2
[2] In the laminate according to [1], the total thickness of the first transparent resin layer and the second transparent resin layer is preferably 10 to 150 μm.
[3] In the laminate according to [1] or [2], it is preferable that the film thickness of the first transparent resin layer and the film thickness of the second transparent resin layer are each independently 5 to 100 μm. .
[4] In the laminate according to any one of [1] to [3], at least one of the transparent resin layers preferably contains a compound having a siloxane structure.
[5] In the laminate according to any one of [1] to [4], it is preferable that the first transparent resin layer includes at least a silicone resin as a binder resin.
[6] In the laminate according to any one of [1] to [5], the second transparent resin layer preferably contains at least silicone rubber as a binder resin.
[7] In the laminated body according to any one of [1] to [6], the elongation at break [phi] of the second transparent resin layer is preferably 20% or more.
[8] In the laminated body according to any one of [1] to [7], the elastic modulus E2 of the second transparent resin layer is preferably 50 MPa or less.
[9] In the laminated body according to any one of [1] to [8], the elastic modulus E1 of the first transparent resin layer is preferably 100 MPa or more.
[10] In the laminate according to any one of [1] to [9], a decoration layer is disposed on a part of one surface of the front plate, and the first transparent resin layer and the second layer are arranged. The transparent resin layer is laminated on a part of the surface of the front plate on which the decoration layer is arranged on the decoration layer and a part on which the decoration layer is not formed. preferable.
[11] a temporary support;
A first transparent resin layer containing at least a silicone resin as a binder resin;
A transfer film having a second transparent resin layer containing at least silicone rubber as a binder resin,
The transfer film having a structure in which the first transparent resin layer is sandwiched between the temporary support and the second transparent resin layer.
[12] The transfer film according to [11] preferably has a thermoplastic resin layer between the temporary support and the first transparent resin layer.
[13] The first transparent resin layer and the second transparent resin layer of the transfer film according to [11] or [12], a front plate, the second transparent resin layer, and the first A step of transferring to a part or all of the front plate so that the transparent resin layer is laminated in this order;
The method for producing a laminate according to any one of [1] to [10], including a step of forming an electrode pattern on the first transparent resin layer.
[14] A second transparent resin layer forming step of transferring a second transparent resin layer containing at least silicone rubber as a binder resin from the transfer film to a part or all of the front plate;
A first transparent resin layer containing at least a silicone resin as a binder resin from the transfer film so that the front plate, the second transparent resin layer, and the first transparent resin layer are laminated in this order. Forming a first transparent resin layer to be transferred onto the second transparent resin layer;
Forming an electrode pattern on the first transparent resin layer,
The production of the laminate according to any one of [1] to [10], wherein the forming step of the second transparent resin layer and the forming step of the first transparent resin layer are simultaneous or continuous transfer steps. Method.
[15] A step of forming a second transparent resin layer in which a resin composition (second coating solution for a transparent resin layer) containing at least silicone rubber as a binder resin is applied to a part or all of the front plate;
The resin composition containing at least a silicone resin as a binder resin, the second transparent resin is laminated so that the front plate, the second transparent resin layer, and the first transparent resin layer are laminated in this order. Forming a first transparent resin layer applied on the resin layer;
Forming an electrode pattern on the first transparent resin layer,
The method for producing a laminate according to any one of [1] to [10], wherein the forming step of the second transparent resin layer and the forming step of the first transparent resin layer are continuous coating steps.
[16] A conductive film laminate having a second electrode pattern electrically insulated from the electrode pattern on the electrode pattern of the laminate according to any one of [1] to [10].
[17] In the conductive film laminate according to [16], it is preferable that the second electrode pattern is a transparent electrode pattern.
[18] A capacitance-type input device including the conductive film laminate according to [16] or [17].
[19] An image display device comprising the capacitive input device according to [18] as a constituent element.

According to the present invention, it is possible to provide a laminate that can suppress the disconnection of the electrode pattern even if the front plate is cracked and bent.

It is sectional drawing which shows the structure of an example of the electrostatic capacitance type input device of this invention. It is explanatory drawing which shows an example of the front plate in this invention. It is explanatory drawing which shows an example of the 1st transparent electrode pattern in this invention, and a 2nd transparent electrode pattern. It is a top view which shows an example of the tempered glass in which the opening part was formed. It is a top view which shows an example of the front board in which the decoration layer was formed. It is a top view which shows an example of the front plate in which the 1st transparent electrode pattern was formed. It is a top view which shows an example of the front plate in which the 1st and 2nd transparent electrode pattern was formed. It is a top view which shows an example of the front plate in which the electroconductive element different from a black decorating layer and the 1st and 2nd transparent electrode pattern was formed. It is explanatory drawing which shows a metal nanowire cross section. It is the schematic which shows the shape after die-cutting of the transfer film used in order to form a decorating layer. It is explanatory drawing which shows the method of die-cutting the transfer film used in order to form a decorating layer. It is explanatory drawing which shows the die-cutting method of the transfer film used in order to form a decorating layer in the X1-X2 cross section of a front plate. It is explanatory drawing which shows the die-cutting method of the transfer film used in order to form a decorating layer in the Y1-Y2 cross section of a front plate. It is sectional drawing which shows the structure of another example of the electrostatic capacitance type input device of this invention. It is a cross-sectional schematic diagram which shows the structure of an example of the laminated body of this invention, and the relationship of the electrode pattern disconnection at the time of a crack having arisen in the front board. It is a section schematic diagram showing composition of other examples of a layered product of the present invention. It is a cross-sectional schematic diagram which shows the structure of laminated bodies, such as Comparative Examples 2 and 3, and the relationship of the electrode pattern disconnection at the time of a crack having arisen in the front plate. It is a cross-sectional schematic diagram which shows the structure of laminated bodies, such as Comparative Examples 4, 5, and 7, and the relationship of the electrode pattern disconnection at the time of a crack having arisen in the front plate.

Hereinafter, the laminate, the transfer film, the laminate production method, the conductive film laminate, the capacitive input device, and the image display device of the present invention will be described.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

[Laminate]
In the laminate of the present invention, at least two transparent resin layers are laminated on a part or all of the front plate (one surface of the front plate), and further on the at least two transparent resin layers (at least the above-mentioned at least The elastic modulus E1 of the first transparent resin layer that is a laminate having an electrode pattern on the surface of the two transparent resin layers opposite to the surface facing the front plate) And the elastic modulus E2 of the second transparent resin layer which is the second transparent resin layer from the electrode pattern side satisfies the following formula 1, and the breaking elongation φ of the second transparent resin layer satisfies the following formula 2. .
E1> E2 Formula 1
φ ≧ 10% Formula 2

<Configuration>
First, the structure of the laminated body of this invention is demonstrated, referring drawings.
FIG. 15A is a schematic cross-sectional view of an example of the laminate of the present invention. This laminate is a laminate having the second transparent resin layer 102 and the first transparent resin layer 101 on the front plate 1 and the electrode pattern 3 on the first transparent resin layer.
Here, the elastic modulus E1 of the first transparent resin layer 101 in contact with the electrode pattern and the elastic modulus E2 of the second transparent resin layer 102 which is the second transparent resin layer from the electrode pattern side are as follows: Expression 1 is satisfied, and the elongation at break φ of the second transparent resin layer 102 satisfies Expression 2 below.
E1> E2 Formula 1
φ ≧ 10% Formula 2
With such a configuration, the laminate of the present invention can suppress electrode pattern disconnection even when the front plate is cracked and bent. That is, as shown in FIG. 15A, the first transparent resin layer 101 having a high elastic modulus that is in contact with the electrode pattern 3 and the second transparent resin layer from the electrode pattern side have a low elastic modulus and a high value. As shown in FIG. 15 (B), an example of the laminate of the present invention provided with the second transparent resin layer 102 having an elongation at break is a second material having a low elastic modulus and a high elongation at break when the front plate 1 is cracked. The transparent resin layer 102 acts as an absorber that absorbs impact without cracking, and the first transparent resin layer 101 having a high elastic modulus that is in contact with the electrode pattern is laminated adjacently, thereby Since the bending of the absorbed second elastic resin layer 102 having a low elastic modulus and high elongation at break does not increase, disconnection of the electrode pattern 3 provided on the first transparent resin layer 101 can be suppressed.

In the laminate of the present invention, at least two transparent resin layers are laminated on part or all of the front plate. The transparent resin layer includes a first transparent resin layer that is in contact with the electrode pattern, and a second transparent resin layer that is a second transparent resin layer from the electrode pattern side. As a transparent resin layer, you may have other transparent resin layers other than a 1st transparent resin layer and a 2nd transparent resin layer. FIG. 16 shows a schematic cross-sectional view of another example of the laminate of the present invention. Another example of the laminate of the present invention shown in FIG. 16 includes a first transparent resin layer 101 that is in contact with the electrode pattern 100 and a second transparent resin layer that is the second transparent resin layer from the electrode pattern side. In addition to the transparent resin layer 102 (the second transparent resin layer 102 in contact with the surface opposite to the surface facing the electrode pattern 100 of the first transparent resin layer 101), the front plate 110 and the second transparent resin Another transparent resin layer 103 is provided between the layers 102. Thus, even if it has other transparent resin layers 103, the first transparent resin layer and the second transparent resin layer function sufficiently, and the laminate of the present invention is bent due to a crack in the front plate. Even in this case, disconnection of the electrode pattern can be suppressed.

In the laminate of the present invention, it is preferable that at least two transparent resin layers are laminated on a part of the front plate, and a decoration formed in a frame shape (frame shape) on a part of the front plate. It is more preferable that at least two transparent resin layers are laminated on the inner region of the frame-shaped decorative layer on the front plate. In the laminate of the present invention, the first transparent resin layer and the second transparent resin layer are in front of the decorative layer arranged on a part of one surface of the front plate and the front plate. It is particularly preferable that the face plate is formed on the same surface as the side on which the decorative layer is formed, on a portion where the decorative layer is not formed and on a part of the decorative layer.
Hereinafter, the preferable aspect of the laminated body of this invention is demonstrated.

<Front plate>
The laminate of the present invention has a front plate. Hereinafter, the front plate may be referred to as a “base material”.
The front plate is preferably a transparent front plate (translucent substrate), more preferably a glass substrate or a resin substrate, and particularly preferably a glass substrate.
As the glass substrate, a special glass plate such as aluminosilicate glass (for example, trade name “Gollilla (manufactured by Corning)”, “Dragonrail (manufactured by Asahi Glass)”) or chemically strengthened soda lime glass may be used. These can be used as a glass substrate serving as both a cover glass and a glass on which a touch panel sensor is formed. Since the touch panel sensor is provided on one piece of glass, the number of parts for one piece of glass can be reduced, and the touch panel can be manufactured at low cost.

<Electrode pattern>
The laminate of the present invention has an electrode pattern on the at least two transparent resin layers (the surface opposite to the surface facing the front plate of the at least two transparent resin layers).
A preferred embodiment of the electrode pattern is as described in the conductive film laminate and the capacitance-type input device of the present invention described later, and the electrode pattern on the at least two transparent resin layers is described in (1 It is preferable that the plurality of pad portions are a plurality of first transparent electrode patterns formed extending in the first direction via the connection portions.
The transparent electrode used for the electrode pattern is made of a material that is transparent and conductive and can be formed into a thin film. Usually, an ITO (Indium Tin Oxide) film is used, and the other is an IZO (Indium Zinc). Oxide, a composite oxide of indium and zinc) and a light-transmitting conductive metal oxide film or metal film such as a SnO ₂ (tin dioxide) film can be used. Examples of such translucent conductive metal oxide films and metal films include metal oxide films such as ITO, IZO, SnO ₂ , and SiO ₂ ; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo And so on. Organic conductive materials such as polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT / PSS), polyaniline, and polypyrrole can also be used. These materials may be used alone or in combination of two or more. Among these, it is preferable to use ITO in terms of transparency and resistance value.
Each film can be formed by a general film forming method such as a PVD method such as a sputtering method or a vacuum evaporation method, or a CVD method.
At this time, the film thickness of the electrode pattern can be 10 to 200 nm. Further, by firing, an amorphous ITO film or the like can be used as a polycrystalline ITO film or the like, and the electrical resistance can be reduced.

<Transparent resin layer>
In the laminate of the present invention, the elastic modulus E1 of the first transparent resin layer and the elastic modulus E2 of the second transparent resin layer satisfy the following formula 1, and the elongation at break φ of the second transparent resin layer Satisfies the following formula 2.
E1> E2 Formula 1
φ ≧ 10% Formula 2

In the laminate of the present invention, it is preferable that at least the gap between the electrode pattern and the front plate is filled with the at least two transparent resin layers.
The method for filling at least the gap between the electrode pattern and the front plate with the at least two transparent resin layers is not particularly limited, but the transfer film of the present invention described later is described in the method for forming a decorative layer described later. The width (L) of the at least two transparent resin layers is adjusted to the same size as the inner diameter (one side) of the decorative layer by using a transfer method that has undergone a half-cut process or a transfer method that has undergone a die-cut process. The at least two transparent resin layers are preferably transferred onto the front plate.
A preferred embodiment of the method for transferring the at least two transparent resin layers to the front plate is the same as the preferred embodiment of the method for forming the decorative layer using the transfer film.
On the other hand, the liquid resist for the at least two transparent resin layers is applied or printed at least in a gap portion between the electrode pattern and the front plate, and cured by a known method, so that at least the electrode pattern and the previous liquid resist are cured. The gap between the face plate and the face plate may be filled with the at least two transparent resin layers.

In the laminate of the present invention, the at least two transparent resin layers are preferably heated to 180 to 300 ° C. in an environment of 0.08 to 1.2 atm from the viewpoint of both transparency and productivity. . The preferable aspect of a heating is the same as the preferable aspect of the post-baking in the formation method of the below-mentioned decorating layer.

The first transparent resin layer and the second transparent resin layer may be in a state where the fluidity is maintained, may be in a state where the fluidity is lost, or may be in a cured or fixed state. Good.
That is, in the laminate of the present invention, even if the first transparent resin layer and the second transparent resin layer exist in the state of a transparent resist that maintains fluidity, the fluidity is lost by drying the transparent resist. It may exist in the state.
In the laminate of the present invention, the first transparent resin layer and the second transparent resin layer may be cured by irradiation with actinic radiation. Hereinafter, preferred embodiments of at least two transparent resin layers will be described.

(Elastic modulus)
In the laminate of the present invention, the elastic modulus E1 of the first transparent resin layer in contact with the electrode pattern and the elastic modulus of the second transparent resin layer that is the second transparent resin layer from the electrode pattern side E2 satisfies the following formula 1.
E1> E2 Formula 1
The elastic modulus E1 of the first transparent resin layer and the elastic modulus E2 of the second transparent resin layer preferably satisfy the following formula 1A, and more preferably satisfy the following formula 1B.
2000 × E2>E1> 5 × E2 Formula 1A
1000 × E2>E1> 10 × E2 Formula 1B
The elastic modulus E1 of the first transparent resin layer is preferably 100 MPa or more, more preferably 300 MPa or more, and particularly preferably 500 MPa or more. Although there is no restriction | limiting in particular in the upper limit of the elasticity modulus E1 of a 1st transparent resin layer, It is preferable that it is 2000 MPa or less, and it is more preferable that it is 1000 MPa or less.
The elastic modulus E2 of the second transparent resin layer is preferably 50 MPa or less, more preferably 30 MPa or less, and particularly preferably 20 MPa or less. The lower limit value of the elastic modulus E2 of the second transparent resin layer is not particularly limited, but is preferably 2 MPa or more, and more preferably 5 MPa or more.

(Elongation at break)
In the laminate of the present invention, the breaking elongation φ of the second transparent resin layer, which is the second transparent resin layer from the electrode pattern side, satisfies the following formula 2.
φ ≧ 10% Formula 2
The breaking elongation φ of the second transparent resin layer is preferably 20% or more, more preferably 30% or more, particularly preferably 100% or more, and particularly preferably 200% or more. . The upper limit of the breaking elongation φ of the second transparent resin layer is not particularly limited, but is preferably 1000% or less, and more preferably 600% or less.

(Thickness)
In the laminate of the present invention, the total thickness of the first transparent resin layer and the second transparent resin layer is preferably 10 to 150 μm, more preferably 20 to 120 μm, A thickness of 30 to 100 μm is particularly preferable. In particular, when the decorative layer is a white decorative layer, it is preferable to increase the thickness of the white decorative layer. Therefore, the gap produced by the height difference between the front plate and the white decorative layer using the first transparent resin layer and the second transparent resin layer (hereinafter also referred to as “step of the decorative layer”). In order to fill the thickness, the total thickness of the first transparent resin layer and the thickness of the second transparent resin layer is more preferably 20 μm or more.
It is preferable that the film thickness of the first transparent resin layer and the film thickness of the second transparent resin layer are each independently 5 to 100 μm.
The film thickness of the first transparent resin layer is preferably 5 to 100 μm, more preferably 10 to 90 μm, and particularly preferably 15 to 70 μm. The first transparent resin layer having a high elastic modulus is preferably thinner from the viewpoint of enhancing the transparency even if it is a heat-colored material such as an acrylic resin.
The film thickness of the second transparent resin layer is preferably 5 to 100 μm, more preferably 10 to 70 μm, and particularly preferably 15 to 40 μm. The second transparent resin layer having a low elastic modulus and high elongation at break can be made more transparent when the film thickness is thinner, even when the second transparent resin layer contains particles such as silica for the purpose of improving physical properties. It is preferable from the viewpoint.

(composition)
-Compound having siloxane structure-
In the laminate of the present invention, at least one of the transparent resin layers contains a compound having a siloxane structure, the transparency after heat-curing the transparent resin layer, and the electrode pattern heat annealing step which is a subsequent step From the viewpoint of increasing the transparency of the transparent resin layer, it is preferable.
The compound having a siloxane structure refers to a compound having at least one siloxane bond in the molecule. The compound having a siloxane structure is preferably a polysiloxane compound (so-called silicone) having a plurality of siloxane bonds in the molecule.
Silicone can be classified into silicone rubber, which is an elastomer having rubber elasticity at room temperature, and other silicone resins.

--silicone rubber--
In the laminate of the present invention, it is preferable that the second transparent resin layer contains at least silicone rubber as a binder resin. Silicone rubber is generally excellent in heat resistance and transparency.
A silicone rubber compound (silicone) containing a compound having a raw rubber-like siloxane structure (for example, highly polymerized dimethylpolysiloxane) and particles (for example, finely divided silica) as reinforcing materials and various additives as necessary. A rubber precursor) is obtained. When this silicone rubber compound is added with a vulcanizing agent such as an organic peroxide or a catalyst as needed and cured by heating, silicone rubber in a narrow sense can be obtained. The silicone rubber in this specification includes both a silicone rubber compound and a narrowly defined silicone rubber after heat curing.

Silicone rubber includes silicone composed of linear polyorganosiloxane having vinyl groups only at both ends, silicone composed of linear polyorganosiloxane having vinyl groups at both ends and side chains, and vinyl groups only at the ends. And a product obtained by crosslinking at least one silicone selected from a silicone comprising a branched polyorganosiloxane having a salt and a silicone comprising a branched polyorganosiloxane having a vinyl group at the terminal and side chain.

The linear polyorganosiloxane having a vinyl group only at both ends is a compound represented by any one of the following general formulas A-1 to A-3. Examples of the silicone rubber include a gum-like dimethylpolysiloxane having a high degree of polymerization and a gum-like dimethylsiloxane / methylphenylsiloxane copolymer.

(In the above general formulas A-1 to A-3, R represents the following organic group, and n represents an integer)

(In the above general formula B, R represents the following organic group, and m represents an integer)
The organic group (R) bonded to the silicon atom other than the vinyl group may be different or of the same type. Specific examples include alkyl groups such as methyl, ethyl and propyl groups, and aryl groups such as phenyl and tolyl groups. Or a monovalent hydrocarbon group other than the same or different unsubstituted or substituted aliphatic unsaturated group in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, a cyano group, or the like. Preferable examples include those having at least 50 mol% of a methyl group. These diorganopolysiloxanes may be used alone or as a mixture of two or more thereof.

A silicone comprising a linear polyorganosiloxane having vinyl groups at both ends and side chains is a compound in which a part of R in the above general formulas A-1 to A-3 is a vinyl group. Silicone comprising a branched polyorganosiloxane having a vinyl group only at the terminal is a compound represented by the above general formula B. A silicone composed of a branched polyorganosiloxane having vinyl groups at the terminals and side chains is a compound in which a part of R in the general formula B is a vinyl group.

