JP2017177546A - Transfer film, electrode protective film of capacitance type input device, laminate and capacitance type input device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer film having photolithography property, less in generation of air bubbles and less in transfer defect, an electrode protective film of a capacitance type input device, a laminate, the capacitance type input device and an image display device.SOLUTION: There is provided a transfer film having a temporary supporter, a curable resin layer, and a protective film in this order, with an oxygen permeability coefficient of the protective film of 100 cm25 μm/m24 hr. atm or more and a surface roughness Ra of a surface in the curable resin layer side of the protective film of 5 to 60 nm.SELECTED DRAWING: None

Description

  The present invention relates to a transfer film, an electrode protective film for a capacitive input device, a laminate, and a capacitive input device.

In recent years, electronic devices such as mobile phones, car navigation systems, personal computers, ticket vending machines, and bank terminals are equipped with a liquid crystal display device having a touch panel type input device, and a finger or a touch pen is used for an image displayed on the liquid crystal display device. There is an electronic device that can input a desired instruction by touching.
Such input devices (touch panels) include a resistance film type and a capacitance type.
The capacitive input device has an advantage that a light-transmitting conductive film is simply formed on a single substrate. In such a capacitance-type input device, for example, electrode patterns are extended in directions intersecting with each other, and when a finger or the like comes in contact, the capacitance between the electrodes is detected to detect an input position. There are types (see, for example, Patent Documents 1 to 3).

Furthermore, Patent Document 4 discloses a transparent substrate having a refractive index of 1.6 to 1.78 so that the transparent electrode pattern of the capacitive input device described in Patent Documents 1 to 3 is not visually recognized. An in-plane region in which a first transparent film having a thickness of 55 to 110 nm, a transparent electrode pattern, and a second transparent film having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm are stacked in this order. The laminated body included in is disclosed.