Here, the crosslinking agent used for the crosslinking reaction may be a known one. Examples of the crosslinking agent include organohydrogenpolysiloxane. Organohydrogenpolysiloxane has at least three hydrogen atoms bonded to silicon atoms in one molecule, but from a practical point of view, it has a total amount of those having two ≡SiH bonds in the molecule. The mass is preferably up to mass%, and the remainder preferably contains at least three ≡SiH bonds in the molecule.

The catalyst used for the crosslinking reaction is preferably a platinum-based catalyst. The platinum-based catalyst may be a known platinum-based catalyst, such as chloroplatinic acid such as chloroplatinic acid and chloroplatinic acid, an alcohol compound of chloroplatinic acid, an aldehyde compound of chloroplatinic acid, or chloroplatinic acid. Complex salts with various olefins are used. The crosslinked silicone layer has flexibility such as silicone rubber, and this flexibility facilitates the close contact with the adherend.

The shape of the commercially available silicone rubber used in the present invention includes a solventless type, a solvent type, and an emulsion type, and any type can be used. Above all, the solventless type is very advantageous in terms of safety, hygiene, and air pollution because it does not use a solvent. In consideration of economy, it is preferable to use a solventless silicone rubber.

The silicone rubber preferably contains particles, more preferably contains inorganic particles, and particularly preferably at least one kind of particles of silica, titania and zirconia.

Examples of the silicone rubber include KE-109, KE-106, KE-1031, KE-103, KE-108, KE-581U, KE-167U, KE-1820 and KE-1886 from Shin-Etsu Chemical Co., Ltd. KE-167U, KE-1820 and KE-1886 are preferred.

--- Silicone resin--
In the laminate of the present invention, the first transparent resin layer preferably contains at least a silicone resin as a binder resin.
A well-known thing can be used as said silicone resin used for a said 1st transparent resin layer.
Silicone resin is a straight resin that utilizes the inherent properties of silicone by dehydrating and condensing a modified silicone resin with various properties and a silane compound having an alkoxy group or silanol group. It can be classified as a silicone resin. In the laminate and transfer film of the present invention, the silicone resin is preferably a modified silicone resin or a straight silicone resin, more preferably a straight silicone resin, and at least the following general formula (1) in the molecule. A straight silicone resin containing a siloxane structure represented by
As the modified silicone resin, an acrylic resin-modified silicone resin (such as KR-9706 manufactured by Shin-Etsu Chemical Co., Ltd.) obtained by polymerizing a monomer obtained by reacting an acrylic monomer such as acrylic acid with a silane compound or copolymerizing it with another acrylic monomer, Polyester resin-modified silicone resins (such as KR-5230 manufactured by Shin-Etsu Chemical Co., Ltd.) obtained by reacting a hydroxyl group of the polyester with a silane compound, and epoxy resin-modified silicone resins obtained by reacting an amino group residue of the resin with an epoxy-containing silane compound An alkyd resin-modified silicone resin obtained by modifying an alkyd resin with a reactive silane compound, a rubber-based silicone resin that directly forms a covalent bond with the resin using an oxime initiator, and the like can be used. Among these, the acrylic-modified silicone resin or the polyester-modified silicone resin, or the silicone resin containing these as a copolymer component further effectively prevents the electrode pattern from being disconnected when the front plate is cracked and bent. From the viewpoint of being able to do so.

As the straight silicone resin, one containing at least a siloxane structure represented by the following general formula (1) in the molecule can be used.

In the general formula (1), R ¹ is independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear or branched structure having 1 to 20 carbon atoms. Or a cyclic alkyl group, a linear, branched or cyclic substituted alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, and an aryl having 6 to 20 carbon atoms A group or an aralkyl group having 7 to 20 carbon atoms, and a plurality of R ¹ may be the same or different. That is, the straight silicone resin having a siloxane structure represented by the general formula (1) may be a condensate having the same siloxane structure or a co-condensate having a different combination.

Examples of the halogen atom represented by R ¹ include a fluorine atom and a chlorine atom.
Examples of the linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms represented by R ¹ include, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group. Group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, cyclopentyloxy group, cyclohexyloxy group and the like.
Examples of the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. Group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like. Among the linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms represented by R ¹ , an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
Examples of the linear, branched or cyclic substituted alkyl group having 1 to 20 carbon atoms represented by R ¹ include an arylalkyl group, a fluoroalkyl group, a chloroalkyl group, a hydroxyalkyl group, and a (meth) acryloxyalkyl group. Groups and mercaptoalkyl groups. Specific examples thereof include, for example, phenylmethyl (benzyl) group, diphenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl-n-propyl group, 2-phenyl-2-propyl (cumyl). ) Group, 3-phenyl-n-propyl group, 1-phenylbutyl group, 2-phenylbutyl group, 3-phenylbutyl group, 4-phenylbutyl group, 1-phenylpentyl group, 2-phenylpentyl group, 3- Phenylpentyl group, 4-phenylpentyl group, 5-phenylpentyl group, 1-phenylhexyl group, 2-phenylhexyl group, 3-phenylhexyl group, 4-phenylhexyl group, 5-phenylhexyl group, 6-phenylhexyl Group, 1-phenylcyclohexyl group, 2-phenylcyclohexyl group, 3-phenylcyclohexyl group 1-phenylheptyl group, 2-phenylheptyl group, 3-phenylheptyl group, 4-phenylheptyl group, 5-phenylheptyl group, 6-phenylheptyl group, 1-phenyloctyl group, 2-phenyloctyl group, 3- Phenyloctyl group, 4-phenyloctyl group, 5-phenyloctyl group, 6-phenyloctyl group, 1-naphthylethyl group, 2-naphthylethyl group, 1-naphthyl-n-propyl group, 2-naphthyl-2-propyl group Group, 3-naphthyl-n-propyl group, 1-naphthylbutyl group, 2-naphthylbutyl group, 3-naphthylbutyl group, 4-naphthylbutyl group, 1-naphthylpentyl group, 2-naphthylpentyl group, 3-naphthyl Pentyl group, 4-naphthylpentyl group, 5-naphthylpentyl group, 1-naphthylhexyl group, 2-naphthyl Hexyl group, 3-naphthylhexyl group, 4-naphthylhexyl group, 5-naphthylhexyl group, 6-naphthylhexyl group, 1-naphthylcyclohexyl group, 2-naphthylcyclohexyl group, 3-naphthylcyclohexyl group, 1-naphthylheptyl group 2-naphthylheptyl group, 3-naphthylheptyl group, 4-naphthylheptyl group, 5-naphthylheptyl group, 6-naphthylheptyl group, 1-naphthyloctyl group, 2-naphthyloctyl group, 3-naphthyloctyl group, 4 -Arylalkyl groups such as naphthyloctyl group, 5-naphthyloctyl group, 6-naphthyloctyl group, etc .; fluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, (trifluoromethyl) methyl group, pentafluoroethyl group , 3-fluoro-n-propyl group, 2- ( (Trifluoromethyl) ethyl group, (pentafluoroethyl) methyl group, heptafluoro-n-propyl group, 4-fluoro-n-butyl group, 3- (trifluoromethyl) -n-propyl group, 2- (pentafluoro Ethyl) ethyl group, (heptafluoro-n-propyl) methyl group, nonafluoro-n-butyl group, 5-fluoro-n-pentyl group, 4- (trifluoromethyl) -n-butyl group, 3- (pentafluoro Ethyl) -n-propyl group, 2- (heptafluoro-n-propyl) ethyl group, (nonafluoro-n-butyl) methyl group, perfluoro-n-pentyl group, 6-fluoro-n-hexyl group, 5- (Trifluoromethyl) -n-pentyl group, 4- (pentafluoroethyl) -n-butyl group, 3- (heptafluoro-n-propyl) -n Propyl group, 2- (nonafluoro-n-butyl) ethyl group, (perfluoro-n-pentyl) methyl group, perfluoro-n-hexyl group, 7- (trifluoromethyl) -n-heptyl group, 6- ( Pentafluoroethyl) -n-hexyl group, 5- (heptafluoro-n-propyl) -n-pentyl group, 4- (nonafluoro-n-butyl) -n-butyl group, 3- (perfluoro-n-pentyl) ) -N-propyl group, 2- (perfluoro-n-hexyl) ethyl group, (perfluoro-n-heptyl) methyl group, perfluoro-n-octyl group, 9- (trifluoromethyl) -n-nonyl Group, 8- (pentafluoroethyl) -n-octyl group, 7- (heptafluoro-n-propyl) -n-heptyl group, 6- (nonafluoro-n-butyl) -n-he Sil group, 5- (perfluoro-n-pentyl) -n-pentyl group, 4- (perfluoro-n-hexyl) -n-butyl group, 3- (perfluoro-n-heptyl) -n-propyl group Fluoroalkyl groups such as 2- (perfluoro-n-octyl) ethyl group, (perfluoro-n-nonyl) methyl group, perfluoro-n-decyl group, 4-fluorocyclopentyl group, 4-fluorocyclohexyl group; Chloromethyl group, 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 3-chlorocyclopentyl group, 4-chlorocyclohexyl group, hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxycyclopentyl group, 4-hydroxycyclohexyl group, 3- (meth) acryloxypropyl group, 3-mercapto A propyl group etc. can be mentioned.
Examples of the linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms represented by R ¹ include, for example, vinyl group, 1-methylvinyl group, 1-propenyl group, allyl group (2-propenyl group). 2-methyl-2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 3-cyclopentenyl group, 3-cyclohexenyl group and the like. Of the linear, branched or cyclic substituted alkyl groups having 1 to 20 carbon atoms represented by R ¹ , arylalkyl groups are preferred, and cumyl groups are more preferred.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹ include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, and 2,4-xylyl group. 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 1-naphthyl group and the like. Among the aryl groups having 6 to 20 carbon atoms represented by R ¹ , other than unsubstituted phenyl groups, that is, o-tolyl group, m-tolyl group, p-tolyl group, , 3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 1-naphthyl, A tolyl group, m-tolyl group, and p-tolyl group are more preferred.
Examples of the aralkyl group having 7 to 20 carbon atoms represented by R ¹ include a benzyl group and a phenethyl group.

In the general formula (1), R ¹ is independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic group having 1 to 6 carbon atoms. Are preferably substituted alkyl groups or aryl groups having 6 to 9 carbon atoms, and more preferably represent a hydrogen atom, a methyl group, a phenyl group or a tolyl group.
The siloxane structure represented by the general formula (1) preferably contains a methyl group as R ¹ from the viewpoint of particularly enhancing the L value of the decorative layer.

The straight silicone resin includes two or more general formulas (1) in which R ¹ are different from each other.
It is also preferable that it is a copolymer of the siloxane structure represented by these. In this case, the siloxane structure represented by the general formula (1) in which R ¹ is an alkyl group and the siloxane structure represented by the general formula (1) in which R ¹ is a hydrogen atom, a substituted alkyl group, or an aryl group. And a copolymer thereof. The copolymerization ratio is not particularly limited, but the siloxane structure represented by the general formula (1) in which R ¹ is an alkyl group is 50 to 50% of all the siloxane structures represented by the general formula (1). The amount is preferably 100 mol%, more preferably 60 to 100 mol%, and particularly preferably 70 to 100 mol%.

As a straight silicone resin used in the present invention, a siloxane structure comprising a co-condensation with a siloxane structure represented by the following general formula (2) in addition to the siloxane structure represented by the general formula (1) in the molecule. The thing containing this can also be used preferably.

In general formula (2), R ² has the same meaning as R ^{1 in} general formula (1), and the preferred range is also the same as R ¹ .

Specific examples of straight silicone resins include alkyl straight silicones prepared from the condensation of silane compounds having an alkyl group having 1 to 20 carbon atoms and an alkoxy group (methyl straight silicones, etc.), alkyl-aryls such as methylphenyl, etc. Straight silicone, aryl straight silicone such as phenyl, and hydrogen straight silicone such as methyl hydrogen can be used.
More preferred are methyl-based straight silicone resins, methyl-tolyl-based straight silicone resins, methyl-phenyl-based straight silicone resins, acrylic resin-modified silicone resins, methyl-hydrogen-based straight silicone resins, and hydrogen-hydrogen-based straight silicone resins. From the viewpoint of preventing the decrease in lightness without generating benzene, methyl straight silicone resin, methyl tolyl straight silicone resin, methyl hydrogen straight silicone resin, and hydrogen tol straight silicone resin are particularly preferable.
These silicone resins may be used alone or in combination of two or more, and the film properties can be controlled by mixing them at an arbitrary ratio.

The weight average molecular weight of the straight silicone resin is preferably 1000 to 5000000, more preferably 2000 to 3000000, and particularly preferably 2500 to 3000000. When the molecular weight is 1000 or more, the film forming property is good.

The weight average molecular weight in this specification can be measured by, for example, gel permeation chromatography (GPC). Specifically, it can be measured under the following conditions.
Column: GPC column TSKgelSuper HZM-H (manufactured by Tosoh Corporation)
・ Solvent: Tetrahydrofuran ・ Standard: Monodisperse polystyrene

As a silane compound used to prepare a modified silicone resin and a straight silicone resin,
Tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltributoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane , Cumyltrimethoxysilane, tolyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropi Trimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxy Silane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycid Xylethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypro Pyrtriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxy Propyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycid Xylbutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycid Xibutyltrimethoxy , Δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4 Epoxycyclohexyl) propyltri Trialkoxy such as toxisilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, triacyloxy or triphenoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropyl Methyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethyldimethoxysilane, γ-mercaptopropyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, vinylmethyl Dimethoxysilane, vinylmethyldiethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethyldiethoxysilane, α-glycidoxyethyl ester Rudimethoxysilane, α-glycidoxyethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxy Propylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ- Glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyl Methoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycid Alkoxysilanes or diacyloxysilanes such as xylpropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, dimethoxymethylsilane, trimethoxysilane, dimethylethoxysilane, diacetoxymethylsilane, diethoxymethylsilane, diethylmethyl Silane, triethylsilane, butyldimethylsilane, dimethylphenylsilane, methylphenylvinylsilane, diphenylmethylsilane, tripropylsilane, tripentyloxysilane, Nylsilane, trihexylsilane, diethylsilane, allyldimethylsilane, methylphenylsilane, diphenylsilane, phenylsilane, octylsilane, 1,4-bis (dimethylsilyl) benzene, and 1,1,3,3-tetramethyldisiloxane , Dimethyltolylsilane, methyltolylvinylsilane, ditolylmethylsilane, tolylylsilane, dimethylbenzylsilane, methylbenzylvinylsilane, dibenzylmethylsilane, tribenzylsilane, diphenylsilane, 2-chloroethylsilane, bis [(p-dimethyl Silyl) phenyl] ether, 1,4-dimethyldisilylethane, 1,3,5-tris (dimethylsilyl) benzene, 1,3,5-trimethyl-1,3,5-trisilane, poly (methylsilylene) phenylene ,as well as Poly (methylsilylene) methylene, tetrachlorosilane, trichlorosilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, fluorotrichlorosilane, fluoro Trimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, methyltrichlorosilane, methyltri-n-propoxy Silane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, 2- (trifluoromethyl) ethyltrichlorosilane, 2- (trifluoromethyl) Rutrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri-i-propoxysilane, 2- (trifluoromethyl ) Ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-hexyl) ethyltrichlorosilane, 2- (perfluoro-n-hexyl) ethyltrimethoxysilane 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysilane, 2- (Perfluoro-n-hexyl) ester Rutri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2- (perfluoro-n-octyl) ethyltri Methoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-octyl) ethyltri-i-propoxy Silane, 2- (perfluoro-n-octyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-octyl) ethyltri-sec-butoxysilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltri Methoxysilane, hydroxyme Tiltly-n-propoxysilane, hydroxymethyltri-i-propoxysilane, hydroxymethyltri-n-butoxysilane, hydroxymethyltri-sec-butoxysilane, 3- (meth) acryloxypropyltrichlorosilane, 3- (meth) Acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltri-i-propoxysilane, 3 -(Meth) acryloxypropyltri-n-butoxysilane, 3- (meth) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltri Toxisilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltri-n-butoxysilane, 3-mercaptopropyltri-sec-butoxysilane, vinyltrichlorosilane, Vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltri -I-propoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane, phenyltrichlorosilane, phenyltri-n-propoxysilane, phenyltri-i Propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, methyldichlorosilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi-i-propoxysilane, methyldi-n-butoxysilane, methyldi -Sec-butoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, (methyl) [2- (Perfluoro-n-octyl) ethyl] dichlorosilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl Til] diethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-i-propoxy Silane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-sec-butoxysilane, (methyl ) (Γ-glycidoxypropyl) dichlorosilane, (methyl) (γ-glycidoxypropyl) dimethoxysilane, (methyl) (γ-glycidoxypropyl) diethoxysilane, (methyl) (γ-glycidoxy Propyl) di-n-propoxysilane, (methyl) (γ-glycidoxypropyl) di-i-propoxysilane, (methyl) (γ-glycidoxypro ) Di-n-butoxysilane, (methyl) (γ-glycidoxypropyl) di-sec-butoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane, (methyl) (3-mercaptopropyl) dimethoxysilane , (Methyl) (3-mercaptopropyl) diethoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) di-i-propoxysilane, (methyl) ( 3-mercaptopropyl) di-n-butoxysilane, (methyl) (3-mercaptopropyl) di-sec-butoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, (methyl) ( Vinyl) diethoxysilane, (methyl) (vinyl) di-n-propoxysilane, (meth) ) (Vinyl) di-i-propoxysilane, (methyl) (vinyl) di-n-butoxysilane, (methyl) (vinyl) di-sec-butoxysilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane , Divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, Diphenyldi-i-propoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, Motrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) ( Vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane, (ethoxy) (methyl) diphenylsilane, etc. Can be mentioned respectively. However, the present invention is not limited to these specific examples.

Commercially available silicone resins such as modified silicone resins and straight silicone resins can be used. In the product name, for example,
KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5842, X-21-5844, X-21-5845, X-21-5845, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X-22-176B, X- 22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40-2672, X-40- 9220, X-40-9225, X-40-9226, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-40- 460M, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR-212, KR-213, KR-217, KR-220, KR- 240, KR-242A, KR-271, KR-282, KR-300, KR-311, KR-400, KR-251, KR-253, KR-255, KR-401N, KR-500, KR-510, KR-5206, KR-5230, KR-5235, KR-9218, KR-9706, KR-165 (above, Shin-Etsu Chemical Co., Ltd.);
SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, Toray Dow Corning);
YR3187, YR3370, TSR127B (Momentive Performance Materials Japan GK)
FZ3711, FZ3722 (above, Nippon Unicar Company);
DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS- 227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (above, Chisso);
Methyl silicate MS51, Methyl silicate MS56 (Mitsubishi Chemical Corporation);
Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (above, Colcoat);
Examples include partial condensates such as glass resin GR100, GR650, GR908, GR950 (above, Showa Denko). However, the present invention is not limited to these specific examples.

Here, the at least two transparent resin layers may not be formed by photocuring a resin composition containing a photocurable resin and a photopolymerization initiator. For forming the at least two transparent resin layers, The resin composition to be used may or may not contain a photocurable resin or a photopolymerization initiator. Among them, when the at least two transparent resin layers contain an antioxidant described later, it does not contain a photopolymerization initiator, and functions of the antioxidant by radicals generated when exposed to the photopolymerization initiator. Is not inhibited, and is preferable from the viewpoint of sufficiently increasing the whiteness after baking. Therefore, the compound having the siloxane structure is preferably thermosetting.

-Antioxidant-
In the present invention, the at least two transparent resin layers preferably contain an antioxidant from the viewpoint of increasing the transparency of the at least two transparent resin layers after baking. Here, when forming a transparent electrode pattern such as ITO on the capacitive input device, it is necessary to bake at a high temperature, but by adding an antioxidant, the at least two layers of transparent after baking are transparent. The transparency of the resin layer can be increased.
Known antioxidants can be used as the antioxidant. For example, hindered phenol antioxidants, semi-hindered phenol antioxidants, phosphoric acid antioxidants, and hybrid antioxidants having phosphoric acid and hindered phenol in the molecule can be used.
Preferably a phosphoric acid antioxidant; a combination of a phosphoric acid antioxidant and a hindered phenol antioxidant or a semi-hindered phenol antioxidant; or a hybrid antioxidant having phosphoric acid and hindered phenol in the molecule is there.
A commercially available antioxidant can also be used as the antioxidant. For example, examples of the phosphoric acid antioxidant include IRGAFOS168 and IRGAFOS38 (both manufactured by BASF Japan). IRGAMOD295 (manufactured by BASF Japan) can be mentioned as a phosphoric acid / hindered phenol-based antioxidant, and Sumiser GP (Sumitomo Chemical Co., Ltd.) as a hybrid type antioxidant having phosphoric acid and hindered phenol in the molecule. Manufactured).
The antioxidant is more preferably a phosphoric acid-based antioxidant from the viewpoint of improving the transparency after baking of the at least two transparent resin layers, and IRGAFOS 168 is particularly preferable.
The amount of the antioxidant added to the total solid content of the at least two transparent resin layers is not particularly limited, but is preferably 0.001 to 10% by mass, and 0.01 to 1% by mass. More preferably, it is 0.05 to 1% by mass.

-catalyst-
It is preferable that the at least two transparent resin layers contain a catalyst from the viewpoint of improving brittleness by curing the at least two transparent resin layers containing the compound having the siloxane structure. In particular, when two or more compounds having a siloxane structure are used, they are preferably used for promoting crosslinking by dehydration / dealcohol condensation reaction.
A known catalyst can be used as the catalyst.
As a preferable catalyst, tin (Sn), zinc (Zn), iron (Fe), titanium (Ti), zirconium (Zr), bismuth (Bi), hafnium (Hf), yttrium (Y), aluminum (as a metal component) Examples thereof include organic metal compound catalysts such as organic complexes or organic acid salts of at least one metal selected from the group consisting of Al), boron (B), and gallium (Ga).
Among these, Sn, Ti, Zn, Zr, Hf, and Ga are preferable from the viewpoint of high reaction activity, Zn or Ti is more preferable from the viewpoint of preventing cracking during baking, and Zn is particularly preferable from the viewpoint of improving pot life.
Examples of the organometallic compound catalyst containing zinc (Zn) include zinc triacetylacetonate, zinc stearate, bis (acetylacetonato) zinc (II) (monohydrate), and the like.
Examples of organometallic compound catalysts containing tin (Sn), titanium (Ti), zirconium (Zr), hafnium (Hf), and gallium (Ga) include, for example, the catalysts described in JP2012-238636A. It can be preferably used.
A commercially available catalyst can also be used as the catalyst. Examples thereof include zinc-based condensation catalyst D-15 (manufactured by Shin-Etsu Chemical Co., Ltd.).
One type of the catalyst may be used alone, or two or more types may be used in any combination and ratio. Moreover, you may use together with a reaction accelerator and reaction inhibitor.
The content of the catalyst is preferably 0.01 to 10% by mass with respect to the compound having the siloxane structure from the viewpoint of preventing cracking during baking and improving pot life, and more preferably 0.03 to 5%. 0.0% by mass.

-Additive-
Further, other additives may be used in the at least two transparent resin layers. Examples of the additive include surfactants described in paragraph 0017 of Japanese Patent No. 4502784, paragraphs 0060 to 0071 of JP-A-2009-237362, and prevention of thermal polymerization described in paragraph 0018 of Japanese Patent No. 4502784. And other additives described in paragraphs 0058 to 0071 of JP-A No. 2000-310706. The concentration of the surfactant contained in the at least two transparent resin layers is preferably 0.01% by mass to 10% by mass.

(Transparent resin layer production method)
Further, the method for producing the at least two transparent resin layers is not particularly limited, but can be formed by applying a preparation solution containing the compound having the siloxane structure and other additives. The preparation liquid used at the time can be prepared using a solvent.
As the solvent for producing at least two transparent resin layers by coating, the solvents described in JP-A-2011-95716, paragraphs 0043 to 0044 can be used.

<Decoration layer>
It is preferable that the laminated body of this invention has a functional layer arrange | positioned at the one surface side of the said front board, and it is preferable that this functional layer is a decoration layer.

In the laminate of the present invention, the thickness of the decorative layer is preferably 5 μm or more, more preferably 10 μm or more, and particularly when the decorative layer is a white decorative layer, the thickness of the white decorative layer Is preferably 30 μm or more.
In the laminate of the present invention, the total thickness of the at least two transparent resin layers is preferably 0.2 to 2.0 times the thickness of the decorative layer, preferably 0.3 to 1.5 times. It is more preferable that the ratio is 0.99 to 1.01 times.

(material)
-Colorant-
The decorative layer includes a colorant.

Examples of the black colorant include carbon black, titanium carbon, iron oxide, titanium oxide, and graphite. Among these, carbon black is preferable. In addition to the black colorant, a mixture of pigments such as red, blue, and green can be used.

As the white colorant, the white pigment described in paragraph 0019 of JP2009-191118A or paragraph 0109 of JP2000-175718A can be used. Also, white pigments described in paragraphs 0015 and 0114 of JP-A-2005-7765 can be used.
Specifically, in the present invention, white inorganic pigments such as titanium oxide (rutile type), titanium oxide (anatase type), zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate are used. Preferably, titanium oxide (rutile type), titanium oxide (anatase type) and zinc oxide are more preferable, titanium oxide (rutile type) and titanium oxide (anatase type) are more preferable, and rutile type titanium oxide is particularly preferable.

Specific examples of titanium dioxide include JR, JRNC, JR-301, 403, 405, 600A, 605, 600E, 603, 701, 800, 805, 806, JA-1, C, 3, 4, 5, MT- 01, 02, 03, 04, 05, 100AQ, 100SA, 100SAK, 100SAS, 100TV, 100Z, 100ZR, 150W, 500B, 500H, 500SA, 500SAK, 500SAS, 500T, SMT-100SAM, 100SAS, 500SAM, 500SAS Manufactured), CR-50, 50-2, 57, 58, 58-2, 60, 60-2, 63, 67, 80, 85, 90, 90-2, 93, 95, 97, 953, Super70, PC -3, PF-690, 691, 711, 736, 737, 739, 740, 42, R-550, 580, 630, 670, 680, 780, 780-2, 820, 830, 850, 855, 930, 980, S-305, UT771, TTO-51 (A), 51 (C), 55 (A), 55 (B), 55 (C), 55 (D), S-1, S-2, S-3, S-4, V-3, V-4, MPT-136, FTL- 100, 110, 200, 300 (Ishihara Sangyo Co., Ltd.), KA-10, 15, 20, 30, KR-310, 380, KV-200, STT-30EHJ, 65C-S, 455, 485SA15, 495M, 495MC ( Titanium Industry Co., Ltd.), TA-100, 200, 300, 400, 500, TR-600, 700, 750, 840, 900 (Fuji Titanium Industry Co., Ltd.) and the like. It may be.

In the present invention, the surface of the white inorganic pigment (particularly titanium oxide) can be used in combination with silica treatment, alumina treatment, titania treatment, zirconia treatment, organic matter treatment and the like.
Thereby, the catalytic activity of the white inorganic pigment (particularly titanium oxide) can be suppressed, and heat resistance, fluorescence, and the like can be improved.
From the viewpoint of the whiteness of the decorative layer after heating, in the present invention, the white pigment is preferably a rutile type titanium oxide surface-treated with an inorganic substance, and at least one of alumina treatment and zirconia treatment was surface-treated. A rutile type titanium oxide is more preferable, and a rutile type titanium oxide surface-treated by an alumina / zirconia combined treatment is particularly preferable.

In order to use it as a decorative layer of other colors, pigments or dyes described in paragraphs 0183 to 0185 of Japanese Patent No. 4546276 may be mixed and used. Specifically, pigments and dyes described in paragraphs 0038 to 0054 of JP-A-2005-17716, pigments described in paragraphs 0068 to 0072 of JP-A-2004-361447, paragraphs of JP-A-2005-17521 The colorants described in 0080 to 0088 can be preferably used.

The content of the inorganic pigment with respect to the total solid content of the decorative layer is 20 to 75% by mass to form a decorative layer having good brightness and whiteness and simultaneously satisfying other required characteristics. It is preferable from the viewpoint. Moreover, when using the transfer film of this invention for the manufacturing method of the laminated body of this invention mentioned later, the content rate of the said inorganic pigment with respect to the total solid of the said decoration layer is also 20 from a viewpoint of fully shortening development time. It is preferable that the content be ˜75% by mass.
The content of the inorganic pigment with respect to the total solid content of the decorative layer is more preferably 25 to 60% by mass, and further preferably 30 to 50% by mass.
The total solid content as used in this specification means the total mass of the non-volatile component except a solvent etc. from the said decoration layer.

It is desirable to use the inorganic pigment (which is the same for other colorants) as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the inorganic pigment and the pigment dispersant in an organic solvent (or vehicle) described later. The above-mentioned vehicle refers to a portion of a medium in which a pigment is dispersed when the paint is in a liquid state, and is a liquid component that binds to the pigment to form a coating film (binder) and dissolves and dilutes it. Component (organic solvent).

The disperser used for dispersing the inorganic pigment is not particularly limited. For example, a kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, First Edition, Asakura Shoten, 2000, p. 438. , Known dispersers such as a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill. Further, fine grinding may be performed using frictional force by mechanical grinding described in page 310 of this document.

The colorant that can be used in the present invention is preferably a colorant having an average primary particle size of 0.16 μm to 0.3 μm, more preferably 0.18 μm to 0.27 μm, from the viewpoint of dispersion stability and hiding power. The colorant is preferred. Further, a colorant of 0.19 μm to 0.25 μm is particularly preferable. When the average particle size of the primary particles is smaller than 0.16 μm, the hiding power is suddenly lowered, and the base of the decorative layer may be easily seen or the viscosity may be increased. On the other hand, when the average particle size exceeds 0.3 μm, the whiteness is lowered particularly when a white inorganic pigment is used, and at the same time, the hiding power is suddenly lowered, and the surface condition when applied may be deteriorated.
The “average particle size of primary particles” as used herein refers to the diameter when the electron micrograph image of the particles is a circle of the same area, and the “number average particle size” refers to the above-mentioned particle size for a large number of particles. The diameter is determined, and among these, an average value of 100 particle diameters arbitrarily selected is referred to.
On the other hand, when measuring by the average particle diameter in a dispersion liquid and a coating liquid, laser scattering HORIBA H (made by Horiba Advanced Techno Co., Ltd.) can be used.

-Binder resin-
It is preferable that a decoration layer contains binder resin. The binder resin is preferably a silicone resin similar to the first transparent resin layer.
Moreover, it is preferable that a catalyst is included from a viewpoint of hardening | curing the said decoration layer containing the said silicone resin, and improving a brittleness. The catalyst is preferably the same as the catalyst that may be contained in the at least two transparent resin layers.

(Method for forming the decorative layer)
Although there is no restriction | limiting in particular in the formation method of the said decoration layer, It is preferable to form using the transfer film which has a temporary support body and a resin layer in this order, and this temporary support body and a photocurable resin layer are made into this. It is more preferable to form using a photosensitive transfer film having in order, and it is particularly preferable to use a photosensitive transfer film having a temporary support, a thermoplastic resin layer, and a photocurable resin layer in this order. . For example, when the white decorative layer 2 is formed, the white light curing is performed on the surface of the front plate 1 by using a photosensitive transfer film described later having a white light curing resin layer as the photocurable resin layer. The conductive resin layer is preferably formed by transferring.
When forming a decoration layer using the said transfer film, a coloring agent can be used for a resin layer. As the colorant, the above-mentioned colorants (organic pigments, inorganic pigments, dyes, etc.) can be suitably used.

The first transparent resin layer 7, the second transparent resin layer 9, the decorative layer 2, or the decorative layer 2 described in FIG. 1 is used by using a transfer film on the front plate having the opening 8 having the configuration shown in FIG. When a mask layer (not shown) or the like is formed, even if the front plate has the opening 8, it can be formed without causing the resist component to protrude from the periphery of the opening 8. In particular, the decorative layer needs to form a light shielding pattern just above the boundary line of the front plate, and by using a transfer film, the resist component does not protrude from the glass edge, that is, the back side of the front plate is A touch panel reduced in thickness and weight can be manufactured through a simple process without contamination.

A method for forming the decorative layer using a transfer film will be described.
In general, when a transfer film is used, it can be formed by an ordinary photolithography method if the decorative layer contains a photocurable resin.
The transfer film may or may not contain the photocurable resin, and the case where the decorative layer contains the photocurable resin and the case where the decorative layer does not contain the photocurable resin. In any case, the decorative layer can be formed by using a transfer film by a transfer method by half-cut or a transfer method by die-cut, which will be described later.

In the case where a permanent material such as a decorative layer is formed using a transfer film, a patterning method using the transfer film will be described using a method of forming the decorative layer as an example.

(1-A) Patterning by photolithography The patterning method will be described for the case where the decorative layer is formed using photolithography.

In the patterning method in the case of forming the decorative layer using a photolithography method, it is a transfer film having at least a temporary support and a photocurable resin layer, and the photocurable resin layer is a photocurable resin and a colorant. A transfer film having
The transfer film having the photocurable resin layer may include a protective film and an intermediate layer in addition to the photocurable resin layer, the temporary support, and the thermoplastic resin layer.
The photocurable resin layer of the transfer film having the photocurable resin layer preferably has the following configuration.

There is no restriction | limiting in particular as long as it is not contrary to the meaning of this invention as said monomer used for the said photocurable resin layer, A well-known polymeric compound can be used.
As the polymerizable compound, polymerizable compounds described in paragraphs 0023 to 0024 of Japanese Patent No. 4098550 can be used.

The binder used in the photocurable resin layer is not particularly limited as long as it is not contrary to the gist of the present invention, and a known polymerizable compound can be used.
When the transfer film having the photocurable resin layer is a negative material, the photocurable resin composition preferably contains an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. Furthermore, although a coloring agent, an additive, etc. are used, it is not restricted to this.
As the alkali-soluble resin, polymers described in paragraph 0025 of JP2011-95716A and paragraphs 0033 to 0052 of JP2010-237589A can be used. On the other hand, when the decorative layer is formed by precutting, it is also preferable to use a silicone resin as the binder resin in the resin layer having the colorant as described above.
When the transfer film having the photocurable resin layer is a positive type material, for example, a material described in JP-A-2005-221726 is used for the photocurable resin layer, but is not limited thereto.

As the photopolymerization initiator used in the photocurable resin layer, the polymerizable compounds described in paragraphs 0031 to 0042 described in JP 2011-95716 A can be used.

Furthermore, an additive may be used for the photocurable resin layer. Examples of the additive include surfactants described in paragraph 0017 of Japanese Patent No. 4502784, paragraphs 0060 to 0071 of JP-A-2009-237362, and prevention of thermal polymerization described in paragraph 0018 of Japanese Patent No. 4502784. And other additives described in paragraphs 0058 to 0071 of JP-A No. 2000-310706.

-solvent-
In addition, as a solvent for producing a transfer film having a photocurable resin layer by coating, the solvents described in paragraphs 0043 to 0044 of JP2011-95716A can be used.

As described above, the case where the transfer film having the photocurable resin layer is a negative type material has been mainly described, but the transfer film may be a positive type material.

The viscosity of the photocurable resin layer measured at 100 ° C. is in the range of 2000 to 50000 Pa · sec, and preferably satisfies the following formula.
Viscosity of thermoplastic resin layer <viscosity of photocurable resin layer

When the transfer film has a photocurable resin layer, the method for forming the decorative layer includes a protective film removing step for removing the protective film from the transfer film, and a method for removing the protective film from the transfer film. A transfer step of transferring the photocurable resin layer onto the substrate, an exposure step of exposing the photocurable resin layer transferred onto the substrate, and developing the exposed photocurable resin layer to form a pattern And a development step for obtaining an image. In this case, it is preferable to further include a step of post-exposing the transferred photocurable resin layer after the transfer step.

After the transfer film is laminated on the front plate (base material), it is exposed to the required pattern, and in the case of negative type material, the unexposed part and in the case of positive type material, the exposed part is developed and removed. A pattern can be obtained. At this time, the development may be carried out by removing the thermoplastic resin layer and the photocurable resin layer with separate liquids, or with the same liquid. You may combine well-known image development facilities, such as a brush and a high pressure jet, as needed. After the development, post-exposure and post-bake may be performed as necessary.
Hereinafter, when forming the said decoration layer using a photolithographic system, the detail of a preferable transfer process, an exposure process, a image development process, and another process is demonstrated.

-Transcription process-
The said transfer process is a process of transferring the said photocurable resin layer of the transfer film from which the said protective film was removed on a base material.
At this time, a method of removing the temporary support after laminating the photocurable resin layer of the transfer film on the substrate is preferable.
Transfer (bonding) of the photocurable resin layer to the surface of the base material is performed by stacking the photocurable resin layer on the surface of the base material, and applying pressure and heating. For laminating, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.

-Exposure process, development process, and other processes-
As examples of the exposure step, the development step, and other steps, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present invention.

The said exposure process is a process of exposing the said photocurable resin layer transcribe | transferred on the base material.
Specifically, there is a method in which a predetermined mask is disposed above the photocurable resin layer formed on the substrate, and then exposed from above the mask through the mask, the thermoplastic resin layer, and the intermediate layer. Can be mentioned.
Here, the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photocurable resin layer (for example, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. The exposure dose is usually about 5 to 200 mJ / cm ² , preferably about 10 to 100 mJ / cm ² .

The developing step is a step of developing the exposed photocurable resin layer.
The development can be performed using a developer. The developer is not particularly limited, and a known developer such as a developer described in JP-A-5-72724 can be used. The developer is preferably a developer in which the photocurable resin layer has a dissolution type development behavior. For example, a developer containing a compound having pKa = 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable. A small amount of an organic solvent miscible with water may be added. Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol And acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass. Further, a known surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

The development method may be any of paddle development, shower development, shower & spin development, dip development, and the like. Here, the shower development will be described. An uncured portion can be removed by spraying a developer onto the photocurable resin layer after exposure. In the case where a thermoplastic resin layer or an intermediate layer is provided, an alkaline liquid having a low solubility of the transparent curable resin layer containing a photocurable resin is sprayed by a shower or the like before development, and the thermoplastic resin layer, It is preferable to remove the intermediate layer and the like. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

(1-B) Patterning by pre-cut method As a method for forming a decorative layer, when an image is not formed by a normal photolithography method, it is necessary to form an image portion on the decorative layer before transfer.

(I-1) a step (half-cut step) in which a part of the transfer film has a depth that penetrates the decorative layer and does not penetrate the temporary support (half-cut step); (i-2) the transfer The step of cutting the penetrating through the temporary support from the decorative layer into a part of the film (die cutting step) is also referred to as (i) the step of precutting the image portion to be transferred in the decorative layer of the transfer film.

The method for forming the decorative layer is as follows: (i-1) Half-cut step, that is, a cut having a depth that penetrates the decorative layer and does not penetrate the temporary support is partly formed in the transfer film. And (iii) removing the decorative layer in at least a part of the region surrounded by the cuts (non-image portion not to be transferred), and (iii) the decoration of the part of the region A step of forming the decorative layer using the transfer film after removing the layer (a step of transferring the image portion of the decorative layer onto the substrate, hereinafter also referred to as “transfer step”). It is preferable.
The method for forming the decorative layer includes: (i-2) a die-cutting step, that is, a step of making a cut through the temporary support from the decorative layer into a part of the transfer film; and (iii) It is also preferable to include the step of forming the decorating layer using the transfer film after removing the decorating layer in the partial area.

Further, when the transfer film includes a protective film, an intermediate layer, or a thermoplastic resin layer, (ii) the step of removing the decorative layer in at least a part of the region surrounded by the notch is (ii- 1) It is preferable that it is the process of removing the protective film and decoration layer of a non-image part, and the protective film of an image part.

Furthermore, when a transfer film contains a protective film, an intermediate | middle layer, and a thermoplastic resin layer, (iii) The said decoration layer is formed using the said transfer film after removing the said decoration layer of the said one part area | region. The step (the step of transferring the image portion of the decorative layer onto the substrate) is (iii-1) the step of transferring the image portion of the decorative layer of the transfer film from which the protective film has been removed onto the substrate. It is preferable that
In this case, further, (iii) the step of forming the decorative layer using the transfer film after removing the decorative layer in the partial area includes (iv) temporary support transferred onto the substrate. It is preferable to include a step of peeling the body.
In this case, the step of (iii) forming the decorative layer using the transfer film after removing the decorative layer in the partial area includes (v) removing the thermoplastic resin layer and the intermediate layer. It is preferable that the process to include is included.

The decorative layer forming method includes (i) a step of pre-cutting the transferred image portion of the decorative layer of the transfer film, and (ii-1) a protective film and a decorative layer for the non-image portion, and protection of the image portion. A step of removing the film; (iii-1) a transfer step of transferring the image portion of the decorative layer of the transfer film from which the protective film has been removed onto the substrate; and (iv) a transfer of the image onto the substrate. More preferably, the method includes a step of peeling the temporary support and a step (v) of removing the thermoplastic resin layer and the intermediate layer.

Also, in order to enhance the adhesion of the decorative layer by lamination in the subsequent transfer process, one surface of the base material (front plate) can be subjected to surface treatment in advance. As the surface treatment, it is preferable to carry out a surface treatment (silane coupling treatment) using a silane compound (silane coupling agent). As the silane coupling agent, those having a functional group that interacts with the photosensitive resin are preferable. For example, a silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3% by mass aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) is sprayed for 20 seconds by a shower, and pure water shower washing is performed. To do. Thereafter, the reaction is carried out by heating. A heating tank may be used, and the reaction can be promoted by preheating the base material of the laminator.

In the transfer method that undergoes a half-cut process, first, after pre-cutting with a razor or the like at the boundary between the image portion and the non-image portion of the decorative layer, the protective film, the decorative layer, and the intermediate layer of the non-image portion are removed with a tape, The protective film in the image area is similarly removed, and the decorative layer pattern is transferred to the substrate.
On the other hand, in the transfer method that passes through the die cutting step, first, as shown in FIGS. 11 to 13, after pre-cutting so as to penetrate the entire layer with a razor or the like at the boundary between the image portion 32 and the non-image portion 31 of the decorative layer, The protective film of the image part 32 which remained after removing the said decoration layer (non-image part 31) of a one part area | region is removed with a tape, and a decoration layer pattern is transcribe | transferred to a base material.
Subsequently, the decorative layer pattern can be formed by removing the thermoplastic resin layer and the intermediate layer by development.
You may combine well-known image development facilities, such as a brush and a high pressure jet, as needed. After development, post-exposure and post-bake may be performed as necessary, and post-bake is preferably performed.
Hereinafter, when forming the said decoration layer using a precut system, the detail of a preferable precut process, a transfer process, an exposure process, a development process, and another process is demonstrated.

-Pre-cut process-
(I-1) Half-cutting step First, in the pre-cutting step, the half-cutting step in the method for forming the decorative layer, that is, a part of the transfer film penetrates the decorative layer, and the temporary support. The process of making a cut with a depth that does not penetrate through will be described below.
There is no restriction | limiting in particular as the method of making the said incision, Incision can be made by arbitrary methods, such as a blade and a laser, and it is preferable to make an incision with a blade. Further, the structure of the blade is not particularly limited.
When the transfer film is composed of, for example, a temporary support, a thermoplastic resin layer, an intermediate layer, a decorative layer, and a protective film, in that order, for example, using a blade or a laser, from above the protective film, By cutting through the protective film, the decorative layer, and the intermediate layer and reaching a part of the thermoplastic resin layer, it is possible to separate the image portion to be transferred and the non-image portion not to be transferred.

In order to selectively transfer the image portion of the decorative layer precut by the half cut to the substrate, it is necessary to devise a method not to transfer the non-image portion. One method is a method of removing the non-image part of the decorative layer before transfer, and after removing the protective film, the non-image part of the decorative layer and the intermediate layer are simultaneously peeled off. The other is a method of peeling off the protective film on the non-image area, subsequently peeling off the decorative layer and the intermediate layer at the same time, and further peeling off the protective film on the image area. From the viewpoint of protecting the image portion of the decorative layer until just before transfer, the latter is preferred.

(I-2) Die-cutting step Next, in the pre-cutting step, a die-cutting step in the method of forming the decorative layer, that is, a cut that penetrates the temporary support from the decorative layer into a part of the transfer film. The process of putting in is demonstrated below.
There is no restriction | limiting in particular as the method of making the said incision like a half cut, It can cut with arbitrary methods, such as a blade and a laser, It is preferable to make an incision with a blade. Further, the structure of the blade is not particularly limited.
When the transfer film is composed of, for example, a temporary support, a thermoplastic resin layer, an intermediate layer, a decorative layer, and a protective film, in that order, for example, using a blade or a laser, from above the protective film, By making a cut through the protective film, the decorative layer, the intermediate layer, the thermoplastic resin layer, and the temporary support, it is possible to separate between the image portion to be transferred and the non-image portion not to be transferred.

-Transcription process-
The said transfer process is a process of transferring the said decoration layer of the said transfer film after a precut process on a base material.
At this time, it is preferable to remove the temporary support after laminating the decorative layer of the transfer film to the substrate.
Transfer (bonding) of the decorative layer to the substrate surface is performed by stacking the decorative layer on the substrate surface, pressurizing and heating. For laminating, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.

-Exposure process, development process-
When a decoration layer contains a photocurable resin, you may perform an exposure process after a precut process, and the preferable aspect of the exposure process after a precut process is the same as the preferable aspect of the exposure process in a photolithography system. When the decorative layer does not contain a photocurable resin, the exposure process may not be performed after the precut process.

After the pre-cut process, the preferred embodiment of the development process following the exposure process is the same as the preferred embodiment of the development process in the photolithography method, and is used in the step of developing the exposed photocurable resin layer by the photolithography method. The developer can be used in the same manner in the development step subsequent to the exposure step after the precut step. Further, a known surfactant can be further added to the alkali developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.
The method of removing the thermoplastic resin layer and the intermediate layer may be any of paddle, shower, shower & spin, dip, and the like used for developing the exposed photocurable resin layer. As an example of the step of removing the thermoplastic resin layer and the intermediate layer, the method described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present invention.

(2) Post-bake The decorative layer forming method preferably includes a post-bake step after the transfer step, and more preferably includes a step of post-bake after the step of removing the thermoplastic resin layer and the intermediate layer. preferable.
The decorative layer can be formed by heating the decorative layer after the transfer step in an environment of 0.08 to 1.2 atm at 180 to 300 ° C. to achieve both whiteness and productivity. It is preferable from the viewpoint.
The post-baking is more preferably performed in an environment of 0.5 atm or more. On the other hand, it is more preferable to carry out in an environment of 1.1 atm or less, and it is particularly preferred to carry out in an environment of 1.0 atm or less. Furthermore, it is more preferable to carry out in an environment of about 1 atm (atmospheric pressure) from the viewpoint of reducing the manufacturing cost without using a special decompression device. Here, conventionally, when the decorative layer is formed by curing by heating, it is performed in a reduced pressure environment of a very low pressure, and the whiteness after baking is maintained by lowering the oxygen concentration. By using a transfer film formed using a coating liquid for a decoration layer containing a silicone resin, the whiteness of the decoration layer can be increased even after baking in the above pressure range.
The post-baking temperature is more preferably 200 to 280 ° C, and particularly preferably 220 to 260 ° C.
The post-baking time is more preferably 20 to 150 minutes, and particularly preferably 30 to 100 minutes.
The post-baking may be performed in an air environment or a nitrogen substitution environment, but it is particularly preferable to perform the post-bake from the viewpoint of reducing the manufacturing cost without using a special decompression device.

(3) Other process The formation method of a decoration layer may have other processes, such as a post-exposure process.
When the said decoration layer has a photocurable resin layer, when forming the said decoration layer, it is preferable that a post-exposure process is included. The post-exposure step may be performed from the surface of the decorative layer that is in contact with the base material, from the surface that is not in contact with the transparent base material, or from both surfaces.

As examples of other steps, the method described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present invention.

[Transfer film]
The transfer film of the present invention is a transfer film having a temporary support, a first transparent resin layer containing at least a silicone resin as a binder resin, and a second transparent resin layer containing at least a silicone rubber as a binder resin, The first transparent resin layer has a structure sandwiched between the temporary support and the second transparent resin layer.
The transfer film of the present invention preferably has a thermoplastic resin layer between the temporary support and the first transparent resin layer.

<Temporary support>
As the temporary support, a material that is flexible and does not cause significant deformation, shrinkage, or elongation under pressure or under pressure and heating can be used. Examples of such a temporary support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film, and among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

The thickness of the temporary support is not particularly limited and is generally in the range of 5 to 200 μm, and in the range of easy handling and versatility, the range of 10 to 150 μm is particularly preferable.
Further, the temporary support may be transparent or may contain dyed silicon, alumina sol, chromium salt, zirconium salt or the like.
Further, the temporary support can be imparted with conductivity by the method described in JP-A-2005-221726.

<Transparent resin layer>
The transfer film of the present invention includes the first transparent resin layer and the second transparent resin layer.
The preferable aspect of the 1st transparent resin layer in the transfer film of this invention is the same as the preferable aspect of the said 1st transparent resin layer in the laminated body of this invention. The preferable aspect of the 2nd transparent resin layer in the transfer film of this invention is the same as the preferable aspect of the said 2nd transparent resin layer in the laminated body of this invention.
The first transparent resin layer and the second transparent resin layer used in the present invention have a desired size in order to fill a gap (step difference in the decorative layer) generated by a difference in height between the front plate and the decorative layer. It is preferable. The transfer film of the present invention can be made to have a desired size by a precut process or the like in order to fill the step of the decorative layer. Therefore, the first transparent resin layer and the second transparent resin layer used in the transfer film of the present invention are the laminate of the present invention, the conductive film laminate of the present invention described later, and the capacitive input device. It is not always necessary to match the size required to fill the step of the decorative layer.
On the other hand, the first transparent resin layer and the second transparent resin layer are used to fill the steps of the decorative layer in the laminate of the present invention, the conductive film laminate of the present invention described later, and the capacitive input device. When forming a transfer film, it is preferable to adjust the thickness to the same level as the height of the decorative layer.

(Viscosity of transparent resin layer)
The viscosity of the first transparent resin layer and the second transparent resin layer measured at 100 ° C. is preferably in the region of 1 to 50000 Pa · sec.

Here, the viscosity of each layer can be measured as follows. A transparent resin layer coating liquid (first coating liquid for transparent resin layer) containing a thermoplastic resin layer or at least a silicone resin as a binder resin, and a transparent resin layer containing at least a silicone rubber as a binder resin by drying under atmospheric pressure and reduced pressure. Remove the solvent from the coating solution for coating (second coating solution for transparent resin layer) to make a measurement sample. For example, use Vibron (DD-III type: manufactured by Toyo Baldwin Co., Ltd.) as a measuring instrument and start measurement. Measurement is performed under conditions of a temperature of 50 ° C., a measurement end temperature of 150 ° C., a temperature increase rate of 5 ° C./min, and a frequency of 1 Hz / deg, and a measured value of 100 ° C. can be used.

<Thermoplastic resin layer>
In the transfer film of the present invention, it is preferable that a thermoplastic resin layer is provided between the temporary support and the first transparent resin layer. The thermoplastic resin layer is preferably alkali-soluble. The thermoplastic resin layer plays a role as a cushioning material so as to be able to absorb unevenness on the base surface (including unevenness due to images already formed, etc.). It is preferable to have a property that can be deformed.

The thermoplastic resin layer preferably includes an organic polymer substance described in JP-A-5-72724 as a component. The Vicat method [specifically, a method for measuring a polymer softening point by American Material Test Method ASTM D1235] An embodiment including at least one selected from organic polymer substances having a softening point of about 80 ° C. or lower is particularly preferable.

Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers with ethylene and vinyl acetate or saponified products thereof, copolymers of ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride and vinyl chloride, Vinyl chloride copolymer with vinyl acetate or saponified product thereof, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer with styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, Vinyl toluene copolymer of vinyl toluene and (meth) acrylic acid ester or saponified product thereof, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymer weight of butyl (meth) acrylate and vinyl acetate, etc. Copolymer, vinyl acetate copolymer nylon, copolymer nylon N- alkoxymethyl nylon, N- dimethylamino nylon or the like of the polyamide resin, polyester, and organic polymers such as.

Further, it is preferable to add a foaming agent or the like for controlling peelability to the thermoplastic resin layer, and those described in paragraphs 0020 to 0028 of JP-A-2007-225939 can be used as appropriate.

It is also preferable to add a surfactant to the thermoplastic resin layer. For example, those described in Paragraph 0017 of Japanese Patent No. 4502784 and Paragraphs 0060 to 0071 of JP-A-2009-237362 can be used as appropriate.

The layer thickness of the thermoplastic resin layer is preferably 3 to 30 μm. When the thickness of the thermoplastic resin layer is 3 μm or more, the followability at the time of lamination is sufficient, and the unevenness of the base surface is easily absorbed. In addition, when the layer thickness is 30 μm or less, it is difficult to apply a load to drying (solvent removal) when forming the thermoplastic resin layer on the temporary support, and development of the thermoplastic resin layer does not take too much time. , Process aptitude is good. The thickness of the thermoplastic resin layer is more preferably 4 to 25 μm, and particularly preferably 5 to 20 μm.

The thermoplastic resin layer can be formed by applying a preparation liquid containing a thermoplastic organic polymer, and the preparation liquid used for the application can be prepared using a solvent. The solvent is not particularly limited as long as it can dissolve the polymer component constituting the thermoplastic resin layer, and examples thereof include methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, and 2-propanol.

The viscosity of the thermoplastic resin layer measured at 100 ° C. is preferably in the region of 1000 to 50000 Pa · sec.

<Other layers>
In the transfer film of the present invention, an intermediate layer is provided between the first transparent resin layer and the thermoplastic resin layer, or a protective film or the like is further provided on the surface of the second transparent resin layer. Can be configured.

In the transfer film of the present invention, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components when applying a plurality of layers and during storage after application. As the intermediate layer, an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724, is preferable, which increases sensitivity during exposure and reduces the time load of the exposure machine. And productivity is improved.

As the intermediate layer and the protective film, those described in paragraphs 0083 to 0087 and 0093 of JP-A-2006-259138 can be appropriately used.

<Production method of transfer film>
The transfer film of the present invention can be produced according to the method for producing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138.
Specifically, when forming the transfer film of the present invention having an intermediate layer, a preparation liquid (thermoplastic resin layer coating liquid) containing an additive together with a thermoplastic organic polymer is applied on a temporary support. After drying and providing a thermoplastic resin layer, a preparation liquid (intermediate layer coating liquid) obtained by adding a resin or an additive to a solvent that does not dissolve the thermoplastic resin layer is applied onto the thermoplastic resin layer, and then dried. Then, an intermediate layer is laminated, and on this intermediate layer, a first transparent resin layer coating solution and a second transparent resin layer coating solution prepared using a solvent that does not dissolve the intermediate layer are further applied. It can produce suitably by making it dry and laminating | stacking a 1st transparent resin layer and a 2nd transparent resin layer.

[Manufacturing method of laminate]
The production method of the laminate of the present invention is not particularly limited, but the first preferred embodiment of the production method of the laminate described below, the second preferred embodiment of the production method of the laminate of the present invention, the present invention, It is preferable that it is one of the 3rd preferable aspects of the manufacturing method of the laminated body of invention.
The 1st preferable aspect of the manufacturing method of the laminated body of this invention is 1st transparent resin layer which contains at least silicone resin as binder resin of the transfer film of this invention, and 2nd transparent resin which contains at least silicone rubber as binder resin. A part of the front plate (one surface of the front plate) or the front plate, the second transparent resin layer, and the first transparent resin layer are laminated in this order. A step of transferring to the whole and a step of forming an electrode pattern on the first transparent resin layer.

The 2nd preferable aspect of the manufacturing method of the laminated body of this invention is 2nd transparent resin which transcribe | transfers the 2nd transparent resin layer to a part or all on a front plate (one side of a front plate) from a transfer film. The layer forming step, the first transparent resin layer from the transfer film, the front plate, the second transparent resin layer, and the first transparent resin layer are laminated in this order, Forming a second transparent resin layer, comprising: forming a first transparent resin layer to be transferred onto the second transparent resin layer; and forming an electrode pattern on the first transparent resin layer. The process and the first transparent resin layer forming process are simultaneous or continuous transfer processes.

In a third preferred embodiment of the method for producing a laminate of the present invention, a resin composition (second coating solution for forming a transparent resin layer) containing at least silicone rubber as a binder resin is placed on the front plate (one surface of the front plate). And a resin composition (first coating solution for forming a transparent resin layer) containing at least a silicone resin as a binder resin, and the front plate, A step of forming a first transparent resin layer applied on the second transparent resin layer such that the second transparent resin layer and the first transparent resin layer are laminated in this order; and A step of forming an electrode pattern on the first transparent resin layer, and the step of forming the second transparent resin layer and the step of forming the first transparent resin layer are continuous coating steps.

<Step of forming at least two transparent resin layers>
The manufacturing method of the laminated body of this invention includes the formation process of the said at least 2 layer of transparent resin layer. In the following, each preferred embodiment will be described separately.

(First preferred embodiment)
In the method for producing a laminate of the present invention, the first preferred embodiment of the step of forming the at least two transparent resin layers is the first transparent resin layer and the second transparent resin layer of the transfer film of the present invention. Is transferred to a part or all of the front plate so that the front plate, the second transparent resin layer, and the first transparent resin layer are laminated in this order.
In the first preferred embodiment, the first transparent resin layer of the transfer film of the present invention is in contact with the electrode pattern. The second transparent resin layer is a second transparent resin layer from the electrode pattern side.
In the first preferred embodiment, the first transparent resin layer and the second transparent resin layer can be simultaneously transferred to form the first transparent resin layer and the second transparent resin layer. The dimensions can be adjusted at the same time, which is preferable.
In the first preferred embodiment, the preferred range of the method of transferring and forming the first transparent resin layer and the second transparent resin layer is the preferred range of the transfer step in the method of forming the decorative layer described above. It is the same.

(Second preferred embodiment)
In the second preferred embodiment of the step of forming the at least two transparent resin layers in the method for producing a laminate of the present invention, the second transparent resin layer is transferred from a transfer film to a part or all of the front plate. The step of forming the second transparent resin layer, the first transparent resin layer from the transfer film, the front plate, the second transparent resin layer, and the first transparent resin layer are laminated in this order. As described above, a first transparent resin layer forming step to be transferred onto the second transparent resin layer, wherein the second transparent resin layer forming step and the first transparent resin layer forming step are: It is a simultaneous or continuous transfer process.
In the second preferred embodiment, the first transparent resin layer and the second transparent resin layer may be formed by transferring at the same time or may be formed by transferring them continuously.
In the second preferred embodiment, the preferred range of the method for transferring and forming the first transparent resin layer and the second transparent resin layer is the first preferred embodiment of the method for producing a laminate of the present invention. The preferred range of the method for transferring and forming the first transparent resin layer and the second transparent resin layer is the same.

(Third preferred embodiment)
In the third preferred embodiment of the step of forming the at least two transparent resin layers in the laminate production method of the present invention, the second transparent resin layer forming coating solution is applied to a part or all of the front plate. The second transparent resin layer forming step, the first transparent resin layer forming coating liquid, the front plate, the first transparent resin layer, and the second transparent resin layer in this order. A step of forming a first transparent resin layer applied on the second transparent resin layer so as to be laminated, the step of forming the second transparent resin layer and the step of forming the first transparent resin layer , A continuous coating process.
The third preferred embodiment is not particularly limited as a formation method by applying the first transparent resin layer and the second transparent resin layer, and the liquid resist for at least two transparent resin layers is at least It can be applied or printed in the gap between the electrode pattern and the front plate and cured by a known method.

<Step of forming electrode pattern>
The manufacturing method of the laminated body of this invention includes the process of forming an electrode pattern on the said 1st transparent resin layer.
The step of forming the electrode pattern is preferably a step of manufacturing using a transfer film having a conductive curable resin layer using conductive fibers described later. In addition, when the electrode pattern is formed of ITO or the like, paragraphs 0014 to 0016 of Japanese Patent No. 4506785 can be referred to.
The step of forming an electrode pattern is common to the first preferred embodiment, the second preferred embodiment, and the third preferred embodiment of the method for producing a laminate of the present invention, and the preferred embodiment is also common.

[Conductive film laminate, capacitance type input device]
The electrically conductive film laminated body of this invention has a 2nd electrode pattern electrically insulated with the said electrode pattern on the electrode pattern of the laminated body of this invention. In the conductive film laminate of the present invention, the second electrode pattern is preferably a transparent electrode pattern.
The conductive film laminate of the present invention includes a front plate (preferably a transparent front plate), a functional layer disposed on a part of one surface of the front plate, and a surface side on which the functional layer of the front plate is disposed. And at least two transparent resin layers or the second transfer film of the present invention so as to fill at least the gap between the electrode pattern and the front plate. It is more preferable to have 1 transparent resin layer and 2nd transparent resin layer.
The capacitance-type input device of the present invention includes the conductive film laminate of the present invention.
In the conductive film laminate of the present invention and the capacitance-type input device of the present invention, the at least two transparent resin layers may maintain a uniform thickness, and some thicknesses May be a non-uniform shape (in other words, a transparent resin layer).

In the conductive film laminate of the present invention, the at least two transparent resin layers comprise at least a first transparent resin layer and a second transparent resin layer contained in the transfer film of the present invention, at least an electrode pattern and a front plate. It is preferably formed by transferring so as to fill a gap between the two.
Here, the gap between the electrode pattern and the front plate in the capacitive input device of the present invention is not particularly limited.
Although there is no restriction | limiting in particular as an above-mentioned functional layer, the electrically conductive film laminated body of this invention can mention the laminated body of a decoration layer, a decoration layer, and a mask layer (shielding layer). Among them, the functional layer described above is preferably a decorative layer or a laminate of a decorative layer and a mask layer (shielding layer), and more preferably a decorative layer.
When the functional layer is a decorative layer, at least a gap between the electrode pattern and the front plate is formed by “a gap generated by a height difference between the front plate and the decorative layer” (the electrode pattern and the front plate). Is more preferably equal to the gap generated by the height difference between the front plate and the decorative layer.

In the conductive film laminate of the present invention, the electrode pattern preferably includes the following (1) to (3) from the viewpoint of use as a capacitive input device.
(1) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (2) electrically insulated from the first transparent electrode pattern, A plurality of second electrode patterns comprising a plurality of pad portions formed extending in a direction crossing the first direction; and (3) electrically connecting the first transparent electrode pattern and the second electrode pattern. However, “the electrode pattern is disposed on the decorative layer” means that a part of (1) or (2) among the above (1) to (3) is the decorative layer. All of (1) to (3) need not be arranged on the decorative layer. Moreover, the electrode pattern may be arrange | positioned adjacent to the said decoration layer, and may be arrange | positioned through another layer.
Furthermore, in the conductive film laminate and the capacitive input device of the present invention, the electrode pattern may further include the following (4).
(4) A conductive element that is electrically connected to at least one of the first transparent electrode pattern and the second electrode pattern, and is different from the first transparent electrode pattern and the second electrode pattern. In the conductive film laminate and the capacitive input device of the present invention, the second electrode pattern may be a transparent electrode pattern. In this specification, the second transparent electrode pattern may be described instead of the second electrode pattern, but the preferred embodiment of the second electrode pattern is the same as the preferred embodiment of the second transparent electrode pattern. is there.
Furthermore, the conductive film laminate and the capacitance-type input device of the present invention are provided on the surface of the decorative layer formed on one surface side of the front plate on the side opposite to the surface facing the front plate. Further, a mask layer may be provided.
Hereinafter, the preferable aspect of the electrically conductive film laminated body and electrostatic capacitance type input device of this invention is demonstrated. In addition to the following preferred embodiments, preferred configurations and embodiments of the conductive film laminate and the capacitance-type input device of the present invention are described in <0016> to <0050> of JP2013-24610A. Embodiments can be employed and the contents of this publication are incorporated herein.

<Structure of conductive film laminate and capacitive input device>
The structures of the conductive film laminate and the capacitance type input device of the present invention will be described. In the following description, the functional layer described above is a decorative layer, and the case where the gap between the electrode pattern and the front plate is equal to the gap caused by the height difference between the front plate and the decorative layer will be described. The present invention is not limited to such an embodiment. FIG. 14 is a cross-sectional view showing a preferred configuration among the capacitance-type input device of the present invention. The capacitive input device shown in FIG. 14 includes a front plate 1, a decorative layer 2 disposed on a part of one surface of the front plate, and one surface side of the front plate (decorative layer 2). The gap formed by the height difference between the front plate 1 and the decorative layer 2 is the second transparent resin. It is filled with the layer 102 and the first transparent resin layer 101. Further, the capacitive input device shown in FIG. 14 has a second electrode pattern 4 on the first transparent electrode pattern 3, and the second electrode pattern 4 is the first transparent electrode pattern. 3 and the insulating layer 5, and the capacitive input device shown in FIG. 14 has another conductive element 6.
As in the capacitive input device shown in FIG. 14, the first transparent resin layer 101 and the second transparent resin layer 102 are the same as the side of the front plate 1 on which the decorative layer 2 is formed. It is more preferable that the decorative layer 2 on the surface of the surface is formed on a portion where the decorative layer 2 is not formed and on a part of the decorative layer 2.

On the other hand, as shown in FIG. 1, the first transparent resin layer 7 and the second transparent resin layer 9 are formed on the same surface as the side of the front plate 1 on which the decorative layer 2 is formed. You may form in the part in which the decoration layer 2 is not formed, and all the said decoration layers 2. However, in the conductive film laminate of the present invention, the first transparent resin layer 101 and the second transparent resin layer 102 are in the laminated state shown in FIG. 14 than in the laminated state shown in FIG. preferable. 1 is a second transparent electrode pattern electrically insulated from the first transparent electrode pattern 3 by the insulating layer 5 on the first transparent electrode pattern 3. 4 and a further conductive element 6.
Further, as shown in FIG. 14, the end portions of the first transparent resin layer 101 and the second transparent resin layer 102 may have the same width (the first transparent resin layer 101 and the second transparent resin Layer 102 may be laminated with their ends aligned), as shown in FIG. 1, the ends of the first transparent resin layer 7 and the second transparent resin layer 9 have different widths. Alternatively, the end portions of the first transparent resin layer 7 and the second transparent resin layer 9 may be laminated unevenly. In the present invention, as shown in FIG. 14, the end portions of the first transparent resin layer 101 and the second transparent resin layer 102 are preferably the same width from the viewpoint of ease of manufacture.

The end of the decorative layer 2 may be tapered, reverse tapered, or not tapered. In FIG. 1, the decoration layer 2 has a tapered end. On the other hand, as shown in FIG. 14, the decoration layer 2 does not need to form a taper shape. As for the electrically conductive film laminated body of this invention, it is preferable that the edge part of the said decoration layer is a taper shape.

In FIG. 1, the inner diameter (one side) L of the decorative layer 2 is equal to the width of the second transparent resin layer 9. On the other hand, when the gap caused by the height difference between the front plate 1 and the decorative layer 2 is filled with the second transparent resin layer 9, the inner diameter (one side of the decorative layer 2 is not deviated from the spirit of the present invention. ) L may be wider than the width of the second transparent resin layer 9, and conversely, it may be narrower than the width of the second transparent resin layer 9. The second transparent resin layer 9 existing on the decorative layer 2 is more than the second transparent resin layer 9 in direct contact with the front plate 1 due to the pressure applied during transfer due to the thickness of the decorative layer 2. However, the film thickness tends to be thin. Here, in the conductive film laminate of the present invention, the end portion of the second transparent resin layer is disposed on at least a part of the surface opposite to the surface facing the front plate of the functional layer (first surface). It is preferable that the end portion of the transparent resin layer 2 is arranged so as to partially ride on the decorative layer, and the inner diameter (one side) L of the decorative layer 2 is narrower than the width of the second transparent resin layer 9. It is preferable. In other words, the width of the second transparent resin layer 9 is preferably wider than the inner diameter (one side) L of the decorative layer 2. The width of the second transparent resin layer 9 is preferably equal to or larger than the inner diameter (one side) L of the decorative layer 2 and equal to or greater than 20 mm (wide at one end is equal to or smaller than 10 mm), and is equal to or greater than equal to or greater than 10 mm (one side) 5 mm or less at the end of the transfer film) is to transfer the first transparent resin layer and / or the second transparent resin layer contained in the transfer film, and to easily fill the gap between the electrode pattern and the front plate. It is particularly preferable from the viewpoint of suppressing new bubbles from being mixed in the vicinity of the end portion of the second transparent resin layer present on the decorative layer 2.

Further, the mask layer that may be installed is a frame-like (frame-like) pattern of the non-image portion 32 formed on one surface side of the front plate 1 so that the lead wiring and the like cannot be seen. Formed.
The decoration layer 2 may be formed for the purpose of decoration between one surface of the front plate 1 and the mask layer.
As shown in FIG. 5, the capacitive input device of the present invention has a decorative layer 2, a mask layer (a mask layer (covering a region other than the input surface in FIG. 5)). (Not shown) is preferably provided. Further, the front plate 1 can be provided with an opening 8 in a part of the front plate as shown in FIG. A pressing mechanical switch can be installed in the opening 8. Since the tempered glass used as a base material has high strength and is difficult to process, it is general to form the opening 8 by forming the opening 8 before the tempering treatment and then performing the tempering treatment. . However, when trying to form the decorative layer 2 using the liquid resist for decorating layer formation or the screen printing ink on the substrate after the strengthening treatment having the opening 8, the resist component mole from the opening, The problem is that the resist component protrudes from the edge of the glass in the decorative layer provided between the mask layer and the front plate that needs to form a light-shielding pattern until the boundary of the front plate, and the back side of the substrate is contaminated. However, when the decorative layer 2 is formed on the base material having the opening 8 by using a transfer film, such a problem can be solved.

FIG. 3 shows a plurality of first transparent electrode patterns 3 formed on one surface of the front plate 1 by extending a plurality of pad portions in a first direction via connecting portions, A plurality of second transparent electrode patterns 4 comprising a plurality of pad portions that are electrically insulated from the transparent electrode pattern 3 and extend in a direction crossing the first direction; and a first transparent electrode pattern The electrode pattern in which the insulating layer 5 which electrically insulates 3 and the 2nd transparent electrode pattern 4 is formed is shown. The preferred composition, film thickness, and manufacturing method of the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 to be described later are the preferred compositions of the electrode pattern in the laminate of the present invention. The film thickness and the manufacturing method are the same.

Further, at least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4 is formed on the second transparent resin layer 102 disposed on one surface of the front plate 1 and on the decorative layer 2. It can be installed across both regions on the surface opposite to the surface facing the front plate 1. In FIG. 14, the second transparent electrode pattern 4 is on the first transparent resin layer 101 disposed on one surface of the front plate 1 and the surface of the decorative layer 2 facing the front plate 1. Is shown installed across both areas on the opposite side. In this manner, electrode patterns are stacked on the decorative layer 2 that requires a certain thickness and on the second transparent resin layer 102 disposed on one surface of the front plate (for example, transfer described later). Even in the case of laminating a film, by using the second transparent resin layer 102, without using expensive equipment such as a vacuum laminator, the generation of bubbles or the electrode pattern at the boundary of the decorative layer can be performed by a simple process. It becomes possible to laminate while suppressing disconnection.

The first transparent electrode pattern 3 and the second transparent electrode pattern 4 will be described with reference to FIG. FIG. 3 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern in the present invention. As shown in FIG. 3, the first transparent electrode pattern 3 is formed such that the pad portion 3a extends in the first direction C via the connection portion 3b. Further, the second transparent electrode pattern 4 is electrically insulated by the first transparent electrode pattern 3 and the insulating layer 5 and intersects the first direction C (second direction D in FIG. 3). It is comprised by the some pad part extended and formed. Here, when the first transparent electrode pattern 3 is formed, the pad portion 3a and the connection portion 3b may be formed integrally, or only the connection portion 3b is formed, and the pad portion 3a and the second portion 3b are formed. The transparent electrode pattern 4 may be integrally formed (patterned). When the pad portion 3a and the second transparent electrode pattern 4 are integrally formed (patterned), a part of the connection part 3b and a part of the pad part 3a are coupled as shown in FIG. Each layer is formed so that the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are electrically insulated by 5.

In FIG. 14, the conductive element 6 is installed on the surface of the decorative layer 2 opposite to the surface facing the front plate 1. The conductive element 6 is electrically connected to at least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4, and is different from the first transparent electrode pattern 3 and the second transparent electrode pattern 4. Another conductive element. In FIG. 14, a diagram in which the conductive element 6 is connected to the second transparent electrode pattern 4 is shown.

Moreover, in FIG. 1, the 1st transparent resin layer 7 is further installed between the said decoration layer 2 and the said electrode pattern, and between the said 2nd transparent resin layer 9 and the said electrode pattern. . The 1st transparent resin layer 7 may be comprised so that only a part of each component may be covered. Across both regions on the second transparent resin layer 9 disposed on one surface of the front plate 1 and on the surface opposite to the surface facing the front plate 1 of the decorative layer 2, Even when the first transparent resin layer 7 is installed, the use of the second transparent resin layer 9 eliminates the need for expensive equipment such as a vacuum laminator. Lamination without any possible becomes possible.
In addition, in FIG. 1, the transparent protective layer (not shown) may be installed so that all of each component may be covered further. The transparent protective layer is sometimes called an overcoat layer.
The insulating layer 5 and the first transparent resin layer 7 may be made of the same material or different materials. The material constituting the insulating layer 5 and the first transparent resin layer 7 is preferably a material having high surface hardness and high heat resistance, and a known photosensitive siloxane resin material, acrylic resin material, or the like is used.

Examples of the embodiment formed in the manufacturing process of the capacitive input device of the present invention include the embodiments shown in FIGS. FIG. 4 is a top view illustrating an example of the tempered glass 11 in which the opening 8 is formed. FIG. 5 is a top view showing an example of the front plate on which the decorative layer 2 is formed. FIG. 6 is a top view showing an example of the front plate on which the first transparent electrode pattern 3 is formed. FIG. 7 is a top view showing an example of a front plate on which a first transparent electrode pattern (not shown) and a second transparent electrode pattern 4 are formed. FIG. 8 is a top view showing an example of a front plate on which conductive elements 6 different from the first and second transparent electrode patterns are formed. These show examples embodying the above description, and the scope of the present invention is not limitedly interpreted by these drawings.

<(1) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions>
In the method of manufacturing the capacitance-type input device, at least one of the first transparent electrode pattern, the second transparent electrode pattern, and the conductive element, the temporary support and the photocurable resin layer are arranged in this order. The transparent electrode layer is preferably formed by etching using an etching pattern formed by a transfer film (transfer film having a photocurable resin layer) having a temporary support, a thermoplastic resin layer, and light. More preferably, the transparent electrode layer is formed by etching using an etching pattern formed by a transfer film having a curable resin layer in this order.
In addition, the method for manufacturing the capacitance-type input device includes: a temporary support, a conductive curable resin layer, and at least one of the first transparent electrode pattern, the second transparent electrode pattern, and the conductive element. Are preferably formed using a transfer film (transfer film having a conductive curable resin layer) in this order, and a transfer having a temporary support, a thermoplastic resin layer, and a conductive curable resin layer in this order. More preferably, it is formed using a film.
Forming at least one of the first transparent electrode pattern, the second transparent electrode pattern, and the conductive element using a transfer film having a temporary support and a conductive curable resin layer in this order. Specifically, a transfer film having at least one of the first transparent electrode pattern, the second transparent electrode pattern, and the conductive element, and a temporary support and a conductive curable resin layer in this order. The conductive curable resin layer is transferred and formed.
That is, the first transparent electrode pattern 3 is preferably formed using an etching process or a transfer film having a conductive curable resin layer.

(Etching process)
When the first transparent electrode pattern 3 is formed by etching, a transparent electrode layer such as ITO is first sputtered on one surface of the front plate 1 on which the decorative layer 2 or the transparent protective layer 7 is formed. Formed by. Next, an etching pattern is formed on the transparent electrode layer by exposure and development using a transfer film having a photocurable resin layer for etching. Thereafter, the transparent electrode layer is etched to pattern the transparent electrode layer, and the etching pattern is removed, whereby the first transparent electrode pattern 3 and the like can be formed.
Also when using the transfer film which further has the said photocurable resin layer as an etching resist (etching pattern), a resist pattern can be obtained like the said method. For the etching, etching and resist stripping can be applied by a known method described in paragraphs 0048 to 0054 of JP2010-152155A.

For example, as an etching method, there is a commonly performed wet etching method of dipping in an etching solution. As an etchant used for wet etching, an acid type or alkaline type etchant may be appropriately selected in accordance with an object to be etched. Examples of acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and mixed aqueous solutions of acidic components and salts of ferric chloride, ammonium fluoride, potassium permanganate, and the like. Is done. The acidic component may combine a plurality of acidic components. In addition, alkaline type etching solutions include sodium hydroxide, potassium hydroxide, ammonia, organic amines, aqueous solutions of alkali components such as organic amine salts such as tetramethylammonium hydroxide, alkaline components and potassium permanganate. A mixed aqueous solution of a salt such as The alkali component may be a combination of a plurality of alkali components.

The temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower. The resin pattern used as an etching mask (etching pattern) in the present invention exhibits particularly excellent resistance to acidic and alkaline etching solutions in such a temperature range. Therefore, the resin pattern is prevented from peeling off during the etching process, and the portion where the resin pattern does not exist is selectively etched.
After the etching, a cleaning process and a drying process may be performed as necessary to prevent line contamination. The cleaning process is performed by cleaning the substrate with pure water for 10 to 300 seconds at room temperature, for example, and the air blowing pressure (about 0.1 to 5 kg / cm ² ) is appropriately adjusted using an air blow for the drying process. Just do it.

Next, the method of peeling the resin pattern is not particularly limited, and examples thereof include a method of immersing the substrate in a peeling solution being stirred at 30 to 80 ° C., preferably 50 to 80 ° C. for 5 to 30 minutes. The resin pattern used as an etching mask in the present invention exhibits excellent chemical resistance at 45 ° C. or lower as described above, but exhibits a property of swelling by an alkaline stripping solution when the chemical temperature is 50 ° C. or higher. . Due to such properties, when the peeling process is performed using a peeling solution of 50 to 80 ° C., there are advantages that the process time is shortened and the resin pattern peeling residue is reduced. That is, by providing a difference in the chemical temperature between the etching process and the peeling process, the resin pattern used as an etching mask in the present invention exhibits good chemical resistance in the etching process, while in the peeling process. Good peelability will be exhibited, and both conflicting properties of chemical resistance and peelability can be satisfied.

Examples of the stripping solution include inorganic alkali components such as sodium hydroxide and potassium hydroxide, organic alkali components such as tertiary amine and quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or these. A stripping solution dissolved in a mixed solution of You may peel by the spray method, the shower method, the paddle method etc. using said peeling liquid.

(Method using transfer film having conductive curable resin layer)
Moreover, a 1st transparent electrode pattern, a 2nd transparent electrode pattern, and another electroconductive member can also be formed using the transfer film which has a temporary support body and a curable resin layer as a lift-off material. An example of the transfer film includes a transfer film having the photocurable resin layer. Also in this case, the transfer film having the photocurable resin layer preferably has the thermoplastic resin layer between the temporary support and the photocurable resin layer. In this case, after patterning using a transfer film having a photocurable resin layer, after forming a transparent conductive layer on the entire surface of the substrate, the transfer film having a decorative layer or a photocurable resin layer together with the deposited transparent conductive layer A desired transparent conductive layer pattern can be obtained by dissolving and removing the photocurable resin layer in (lift-off method).

When the first transparent electrode pattern 3 is formed using a transfer film having a conductive curable resin layer, it can be formed by transferring the conductive curable resin layer to the surface of the front plate 1. it can.

When the first transparent electrode pattern 3 is formed using a transfer film having the conductive curable resin layer, the front plate (base material) having an opening has no resist component leakage from the opening. Without contaminating the back side, it is possible to manufacture a touch panel having the advantages of thinning and light weight by a simple process.
Furthermore, in forming the first transparent electrode pattern 3, a transfer film having a specific layer structure having a thermoplastic resin layer between the conductive curable resin layer and the temporary support is used to laminate the transfer film. Bubble generation is prevented, and the first transparent electrode pattern 3 having excellent conductivity and low resistance can be formed.

In addition, when the transfer film has a conductive curable resin layer, the conductive curable resin layer contains conductive fibers and the like.

-Conductive curable resin layer (conductive fiber)-
When the transfer film on which the conductive curable resin layer is laminated is used for forming a transparent electrode pattern or another conductive element, the following conductive fibers can be used for the conductive curable resin layer.

There is no restriction | limiting in particular as a structure of an electroconductive fiber, Although it can select suitably according to the objective, A solid structure or a hollow structure is preferable.
Here, the fiber having a solid structure may be referred to as “wire”, and the fiber having a hollow structure may be referred to as “tube”. A conductive fiber having an average minor axis length of 1 nm to 1,000 nm and an average major axis length of 1 μm to 100 μm may be referred to as “nanowire”.
In addition, a conductive fiber having an average minor axis length of 1 nm to 1,000 nm, an average major axis length of 0.1 μm to 1,000 μm, and having a hollow structure may be referred to as “nanotube”.
The material of the conductive fiber is not particularly limited as long as it has conductivity, and can be appropriately selected according to the purpose. However, at least one of metal and carbon is preferable. The conductive fiber is particularly preferably at least one of metal nanowires, metal nanotubes, and carbon nanotubes.

-Metal nanowires-
--metal--
The material of the metal nanowire is not particularly limited. For example, at least one metal selected from the group consisting of the fourth period, the fifth period, and the sixth period of the long periodic table (IUPAC 1991) is preferable. More preferably, at least one metal selected from Group 2 to Group 14 is selected from Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, and Group 14. At least one metal selected from the group is more preferable, and it is particularly preferable to include it as a main component.

Examples of the metal include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, antimony, and lead. And alloys thereof. Among these, in view of excellent conductivity, those mainly containing silver or those containing an alloy of silver and a metal other than silver are preferable.
Containing mainly silver means that the metal nanowire contains 50% by mass or more, preferably 90% by mass or more.
Examples of the metal used in the alloy with silver include platinum, osmium, palladium and iridium. These may be used alone or in combination of two or more.

--shape--
The shape of the metal nanowire is not particularly limited and may be appropriately selected depending on the purpose. In applications where high transparency is required, a cylindrical shape and a cross-sectional shape with rounded polygonal corners are preferred.
The cross-sectional shape of the metal nanowire can be examined by applying a metal nanowire aqueous dispersion on a substrate and observing the cross-section with a transmission electron microscope (TEM).
The corner of the cross section of the metal nanowire means a peripheral portion of a point that extends each side of the cross section and intersects with a perpendicular drawn from an adjacent side. Further, “each side of the cross section” is a straight line connecting these adjacent corners. In this case, the ratio of the “outer peripheral length of the cross section” to the total length of the “each side of the cross section” was defined as the sharpness. For example, in the metal nanowire cross section as shown in FIG. 9, the sharpness can be represented by the ratio of the outer peripheral length of the cross section indicated by the solid line and the outer peripheral length of the pentagon indicated by the dotted line. A cross-sectional shape having a sharpness of 75% or less is defined as a cross-sectional shape having rounded corners. The sharpness is preferably 60% or less, and more preferably 50% or less. If the sharpness exceeds 75%, the electrons may be localized at this corner and plasmon absorption may increase, or the transparency may be deteriorated due to the yellowness remaining. Moreover, the linearity of the edge part of a pattern may fall and a shakiness may arise. The lower limit of the sharpness is preferably 30%, more preferably 40%.

--- Average minor axis length and average major axis length--
The average minor axis length of the metal nanowire (sometimes referred to as “average minor axis diameter” or “average diameter”) is preferably 150 nm or less, more preferably 1 nm to 40 nm, still more preferably 10 nm to 40 nm, 15 nm to 35 nm is particularly preferable.
When the average minor axis length is less than 1 nm, the oxidation resistance may be deteriorated and the durability may be deteriorated. When the average minor axis length is more than 150 nm, scattering due to metal nanowires occurs and sufficient transparency is obtained. There are times when you can't.
The average short axis length of the metal nanowires was measured using a transmission electron microscope (TEM; JEM-2000FX, JEM-2000FX), and 300 metal nanowires were observed. The average minor axis length of was determined. In addition, the shortest axis length when the short axis of the metal nanowire is not circular was the shortest axis.

The average major axis length (sometimes referred to as “average length”) of the metal nanowire is preferably 1 μm to 40 μm, more preferably 3 μm to 35 μm, and even more preferably 5 μm to 30 μm.
If the average major axis length is less than 1 μm, it may be difficult to form a dense network and sufficient conductivity may not be obtained. If it exceeds 40 μm, the metal nanowires are too long and manufactured. Sometimes entangled and agglomerates may occur during the manufacturing process.
The average major axis length of the metal nanowires was measured using, for example, a transmission electron microscope (TEM; JEM-2000FX, JEM-2000FX), and 300 metal nanowires were observed. The average major axis length of the wire was determined. In addition, when the said metal nanowire was bent, the circle | round | yen which makes it an arc was considered and the value calculated from the radius and curvature was made into the major axis length.

The thickness of the conductive curable resin layer is preferably from 0.1 to 20 μm, more preferably from 0.5 to 18 μm, from the viewpoint of process stability such as the stability of the coating solution and the drying time during coating and the development time during patterning. 1 to 15 μm is preferable. The content of the conductive fiber based on the total solid content of the conductive curable resin layer is preferably 0.01 to 50% by mass, and 0.05 to 30% by mass from the viewpoint of conductivity and stability of the coating solution. Is more preferable, and 0.1 to 20% by mass is particularly preferable.

<(2) A plurality of second electrode patterns composed of a plurality of pad portions that are electrically insulated from the first transparent electrode pattern and extend in a direction crossing the first direction>
The second electrode pattern is preferably a transparent electrode pattern. The second transparent electrode pattern 4 can be formed using the transfer film having the etching treatment or the conductive curable resin layer. A preferred embodiment at that time is the same as the method for forming the first transparent electrode pattern 3.

<(3) Insulating layer that electrically insulates first transparent electrode pattern and second transparent electrode pattern>
When the insulating layer 5 is formed, a first transparent electrode pattern is formed by using a transfer film having the photocurable resin layer having an insulating photocurable resin layer as the photocurable resin layer. Further, it can be formed by transferring an insulating photocurable resin layer to the surface of the front plate 1.
When forming an insulating layer using a transfer film, the thickness of the insulating layer is preferably 0.1 to 5 μm, more preferably 0.3 to 3 μm, and more preferably 0.5 to 3 μm from the viewpoint of maintaining insulation. 2 μm is particularly preferable.

<(4) Conductive element that is electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern and is different from the first transparent electrode pattern and the second transparent electrode pattern>
Said another electroconductive element 6 can be formed using the said etching process or the transfer film which has the said electroconductive curable resin layer.
Another conductive element 6 is sometimes referred to as a lead-out wiring.
Conventionally, MAM is generally used as the lead-out wiring because it is highly conductive and easy to finely process. However, Au (gold), Ag (silver), Cu (copper), Al (aluminum), Mo Metals such as (molybdenum), Pd (palladium), Pt (platinum), C (carbon), and Fe (iron) can also be preferably used. By forming a conductive paste or conductive ink containing these metals into a film by a wet method, it is possible to obtain a lead-out wiring by a cheaper process than the vapor deposition method.

<(5) Transparent protective layer>
When forming a transparent protective layer, the said front board 1 in which each element was formed using the transfer film which has the said photocurable resin layer which has a transparent photocurable resin layer as said photocurable resin layer. It can be formed by transferring a transparent photocurable resin layer to the surface.
In the case of forming a transparent protective layer using a transfer film, the thickness of the transparent protective layer is preferably 0.5 to 10 μm, more preferably 0.8 to 5 μm, from the viewpoint of exhibiting sufficient surface protection ability. Particularly preferred is ˜3 μm.

[Image display device]
The image display device of the present invention includes the capacitive input device of the present invention as a component.
The image display device including the capacitive input device of the present invention as a constituent element is “latest touch panel technology” (published July 6, 2009, Techno Times), supervised by Yuji Mitani, “Touch Panel Technology and Development. The configurations disclosed in CM Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. can be applied.

Hereinafter, the present invention will be described more specifically with reference to examples.
The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below. Unless otherwise specified, “%” and “parts” are based on mass.

[Example 1]
<Preparation of transfer film for forming second transparent resin layer>
On a 75 μm thick polyethylene terephthalate film (temporary support), a thermoplastic resin layer coating liquid: Formulation H1 was applied using a slit nozzle and dried to form a thermoplastic resin layer. Next, the intermediate layer coating solution: Formulation P1 was applied on the thermoplastic resin layer and dried to form an intermediate layer. Furthermore, on the intermediate layer, the second transparent resin layer coating liquid: Formulation C1 was applied and dried to form a transparent resin layer A used as the second transparent resin layer. Thus, the thermoplastic resin layer having a dry film thickness of 15.1 μm, the intermediate layer having a dry film thickness of 1.6 μm, and the second transparent resin layer having a dry film thickness of 30 μm are used on the temporary support. A transparent resin layer A was provided. Finally, a protective film (12 μm thick polypropylene film) was pressure-bonded on the transparent resin layer A. In this way, the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), the transparent resin layer A, and the protective film are integrated to form a second transparent resin layer (transparent resin as the second transparent resin layer). A transfer film having a layer A was prepared.

(Coating solution for thermoplastic resin layer: Formulation H1)
Methanol: 11.1 parts by mass Propylene glycol monomethyl ether acetate: 6.36 parts by mass Methyl ethyl ketone: 52.4 parts by mass Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio) (Molar ratio) = 55 / 11.7 / 4.5 / 28.8, weight average molecular weight = 100,000, Tg (glass transition temperature) ≈70 ° C.): 5.83 parts by mass / styrene / acrylic acid copolymer (Copolymerization composition ratio (molar ratio) = 63/37, weight average molecular weight = 10,000, Tg≈100 ° C.): 13.6 parts by mass / monomer 1 (trade name: BPE-500, Shin-Nakamura Chemical Co., Ltd.) 9.1 parts by mass / surfactant (fluorine polymer, trade name: MegaFuck F780F, Dainippon · The Chemical Industries, Ltd.): 0.54 parts by mass The above fluorine-containing _{_{_{_{polymer, C 6 F 13 CH 2 CH}}}} 2 OCOCH = CH 2 40 parts of _{_{_{H (OCH (CH 3) CH}}} 2) 7 OCOCH = CH ₂ 55 parts and a copolymer of 5 parts H (OCH ₂ CH ₂ ) ₇ OCOCH═CH ₂ , a weight average molecular weight of 30,000 and a 30% by mass solution of methyl ethyl ketone.
The viscosity at 120 ° C. after removing the solvent of the coating solution for thermoplastic resin layer: Formulation H1 was 1500 Pa · sec.

(Coating liquid for intermediate layer: prescription P1)
Polyvinyl alcohol: 32.2 parts by mass (trade name: PVA205, manufactured by Kuraray Co., Ltd., saponification degree = 88%, polymerization degree 550)
・ Polyvinylpyrrolidone: 14.9 parts by mass (trade name: K-30, manufactured by IS Japan Co., Ltd.)
-Distilled water: 524 parts by mass-Methanol: 429 parts by mass

(Second coating solution for transparent resin layer: Formulation C1)
-Xylene: 800 parts by mass-Silicone rubber KE-167U (manufactured by Shin-Etsu Chemical Co., Ltd.)
Compound type containing silica): 200 parts by mass / Pt catalyst C25A (manufactured by Shin-Etsu Chemical Co., Ltd.): 0.1 part by mass / crosslinking agent KF9901 (manufactured by Shin-Etsu Chemical Co., Ltd.): 2 parts by mass

<Preparation of first transparent resin layer forming transfer film L1>
On a 75 μm thick polyethylene terephthalate film (temporary support), a thermoplastic resin layer coating liquid: Formulation H1 was applied using a slit nozzle and dried to form a thermoplastic resin layer. Next, the intermediate layer coating solution: Formulation P1 was applied and dried to form an intermediate layer. Furthermore, the 1st coating liquid for transparent resin layers: Formula L1 was apply | coated and dried, and the transparent resin layer F used as a 1st transparent resin layer was formed. Thus, the thermoplastic resin layer having a dry film thickness of 15.1 μm, the intermediate layer having a dry film thickness of 1.6 μm, and the first transparent resin layer having a dry film thickness of 50 μm are used on the temporary support. A transparent resin layer F was provided. Finally, a protective film (12 μm thick polypropylene film) was pressure-bonded on the transparent resin layer F. Thus, the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), the transparent resin layer F, and the protective film are integrated to form a first transparent resin layer (transparent resin as the first transparent resin layer). A transfer film having a layer F) was prepared.

(First coating liquid for transparent resin layer: Formula L1)
・ Methyl ethyl ketone (manufactured by Tonen Chemical Co., Ltd.): 380 parts by mass ・ Silicone resin KR-300 (manufactured by Shin-Etsu Chemical Co., Ltd.);
Xylene solution of straight silicone (solid content 50% by mass): 300 parts by mass Silicone resin KR-311 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Xylene solution of straight silicone (solid content 60% by mass): 2220 parts by mass Phosphoric acid antioxidant (Irgafos168, manufactured by BASF Corp.): 1.5 parts by mass Zn catalyst for silicone resin D-15 (Shin-Etsu) Manufactured by Chemical Industry Co., Ltd .;
Xylene solution (solid content: 25% by mass): 59 parts by mass. Surfactant (trade name: Megafac F-780F, manufactured by DIC Corporation): 6.0 parts by mass

<Preparation of transfer film L100 for forming white decorative layer (frame shape) for touch panel>
On a 75 μm thick polyethylene terephthalate film (temporary support), a thermoplastic resin layer coating liquid: Formulation H1 was applied using a slit nozzle and dried to form a thermoplastic resin layer. Next, the intermediate layer coating solution: Formulation P1 was applied and dried to form an intermediate layer. Further, a decorative layer coating solution: Formula L100 was applied and dried to form a decorative layer. In this way, a thermoplastic resin layer having a dry film thickness of 15.1 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a white decorative layer having a dry film thickness of 35 μm were provided on the temporary support. . Finally, a protective film (thickness 12 μm polypropylene film) was pressure-bonded on the decorative layer. In this way, a transfer film for forming a white decorative layer was produced in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), the decorative layer, and the protective film were integrated.

(Coating liquid for decoration layer: Formula L100)
・ Methyl ethyl ketone (manufactured by Tonen Chemical Co., Ltd.): 56 parts by mass ・ Silicone resin KR-300 (manufactured by Shin-Etsu Chemical Co., Ltd.);
Straight silicone xylene solution (solid content 50% by mass): 584 parts by mass. Silicone resin catalyst D-15 (manufactured by Shin-Etsu Chemical Co., Ltd.);
Xylene solution (solid content: 25% by mass): 12 parts by mass, white pigment dispersion 1 (the following composition): 346 parts by mass, antioxidant (Irgafos 168, manufactured by BASF Corp.): 0.6 parts by mass, interface Activator (Brand name: MegaFuck F-780F, manufactured by DIC Corporation)
: 2.2 parts by mass

-Composition of white pigment dispersion 1-
・ Titanium oxide (CR97 manufactured by Ishihara Sangyo; alumina / zirconia-treated rutile type,
Primary particle diameter 0.25 μm): 70.0 mass%
-Random copolymer (weight average molecular weight 37,000) of benzyl methacrylate / methacrylic acid = 72/28 molar ratio: 3.5% by mass
・ Methyl ethyl ketone (manufactured by Tonen Chemical Co., Ltd.): 26.5% by mass

Using the CO ₂ laser cutter (L-CPNC550, manufactured by Crime Products Co., Ltd.), all the white decorative layer forming transfer films (protective film, decorative layer, intermediate) Layer, thermoplastic resin layer and temporary support) were penetrated from the protective film side and punched out. As shown in FIG. 10, the white decorative layer forming transfer film after punching is formed with an outer peripheral portion 42, a frame inside 41 having a straight portion, and a wiring extraction portion 43 having a straight portion.

<Preparation of front plate with decorative layer (frame shape)>
Using tempered glass (300mm x 400mm x 0.7mm) with an opening (15mmΦ) as a transparent front plate (glass substrate), nylon hair while spraying glass cleaner adjusted to 25 ° C for 20 seconds by shower After washing with a rotating brush having a pure water shower wash, a silane coupling liquid (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3% by mass aqueous solution, trade name: KBM603, Shin-Etsu Chemical Co., Ltd.) )) Was sprayed for 20 seconds with a shower and washed with pure water. This glass substrate was preheated at 90 ° C. for 2 minutes with a base material preheating device to obtain a tempered glass having been subjected to silane coupling treatment.

As shown in FIGS. 11 and 12, the white decorative layer forming transfer film (white decorative layer forming transfer film after punching) punched with the blade 33 is used to protect the non-image portion 31 with a tape. Only 25 was peeled off, and similarly, the two layers of the decorative layer 24 and the intermediate layer 23 of the non-image part 31 were peeled off simultaneously using a tape. Further, only the protective film 25 in the region corresponding to the image portion 32 was peeled off.
Laminator (() The product was laminated at a rubber roller temperature of 120 ° C., a linear pressure of 100 N / cm, and a conveying speed of 2.5 m / min. Using Hitachi Industries, Ltd. (Lamic II type). Subsequently, the polyethylene terephthalate temporary support 21 was peeled off at the interface with the thermoplastic resin layer 22 to remove the temporary support 21.
Thus, the decorative layer 24, the intermediate layer 23, and the thermoplastic resin layer 22 are transferred from the white decorative layer forming transfer film to the image portion 32 of the glass substrate, and the non-image portion 31 of the glass substrate is heated. Only the plastic resin layer 22 was transferred from the white decorative layer forming transfer film.

Next, using a triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) diluted 10 times with pure water) at 30 ° C. For 60 seconds, shower development was performed at a flat nozzle pressure of 0.1 MPa to remove the thermoplastic resin layer 22 and the intermediate layer 23 of the image portion 32 of the glass substrate and the thermoplastic resin layer 22 of the non-image portion 31. Subsequently, air was blown onto the upper surface of the glass substrate to drain the liquid, and then pure water was sprayed for 10 seconds by a shower, pure water shower washing was performed, and air was blown to reduce a liquid pool on the glass substrate.
Thereafter, a white decoration layer 24 is formed by performing post-baking treatment at 240 ° C. for 60 minutes in air under atmospheric pressure (1 atm), and a white decoration layer having a thickness of 35 μm is formed on the upper surface of the glass substrate. A front plate (hereinafter also referred to as “front plate on which a decorative layer is formed”) was obtained. The obtained white decorative layer has a frame shape (also referred to as a frame shape), the length of one side inside the frame (frame) is 70 mm, and the length of the outer side parallel to the inner side is It was 90 mm.

<Preparation of front plate on which first transparent resin layer and second transparent resin layer are formed>
For forming a second transparent resin layer before punching of A5 size (for filling the gap caused by the difference in height between the front plate and the white decorative layer having the transparent resin layer A as the second transparent resin layer) Using a CO ₂ laser cutter (L-CPNC550, manufactured by Climb Products Co., Ltd.), a transfer film and a transfer film for forming the first transparent resin layer (having the transparent resin layer F as the first transparent resin layer) All of the transfer film for forming the second transparent resin layer was penetrated from the protective film side and punched out by a die-cut method. The transfer film for forming a second transparent resin layer after punching has a white decorative layer (frame shape), although each side is 5 mm larger on each side than the length of the inner side of the white decorative layer (frame shape). It is punched out so as to fit inside (region where the white decorative layer is not formed).

The front plate on which the decorative layer was formed was preheated at 90 ° C. for 2 minutes with a base material preheating device.
Only the protective film was peeled off using a tape to the transfer film for forming the second transparent resin layer after punching (having the transparent resin layer A as the second transparent resin layer).
The surface of the transparent resin layer A used as the second transparent resin layer of the image portion exposed after peeling off the protective film, and the surface of the front plate (tempered glass that has been subjected to silane coupling treatment) preheated at 90 ° C. (Laminator (manufactured by Hitachi Industries (Lamic II type)), rubber roller temperature 100 ° C., linear pressure 100 N / cm, conveyance speed 2.5 m / min). The preheated front plate and the transfer film for forming the second transparent resin layer are arranged such that the transfer film for forming the second transparent resin layer is disposed in the frame portion (frame portion) of the white decorative layer without any gap. The steps formed by the height difference between the front plate and the white decorative layer are filled with the transparent resin layer A that is the second transparent resin layer, and each of the transparent resin layers A that are the second transparent resin layers The end portions are fitted on the white decorative layer so as to run 5 mm each from the end portion (inner end portion) of the white decorative layer. Since the edge part of a decoration layer has a taper shape, the reference | standard of the edge part of a decoration layer was made into the part equal to the maximum height of a decoration layer. Subsequently, the polyethylene terephthalate temporary support was peeled off at the interface with the thermoplastic resin layer to remove the temporary support.

Next, using a triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) diluted 10 times with pure water) at 30 ° C. For 60 seconds, shower development was performed at a flat nozzle pressure of 0.1 MPa to remove the thermoplastic resin layer 22 and the intermediate layer 23 in the image area of the front plate and the thermoplastic resin layer 22 in the non-image area. Subsequently, air was blown onto the upper surface of the front plate to drain the liquid, and then pure water was sprayed for 10 seconds by showering, followed by pure water shower washing, and air was blown to reduce the liquid pool on the front plate. Thus, the transparent resin layer A which is the second transparent resin layer was formed on the front plate.
Further, in the same manner as the formation of the transparent resin layer A which is the second transparent resin layer on the front plate, transfer for forming the first transparent resin layer (having the transparent resin layer F as the first transparent resin layer) A transparent resin layer F, which is a first transparent resin layer, was formed on the transparent resin layer A, which is a second transparent resin layer, using a film.
Then, the post-baking process was performed for 60 minutes at 240 degreeC in the air under atmospheric pressure (1 atm), and the laminated body was obtained. Inside the frame portion (frame portion) of the white decorative layer on the front plate of the obtained laminate, the transparent resin layer A that is the second transparent resin layer and the transparent resin layer F that is the first transparent resin layer Are laminated without gaps in this order, the step between the front plate and the white decorative layer is filled with the first transparent resin layer and the second transparent resin layer, and the first transparent resin layer and the first decorative resin layer Fit each edge of the transparent resin layer 2 on the part of the surface on the opposite side of the front panel of the white decorative layer by 5mm from the (inner) edge of the white decorative layer. It is rare.
The second transparent resin layer and the first transparent resin layer are formed by successive transfer processes using the second transparent resin layer forming transfer film and the first transparent resin layer forming transfer film, respectively. This was shown as sequential transfer in Table 2 below.

(Measurement of elastic modulus and elongation at break)
A transfer film for forming a second transparent resin layer (having transparent resin layer A as the second transparent resin layer) was transferred onto a glass substrate to form transparent resin layer A. After a post-bake treatment at 240 ° C. for 60 minutes in air under atmospheric pressure (1 atm), a self-supporting film having a size of 30 mm × 0.5 mm was cut from the substrate to obtain a sample film.
Next, the sample film was pulled using a tensile tester (Tensilon, manufactured by A & D Co., Ltd.), and the elastic modulus E2 and elongation at break φ of the self-supporting film of the transparent resin layer A, which is the second transparent resin layer. Was measured. The measurement was performed at a distance between chucks of 20 mm, a temperature of 23 ° C., and a relative humidity of 55%.
Also, instead of the transfer film for forming the second transparent resin layer (having the transparent resin layer A as the second transparent resin layer), the first transparent resin layer forming (transparent resin as the first transparent resin layer) The elastic modulus E1 of the self-supporting film of the transparent resin layer F, which is the first transparent resin layer, was measured in the same manner as in the elastic modulus measurement method of the transparent resin layer A except that the transfer film (with layer F) was used. .
The obtained results are shown in Table 2 below.

(Measurement of film thickness)
In the sample film used in the tensile test, a notch penetrating to the glass substrate is prepared, and the distance between the glass surface and the film surface of the transparent resin layer A and the distance between the glass surface and the film surface of the transparent resin layer F are determined. It was measured with a Zygo 3D non-contact surface roughness meter.
Furthermore, based on the film thickness of the transparent resin layer A and the film thickness of the transparent resin layer F, the total film thickness of the transparent resin layer was determined.
The obtained results are shown in Table 2 below.

(Evaluation of transparency)
A laminate in which the transparent resin layer A, which is the second transparent resin layer, and the transparent resin layer F, which is the first transparent resin layer, are laminated as described above (this laminate is a first transparent electrode described later) The pattern, insulating layer, second transparent electrode pattern, and transparent protective layer were not allowed to be observed by 60 people, and transparency was evaluated according to the following evaluation criteria. A, B, C or D evaluation is preferable, A, B or C evaluation is more preferable, A or B evaluation is particularly preferable, and A evaluation is more preferable.
<Evaluation criteria>
A: Number of people recognized as yellowish or cloudy 0 to 1 B: Number of people recognized as yellowish or cloudy 2 to 3 people C: Yellowish Or the number of people who recognized that it was cloudy 4-5 people D: The number of people who recognized yellowish or cloudy 6-10 people E: We recognized that it was yellowish or cloudy Number of people 11 or more Evaluation results are shown in Table 2 below.

<Manufacture of the laminate of the present invention>
(Formation of first transparent electrode pattern)
-Formation of transparent electrode layer-
A front plate on which a decorative layer and transparent resin layers (transparent resin layer A and transparent resin layer F) are laminated is introduced into a vacuum chamber, and an ITO target having a SnO ₂ content of 10 mass% (indium: tin = 95). : 5 (molar ratio)), a 40 nm thick ITO thin film was formed by DC magnetron sputtering (conditions: substrate temperature 250 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), and a transparent electrode A front plate with a layer formed was obtained. The surface resistance of the ITO thin film was 80Ω / □.

-Production of transfer film E1 for etching-
In the production of the first transparent resin layer forming transfer film L1, the etching liquid photocurable resin layer coating solution: Formula E1 was used instead of the first transparent resin layer forming coating solution: Formula L1. Except for the above, the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), the photocurable resin layer for etching and the protective film are integrated in the same manner as in the production of the first transfer film L1 for forming the transparent resin layer. Thus, an etching transfer film E1 was obtained (the film thickness of the photocurable resin layer for etching was 2.0 μm).

--- Photocurable resin layer coating solution for etching: Formula E1--
-Methyl methacrylate / styrene / methacrylic acid copolymer (copolymer composition (mass%): 31/40/29, weight average molecular weight 60000,
Acid value 163 mg KOH / g): 16 parts by mass Monomer 1 (Brand name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.): 5.6 parts by mass Addition of 0.5 mol of tetramethylene oxide monomethacrylate of hexamethylene diisocyanate Product: 7 parts by mass-cyclohexanedimethanol monoacrylate as a compound having one polymerizable group in the molecule: 2.8 parts by mass-2-chloro-N-butylacridone: 0.42 parts by mass Biimidazole: 2 .17 parts by mass-Leuco Crystal Violet: 0.26 parts by mass-Phenothiazine: 0.013 parts by mass-Surfactant (trade name: MegaFuck F-780F, manufactured by Dainippon Ink Co., Ltd.): 0.03 parts by mass・ Methyl ethyl ketone: 4 Parts by weight of 1-methoxy-2-propanol 20 parts by weight

-Formation of the first transparent electrode pattern-
The decorative layer, the laminated transparent resin layers (transparent resin layer A and transparent resin layer F), and the transparent electrode layer in the same manner as the cleaning of the tempered glass in the formation of the first transparent resin layer and the second transparent resin layer The front plate on which the film was formed was washed, and then the transfer film E1 for etching from which the protective film was removed was laminated (base material temperature: 130 ° C., rubber roller temperature 120 ° C., linear pressure 100 N / cm, conveying speed 2.2 m / cm). Min). After peeling off the temporary support, the distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the photocurable resin layer for etching is set to 200 μm, and the exposure amount is 50 mJ / cm ² (i-line). ) For pattern exposure.
Next, using a triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) diluted 10 times with pure water) at 25 ° C. Developed for 100 seconds, washed with surfactant-containing cleaning solution (trade name: T-SD3 (manufactured by FUJIFILM Corporation) 10 times with pure water) at 33 ° C. for 20 seconds, The front plate was rubbed with a rotating brush, and the residue was removed by spraying pure water from an ultra-high pressure cleaning nozzle. Furthermore, the post-baking process for 30 minutes was performed at 130 degreeC, and the front board which formed the decorating layer, the laminated | stacked transparent resin layer, the transparent electrode layer, and the photocurable resin layer pattern for an etching was obtained.

A front plate on which a decorative layer, a laminated transparent resin layer, a transparent electrode layer and a photocurable resin layer pattern for etching are formed is placed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.). Immersion, treatment for 100 seconds (etching treatment), dissolution removal of the transparent electrode layer in the exposed area not covered with the photo-curable resin layer for etching, decorative layer, laminated transparent resin layer, transparent electrode layer pattern A front plate (hereinafter also referred to as “front plate with a transparent electrode layer pattern”) on which a photocurable resin layer pattern for etching was formed was obtained.

Next, a front plate with a transparent electrode layer pattern with a photocurable resin layer pattern for etching is applied to a resist stripping solution (N-methyl-2-pyrrolidone, monoethanolamine, a surfactant (trade name: Surfynol 465). , Manufactured by Air Products Co., Ltd., liquid temperature 45 ° C.), immersed in a resist stripping tank, treated for 200 seconds (peeling treatment), removed the photocurable resin layer pattern for etching, and obtained the laminate of Example 1 It was. The obtained laminate is opposed to the front plate, the decorative layer, the second transparent resin layer A, the first transparent resin layer F, one surface of the front plate, and the front plate of the laminated transparent resin layer. 14 has a first transparent electrode pattern (3) installed as shown in FIG. 14 across both regions of the surface opposite to the surface to be performed.
In the laminate of Example 1, the first transparent resin layer F (first transparent resin layer 101) and the second transparent resin layer A (second transparent resin layer 102) are added to the front plate 1. It is laminated | stacked on a part on the decoration layer 2 of the surface by which the decoration layer 2 is arrange | positioned, and the part in which the decoration layer 2 is not arrange | positioned.

(Evaluation of electrode pattern disconnection (bending resistance evaluation))
The laminated body of Example 1 in which the front plate, the second transparent resin layer A, the first transparent resin layer F, and the first transparent electrode pattern were laminated in this order (the laminated body of Example 1 is described later) In the insulating layer, the second transparent electrode pattern, and the transparent protective layer, the surface of the front plate on the side where the second transparent resin layer of the front plate is formed perpendicular to the first transparent electrode pattern. A crack was made from the opposite side. After the front plate is bent by 12 ° starting from the point where the crack arrives on the surface of the front plate on which the second transparent resin layer is formed, the transparency of the region including the position where the front plate is cracked is transparent. The surface resistance value of the electrode pattern was measured across the crack. Subsequently, bending until the transparent electrode pattern was disconnected (that is, the surface resistance value of the transparent electrode pattern overflowed) was repeated, the number of bending until the transparent electrode pattern was disconnected was counted, and bending resistance was evaluated according to the following criteria. A, B or C evaluation is a practical level, A or B evaluation is preferable, and A evaluation is more preferable.

<Evaluation criteria>
A: 300 times or more B: 100 times or more, less than 300 times C: 30 times or more, less than 100 times D: 10 times or more, less than 30 times E: less than 10 times Evaluation results are shown in Table 2 below.

<Formation of insulating layer pattern>
On the laminate of Example 1, an insulating layer pattern, a second transparent electrode pattern, a conductive element different from the first and second transparent electrode patterns and a transparent protective layer-A are formed by the following method. A capacitive input device of Example 1 was produced.
First, a method for forming an insulating layer pattern is described below.

(Preparation of transfer film W1 for forming an insulating layer)
In the production of the decorative layer forming transfer film L100, the decorative layer forming transfer film L100 was prepared except that the insulating layer forming coating liquid: prescription W1 was used instead of the decorative layer coating liquid: prescription L100. Similarly, a transfer film W1 for forming an insulating layer was obtained in which a temporary support, a thermoplastic resin layer, an intermediate layer (oxygen barrier film), a photocurable resin layer for an insulating layer, and a protective film were integrated ( The film thickness of the photocurable resin layer for the insulating layer is 1.4 μm).

-Insulating layer forming coating solution: Formula W1-
Binder 3 (cyclohexyl methacrylate (a) / methyl methacrylate (b) / methacrylic acid copolymer (c) glycidyl methacrylate adduct (d) (composition (% by mass): a / b / c / d = 46/1) / 10/43, weight average molecular weight: 36000, acid value 66 mgKOH / g) 1-methoxy-2-propanol, methyl ethyl ketone solution (solid content: 45%))
: 12.5 parts by mass · DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku Co., Ltd.) propylene glycol monomethyl ether acetate solution (76% by mass): 1.4 parts by mass · Urethane monomer (trade name: NK Oligo UA-32P, manufactured by Shin-Nakamura Chemical Co., Ltd .: non-volatile content 75%, propylene glycol monomethyl ether acetate: 25%: 0.68 parts by mass, tripentaerythritol octaacrylate (trade name: V # 802, Osaka Organic Chemical) Manufactured by Kogyo Co., Ltd.): 1.8 parts by mass. Diethylthioxanthone: 0.17 parts by mass. 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone (trade name: Irgacu) re379, manufactured by BASF): 0.17 parts by mass, dispersant (trade name: Solsperse 20000, manufactured by Avisia): 0.19 parts by mass, surfactant (trade name: MegaFuck F-780F, manufactured by Dainippon Ink): 0.05 part by mass, methyl ethyl ketone: 23.3 parts by mass, MMPGAc (manufactured by Daicel Chemical Co., Ltd.): 59.8 parts by mass The viscosity at 100 ° C. after removing the solvent of the coating liquid W1 for forming the insulating layer is 4000 Pa · sec.

In the same manner as the cleaning of the tempered glass substrate in the formation of the decorative layer, the decorative layer, the second transparent resin layer in which the steps of the decorative layer are embedded, the first transparent resin layer, and the first transparent electrode pattern After the formed laminate of Example 1 was washed, a transfer film W1 for forming an insulating layer was removed by silane coupling treatment and the protective film was removed (base material temperature: 100 ° C., rubber roller temperature 120 ° C., linear pressure). 100 N / cm, transport speed 2.3 m / min). After removing the temporary support, the distance between the exposure mask (quartz exposure mask having the insulating layer pattern) surface and the insulating layer was set to 100 μm, and pattern exposure was performed at an exposure amount of 30 mJ / cm ² (i-line). .

Next, using a triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) diluted 10 times with pure water) at 33 ° C. Using a sodium carbonate / sodium hydrogen carbonate developer (trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 5 times with pure water) at 25 ° C. for 60 seconds. Developed for 50 seconds. Next, using a surfactant-containing cleaning solution (trade name: T-SD3 (manufactured by FUJIFILM Corporation) diluted 10-fold with pure water), the substrate was cleaned at 33 ° C. for 20 seconds, and then cleaned with a rotating brush. The residue was removed by rubbing the face plate and spraying pure water from an ultra-high pressure cleaning nozzle. Furthermore, the post-baking process for 230 degreeC and 60 minutes is performed, the 2nd transparent resin layer and 1st transparent resin layer which embedded the level | step difference of the said decoration layer and a decoration layer, a 1st transparent electrode pattern, an insulating layer A front plate on which a pattern was formed was obtained.

<Formation of second transparent electrode pattern>
(Formation of transparent electrode layer)
Similarly to the formation of the first transparent electrode pattern, the decorative layer, the second transparent resin layer and the first transparent resin layer in which the step of the decorative layer is embedded, the first transparent electrode pattern, the insulating layer The front plate on which the pattern was formed was subjected to DC magnetron sputtering treatment (conditions: substrate temperature 50 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa) to form an ITO thin film having a thickness of 80 nm, and the decorative layer The front plate on which the second transparent resin layer and the first transparent resin layer, the first transparent electrode pattern, the insulating layer pattern, and the transparent electrode layer in which the step of the decorative layer is embedded (hereinafter referred to as “second transparent resin layer”). Also referred to as a “front plate on which an electrode layer is formed”. The surface resistance of the ITO thin film was 110Ω / □.

Similarly to the formation of the first transparent electrode pattern, the transfer film E1 for etching is laminated on the front plate on which the second transparent electrode layer is formed, and the second step in which the step between the decorative layer and the decorative layer is embedded. A front plate on which a transparent resin layer and a first transparent resin layer, a first transparent electrode pattern, an insulating layer pattern, a transparent electrode layer, and a photocurable resin layer pattern for etching were formed (post-baking treatment; 130 ° C., 30 minutes).
Further, in the same manner as the formation of the first transparent electrode pattern, an etching process (30 ° C., 50 seconds) is performed, and then the photocurable resin layer for etching is removed (peeling process: 45 ° C., 200 seconds). The second transparent resin layer and the first transparent resin layer, the first transparent electrode pattern, the insulating layer pattern, the decorative layer and the first transparent resin layer in which the steps of the decorative layer and the decorative layer are embedded And a front plate on which a second transparent electrode pattern formed across the region of the insulating layer was formed.

<Formation of Conductive Element Different from First and Second Transparent Electrode Pattern>
Similar to the formation of the first and second transparent electrode patterns, the second transparent resin layer, the first transparent resin layer, and the first transparent electrode in which the step of the decorative layer and the decorative layer is embedded. The front plate on which the pattern, the insulating layer pattern, and the second transparent electrode pattern were formed was subjected to DC magnetron sputtering treatment to obtain a front plate on which an aluminum (Al) thin film having a thickness of 200 nm was formed.

Similarly to the formation of the first and second transparent electrode patterns, the transfer film E1 for etching is laminated on the front plate on which the aluminum (Al) thin film is formed, and the steps of the decorative layer and the decorative layer are embedded. A front plate on which a second transparent resin layer and a first transparent resin layer, a first transparent electrode pattern, an insulating layer pattern, a second transparent electrode pattern, an aluminum thin film, and a photocurable resin layer pattern for etching are formed. Obtained (post-bake treatment; 130 ° C., 30 minutes).
Further, in the same manner as the formation of the first transparent electrode pattern, by performing an etching process (30 ° C., 50 seconds), and then removing the photocurable resin layer for etching (peeling process: 45 ° C., 200 seconds), The decorative layer, the second transparent resin layer and the first transparent resin layer in which the steps of the decorative layer are embedded, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, the first and second A front plate having a conductive element different from the transparent electrode pattern was obtained.

<Preparation of transparent protective layer>
(Method for forming transparent protective layer-A)
Using the coating solution formulation 1 for photosensitive resin layer described in Example 1 of JP2012-78528A, according to the method described in paragraphs 0103 to 0113 of the same publication, a temporary support (PET) and a thermoplastic resin A photosensitive transfer film in which a layer, an intermediate layer, and a photosensitive resin layer were integrated was produced.
Front plate having a white decorative layer (frame shape) in which the second transparent resin layer and the first transparent resin layer are embedded (the second transparent resin layer in which the step between the decorative layer and the decorative layer is embedded, and the first 1 transparent resin layer, first transparent electrode pattern, insulating layer pattern, second transparent electrode pattern, front plate on which conductive elements different from the first and second transparent electrode patterns are formed) The photosensitive resin layer of the photosensitive transfer film was peeled off at the interface with the temporary support (PET), and then transferred together with the thermoplastic resin layer and the intermediate layer (layer forming step).
Next, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp, the entire surface was exposed from the thermoplastic resin layer side at i line and 40 mJ / cm ² . Next, triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) 10 times with pure water (1 part of T-PD2 and 9 parts of pure water). The mixture was diluted to 30) at 30 C for 60 seconds at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin and the intermediate layer. Subsequently, air was blown onto the upper surface (photosensitive resin layer side) of the glass substrate to drain the liquid, and then pure water was blown for 10 seconds by a shower, washed, and air was blown to reduce the liquid pool on the glass substrate. . Next, the substrate is subjected to a heat treatment (post-bake) at 230 ° C. for 60 minutes, and the second transparent resin layer and the first transparent resin layer in which the steps of the decoration layer and the decoration layer are embedded, the first A front plate in which a transparent electrode pattern, an insulating layer pattern, a second transparent electrode pattern, a conductive element different from the first and second transparent electrode patterns and a transparent protective layer-A are laminated is obtained. A conductive film laminate and a capacitive input device were obtained.

[Examples 2 to 17]
In the preparation of the second transparent resin layer coating liquid: Formulation C1 used in the manufacture of the laminate of Example 1, the second transparent resin layer coating liquid shown in Table 1 below: Formulation instead of Formulation C1 The second transparent resin layer was obtained in the same manner as in Example 1 except that C2 to C5 were used, and the thicknesses of the first transparent resin film and the second transparent resin film were changed to those shown in Table 2 below. Formation transfer films B to E were prepared.
Next, in the preparation of the first transparent resin layer coating liquid: formulation L1 used for the production of the laminate of Example 1, the first transparent resin layer coating liquid shown in Table 1 below is used instead of the formulation L1. The first and second transparent resin films were prepared in the same manner as in Example 1 except that the thicknesses of the first transparent resin film and the second transparent resin film were changed to the specified film thicknesses shown in Table 2 below. The transparent resin layer forming transfer films G to J were prepared.
In Table 1 below, KE-1820 and KE-1886 are one-part silicone rubbers (both manufactured by Shin-Etsu Chemical Co., Ltd.).
In Table 1 below, KR-251, X-40-9246, KR9706, and KR5206 are all silicone resins (all manufactured by Shin-Etsu Chemical Co., Ltd.).
The acrylic resin 1 in Table 1 below is a methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio)) = 55 used in Example 17 and Comparative Example 6 described later. /11.7/4.5/28.8, weight average molecular weight = 100,000, Tg (glass transition temperature) ≈70 ° C.).
In addition, acrylic resin F in the following Table 1 is a random copolymer of benzyl methacrylate / methacrylic acid = 68/32 molar ratio, weight average molecular weight 50,000 used in Comparative Example 7 described later.

In the production of the laminate of Example 1, the types of the first transparent resin layer-forming transfer film and second transparent resin layer-forming transfer film used in Example 1, the first transparent resin layer, and the second The front plate, the second transparent resin layer, and the first transparent resin layer were prepared in the same manner as in the production of the laminate of Example 1 except that the film thickness of the transparent resin layer was changed as shown in Table 2 below. The laminated body which formed the 1st transparent electrode pattern was obtained. The obtained laminates were made into the laminates of Examples 2 to 17, respectively.
Thereafter, in the manufacture of the capacitive input device of Example 1, the front plate, the same as in Example 1 except that the laminates of Examples 2 to 17 were used instead of the laminate of Example 1, respectively. The second transparent resin layer, the first transparent resin layer, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, a conductive element different from the first and second transparent electrode patterns, and transparent A front plate on which the protective layer-A was formed was produced, and the capacitive input devices of Examples 2 to 17 were obtained.
The transparency and bending resistance of the laminates of Examples 2 to 17 (the laminates of Examples 2 to 17 do not include the insulating layer, the second transparent electrode pattern, and the transparent protective layer) are the same as those of Example 1. The evaluation results are shown in Table 2 below.

[Example 18]
<Preparation of Multilayer Transfer Film of First Transparent Resin Layer and Second Transparent Resin Layer>
On a 75 μm thick polyethylene terephthalate film (temporary support), a thermoplastic resin layer coating liquid: Formulation H1 was applied using a slit nozzle and dried to form a thermoplastic resin layer. Next, the intermediate layer coating solution: Formulation P1 was applied and dried to form an intermediate layer. Furthermore, the 1st coating liquid for transparent resin layers: Formula L1 was apply | coated and dried, and the transparent resin layer F was formed.

Further, a second transparent resin layer coating solution: Formula C6 was applied on the transparent resin layer F and dried to form a transparent resin layer A-2. Thus, a thermoplastic resin layer having a dry film thickness of 15.1 μm, an intermediate layer having a dry film thickness of 1.6 μm, a transparent resin layer F having a dry film thickness of 50 μm, and a dry film thickness on the temporary support. Provided a transparent resin layer A-2 having a thickness of 30 μm. Finally, a protective film (12 μm thick polypropylene film) was pressure-bonded on the transparent resin layer A-2. Thus, the first transparent resin layer (transparent resin layer F) in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), the transparent resin layer F, the transparent resin layer A-2, and the protective film are integrated. Then, a transfer film having a multilayer of the second transparent resin layer (transparent resin layer A-2) was produced.

(Second coating solution for transparent resin layer: Formula C6)
-Xylene: 500 parts by mass-Methyl ethyl ketone (manufactured by Tonen Chemical Co., Ltd.): 300 parts by mass-Silicone rubber KE-167U (manufactured by Shin-Etsu Chemical Co., Ltd., compound type containing silica): 200 parts by mass-Pt catalyst C25A (Shin-Etsu Chemical) (Made by Co., Ltd.): 0.1 parts by mass / crosslinking agent KF9901 (produced by Shin-Etsu Chemical Co., Ltd.): 2 parts by mass

In the production of the laminate of Example 1, instead of forming the transparent resin layer A as the second transparent resin layer on the preheated front plate, the first transparent resin layer (transparent resin layer F) and The second transparent resin layer and the first transparent resin layer are simultaneously laminated using the transfer film of the second transparent resin layer (transparent resin layer A-2), and the subsequent first transparent resin layer. Except that the transparent resin layer F was not formed, the front plate, the second transparent resin layer, the first transparent resin layer, and the first transparent electrode pattern were formed in the same manner as in the production of the laminate of Example 1. A laminated body was obtained. The obtained laminated body was taken as the laminated body of Example 18.
Thereafter, in the manufacture of the capacitive input device of Example 1, the front plate and the second plate were obtained in the same manner as in Example 1 except that the laminate of Example 18 was used instead of the laminate of Example 1. Transparent resin layer, first transparent resin layer, first transparent electrode pattern, insulating layer pattern, second transparent electrode pattern, conductive element different from first and second transparent electrode patterns, and transparent protective layer- A front plate on which A was formed was produced, and the capacitive input device of Example 18 was obtained.
The results of evaluating the transparency and bending resistance of the laminate of Example 18 (the laminate of Example 18 does not include the insulating layer, the second transparent electrode pattern, and the transparent protective layer) in the same manner as in Example 1. It described in Table 2 below.

[Example 19]
In Example 19, instead of forming a transparent resin layer using a transfer film, a first transparent resin layer and a second transparent resin layer were prepared by application using a liquid resist.
The two types of transparent resists for preparing the transparent resin layer used in Example 19 were formulated in accordance with the second transparent resin layer coating liquid used in Example 1: Formulation C1 and the first transparent resin layer coating liquid: It is the same as each prescription L1.
Using a glass substrate coater (manufactured by FS Japan Co., Ltd., trade name: MH-1600) having a slit nozzle on the front plate on which the decorative layer is formed, a second transparent resin layer is prepared. A transparent resist (prescription: C1) was applied to obtain a coating layer. Subsequently, after part of the solvent was dried by VCD (vacuum drying device, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, the front was removed using EBR (edge bead remover). Unnecessary transparent resist around the face plate was removed and pre-baked at 120 ° C. for 3 minutes to obtain a 10.0 μm-thick transparent resin layer on the front plate (liquid resist method). The application of the transparent resist for preparing the transparent resin layer (prescription: C1) was repeated three times to obtain a second transparent resin layer having a thickness of 30.0 μm on the front plate. The second transparent resin layer obtained by repeating the coating three times was a single layer.
Next, the transparent resist for preparing the first transparent resin layer (prescription: L1) is applied and dried on the second transparent resin layer in the same manner as the transparent resist for preparing the second transparent resin layer (prescription: C1). A transparent resin layer having a thickness of 10.0 μm was obtained. The application of the transparent resist for preparing the transparent resin layer (prescription: L1) was repeated five times to obtain a first transparent resin layer having a thickness of 50.0 μm. The first transparent resin layer obtained by repeating the coating 5 times was a single layer.
Thereafter, post-baking treatment is performed at 240 ° C. for 60 minutes in air under atmospheric pressure (1 atm), and the front plate, the second transparent resin layer A, and the first transparent resin layer F are laminated in this order. Got the body. A first transparent electrode pattern is formed on the first transparent resin layer F in the same manner as in the production of the laminated body of Example 1 except that the obtained laminated body is used. The laminated body which formed the transparent resin layer, the 1st transparent resin layer, and the 1st transparent electrode pattern was obtained. The obtained laminated body was taken as the laminated body of Example 19.
Thereafter, in the manufacture of the capacitive input device of Example 1, the same as the manufacture of the capacitive input device of Example 1, except that the laminate of Example 19 was used instead of the laminate of Example 1. Thus, a capacitance type input device of Example 19 was produced.
The results of evaluating the transparency and bending resistance of the laminate of Example 19 (the laminate of Example 19 does not include the insulating layer, the second transparent electrode pattern, and the transparent protective layer) in the same manner as in Example 1. It described in Table 2 below.
In addition, the 2nd transparent resin layer and the 1st transparent resin layer were formed by the continuous application | coating process using the coating liquid for 2nd transparent resin layers, and the coating liquid for 1st transparent resin layers, respectively. This is shown as slit coating in Table 2 below.

[Comparative Example 1]
In the production of the laminate of Example 1, the first transfer film for forming a transparent resin layer and the second transfer film for forming a transparent resin layer are not transferred, that is, there is no transparent resin layer on the front plate. A first transparent electrode pattern was directly formed on the front plate in the same manner as in the production of the laminate of Example 1 except that the state was changed to obtain a laminate of Comparative Example 1.
Thereafter, in the manufacture of the capacitive input device of Example 1, the same as the manufacture of the capacitive input device of Example 1, except that the laminate of Comparative Example 1 was used instead of the laminate of Example 1. Before forming the front plate, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, the conductive element different from the first and second transparent electrode patterns, and the transparent protective layer-A A face plate was produced and used as a capacitive input device of Comparative Example 1.
The results of evaluating the transparency and bending resistance of the laminate of Comparative Example 1 (the laminate of Comparative Example 1 does not include an insulating layer, a second transparent electrode pattern, and a transparent protective layer) in the same manner as in Example 1. It described in Table 2 below.

[Comparative Examples 2 to 8]
In Comparative Examples 2 and 3, in the production of the laminate of Example 1, the film thickness of the second transparent resin layer formed on the preheated front plate was changed as shown in Table 2 below. In the same manner as in the production of the laminate of Example 1, except that the transparent resin layer A was formed and the subsequent transparent resin layer F, which was the first transparent resin layer, was not formed, the front plate and the single-layer transparent A laminate in which the resin layer A and the first transparent electrode pattern were formed was obtained. The obtained laminated body was made into the laminated body of Comparative Examples 2 and 3, respectively.

In Comparative Examples 4 and 5, in the production of the laminates of Comparative Examples 2 and 3, the type of the second transparent resin layer forming transfer film and the thickness of the second transparent resin layer are shown in Table 2 below. A laminated body in which a front plate, a single second transparent resin layer F, and a first transparent electrode pattern were formed was obtained in the same manner as in Comparative Examples 2 and 3 except that the procedure was changed as described above. The obtained laminated body was made into the laminated body of Comparative Examples 4 and 5, respectively.

Comparative Example 7 was the same as Example 1 except that the second transparent resin layer coating liquid: Formulation C1 in Example 1 was used except that the transparent resin layer coating liquid: Formulation C7 shown in Table 1 below was used. Thus, a transfer film for forming the second transparent resin layer (having the transparent resin layer L as the second transparent resin layer) was produced.
(Second coating solution for transparent resin layer: Formula C7)
Methyl ethyl ketone (manufactured by Tonen Chemical Co., Ltd.): 800 parts by mass Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 /28.8, weight average molecular weight = 100,000, Tg (glass transition temperature) ≈70 ° C.): 200 parts by mass / surfactant (trade name: Megafac F-780F, manufactured by DIC Corporation)
: 2.0 parts by mass In the production of the laminate of Comparative Example 2, the transfer film for forming a transparent resin layer in which the type of the second transfer film for forming a transparent resin layer was changed as shown in Table 2 below was used. Except for the above, in the same manner as in the production of the laminate of Comparative Example 2, a laminate having a front plate, a single second transparent resin layer L, and a first transparent electrode pattern was obtained. The obtained laminated body was made into the laminated body of the comparative example 7, respectively.

In Comparative Examples 6 and 8, in the production of the laminate of Example 1, the types of the first transparent resin layer-forming transfer film and the second transparent resin layer-forming transfer film used in Example 1, and the first A front plate and a second transparent resin were prepared in the same manner as in the production of the laminate of Example 1, except that the film thicknesses of the transparent resin layer and the second transparent resin layer were changed as shown in Table 2 below. The laminated body which formed the layer, the 1st transparent resin layer, and the 1st transparent electrode pattern was obtained. The obtained laminated body was made into the laminated body of Comparative Examples 6 and 8, respectively.

Thereafter, in the manufacture of the capacitive input device of Example 1, the front plate, the same as Example 1 except that the laminates of Comparative Examples 2 to 8 were used instead of the laminate of Example 1, respectively. A front plate on which a transparent resin layer, a first transparent electrode pattern, an insulating layer pattern, a second transparent electrode pattern, a conductive element different from the first and second transparent electrode patterns, and a transparent protective layer-A are formed. The capacitance type input devices of Comparative Examples 2 to 8 were manufactured.
The transparency and bending resistance of the laminates of Comparative Examples 2 to 8 (the laminates of Comparative Examples 2 to 8 do not include the insulating layer, the second transparent electrode pattern, and the transparent protective layer) are the same as in Example 1. The evaluation results are shown in Table 2 below.

From Table 2 above, in the laminate of the present invention in which at least two transparent resin layers satisfying the elastic modulus and elongation at break specified in the present invention are provided between the front plate and the transparent electrode pattern, the front plate has cracks. It was found that the electrode pattern disconnection can be suppressed even if it occurs and bends. Therefore, the capacitance-type input device of the present invention using the laminate of the present invention can operate a module (for example, a touch panel) even if the front plate cracks and bends, extracts data, etc. Is possible.
On the other hand, from Comparative Example 1, it was found that when the transparent resin layer was not provided between the front plate and the transparent electrode pattern, the electrode pattern was easily disconnected when the front plate was cracked and bent.
From Comparative Examples 2 and 3, when the transparent resin layer having a low elastic modulus and high elongation at break is provided between the front plate and the transparent electrode pattern, the front plate is cracked even if the film thickness is increased. It was found that the electrode pattern is easily disconnected when bent. FIG. 17 shows a schematic diagram of a laminate in which a transparent resin layer having a low elastic modulus and high elongation at break is provided as a single layer between the front plate and the transparent electrode pattern. In the laminate shown in FIG. 17 (A), when the front plate 110 is cracked as shown in FIG. 17 (B), the transparent resin layer 102 having a low elastic modulus and high elongation at break does not break, but the bending becomes large. It is considered that the electrode pattern 100 that is harder than the transparent resin layer was cracked.
From Comparative Examples 4, 5 and 7, when a transparent resin layer having a high elastic modulus is provided between the front plate and the transparent electrode pattern as a single layer, the front plate is cracked and bent even if the film thickness is increased. In this case, it was found that the electrode pattern was easily disconnected. FIG. 18 shows a schematic view of a laminate in which a transparent resin layer having a high elastic modulus is provided as a single layer between the front plate and the transparent electrode pattern. In the laminate shown in FIG. 18A, when the front plate 110 is cracked as shown in FIG. 18B, the transparent resin layer 101 having a high elastic modulus is also cracked. It is thought that it broke.
From Comparative Example 6, when the breaking elongation φ of the second transparent resin layer, which is the second transparent resin layer from the electrode pattern side, is lower than the lower limit specified in the present invention, the front plate is cracked and bent It was found that the electrode pattern was easily broken.
From Comparative Example 8, the elastic modulus E1 of the first transparent resin layer in contact with the electrode pattern is smaller than the elastic modulus E2 of the second transparent resin layer that is the second transparent resin layer from the electrode pattern side. In this case, it was found that the electrode pattern was easily broken when the front plate was bent due to a crack.

Moreover, from the said Table 2, in the preferable aspect of the laminated body of this invention, it turned out that transparency becomes further favorable.
The capacitive input device of each example in which an insulating layer, a second transparent electrode pattern, and a transparent protective layer are further laminated on the laminate of each example is the same as the laminate of each example. As a result of evaluation, the transparency and the bending resistance with respect to the disconnection of the electrode pattern when the front plate cracked and bent were good.

1, 110 Front plate 2

Decorating layer

3, 100 Electrode pattern (first transparent electrode pattern)
3a Pad portion 3b Connection portion 4 Second transparent electrode pattern 5 Insulating layer 6 Conductive element 7 First transparent resin layer (transparent resin layer having high elastic modulus)
8 Opening 9 Second transparent resin layer (transparent resin layer having low elastic modulus and high elongation at break)
L Inner diameter of decorative layer (one side)
DESCRIPTION OF SYMBOLS 11 Tempered glass C 1st direction D 2nd direction 21 Temporary support body 22 Thermoplastic resin layer 23 Intermediate | middle layer 24 Decorating layer 25 Cover film (protective film)
31 Non-image part 32 Image part 33 Blade 40 Transfer material 41 Inside frame 42 Outside frame 43 Wiring extraction part 44 Decoration layer (region not removed)
45 Region 101 from which decorative layer is removed First transparent resin layer (transparent resin layer with high elastic modulus)
102 2nd transparent resin layer (transparent resin layer of low elastic modulus and high elongation at break)
103 Other transparent resin layers

Claims

A laminate having at least two transparent resin layers laminated on a part or all of the front plate, and further having an electrode pattern on the at least two transparent resin layers,
The elastic modulus E1 of the first transparent resin layer in contact with the electrode pattern and the elastic modulus E2 of the second transparent resin layer that is the second transparent resin layer from the electrode pattern side satisfy the following formula 1. ,
A laminate in which the elongation at break φ of the second transparent resin layer satisfies the following formula 2.
E1> E2 Formula 1
φ ≧ 10% Formula 2
The laminate according to claim 1, wherein the total thickness of the first transparent resin layer and the second transparent resin layer is 10 to 150 µm.
The laminate according to claim 1 or 2, wherein the thickness of the first transparent resin layer and the thickness of the second transparent resin layer are each independently 5 to 100 µm.
The laminate according to any one of claims 1 to 3, wherein at least one of the transparent resin layers contains a compound having a siloxane structure.
The laminate according to any one of claims 1 to 4, wherein the first transparent resin layer contains at least a silicone resin as a binder resin.
The laminate according to any one of claims 1 to 5, wherein the second transparent resin layer contains at least silicone rubber as a binder resin.
The laminate according to any one of claims 1 to 6, wherein the elongation at break φ of the second transparent resin layer is 20% or more.
The laminate according to any one of claims 1 to 7, wherein the elastic modulus E2 of the second transparent resin layer is 50 MPa or less.
The laminate according to any one of claims 1 to 8, wherein the elastic modulus E1 of the first transparent resin layer is 100 MPa or more.
A decorative layer is disposed on a part of one surface of the front plate;
The first transparent resin layer and the second transparent resin layer are arranged on a part of the surface of the front plate on which the decorative layer is disposed, on the decorative layer, and the decorative layer is disposed. The laminated body according to any one of claims 1 to 9, wherein the laminated body is laminated on a portion not formed.
A temporary support;
A first transparent resin layer containing at least a silicone resin as a binder resin;
A transfer film having a second transparent resin layer containing at least silicone rubber as a binder resin,
The transfer film having a structure in which the first transparent resin layer is sandwiched between the temporary support and the second transparent resin layer.
The transfer film according to claim 11, further comprising a thermoplastic resin layer between the temporary support and the first transparent resin layer.
The first transparent resin layer and the second transparent resin layer of the transfer film according to claim 11 or 12, a front plate, the second transparent resin layer, the first transparent resin layer, Are transferred to a part or all of the front plate, so that are stacked in this order,
The method for producing a laminate according to any one of claims 1 to 10, further comprising a step of forming an electrode pattern on the first transparent resin layer.
A second transparent resin layer forming step of transferring a second transparent resin layer containing at least silicone rubber as a binder resin from the transfer film to a part or all of the front plate;
A first transparent resin layer containing at least a silicone resin as a binder resin from the transfer film so that the front plate, the second transparent resin layer, and the first transparent resin layer are laminated in this order. Forming a first transparent resin layer to be transferred onto the second transparent resin layer;
Forming an electrode pattern on the first transparent resin layer,
The method for producing a laminate according to any one of claims 1 to 10, wherein the forming step of the second transparent resin layer and the forming step of the first transparent resin layer are simultaneous or continuous transfer steps. .
A step of forming a second transparent resin layer, wherein a resin composition containing at least silicone rubber as a binder resin is applied to a part or all of the front plate;
The resin composition containing at least a silicone resin as a binder resin, the second transparent resin layer, the second transparent resin layer, and the second transparent resin layer are laminated in this order. Forming a first transparent resin layer applied on the resin layer;
Forming an electrode pattern on the first transparent resin layer,
The method for producing a laminate according to any one of claims 1 to 10, wherein the forming step of the second transparent resin layer and the forming step of the first transparent resin layer are continuous coating steps.
A conductive film laminate having a second electrode pattern electrically insulated from the electrode pattern on the electrode pattern of the laminate according to any one of claims 1 to 10.
The conductive film laminate according to claim 16, wherein the second electrode pattern is a transparent electrode pattern.
A capacitance-type input device comprising the conductive film laminate according to claim 16 or 17.
An image display device comprising the capacitive input device according to claim 18 as a constituent element.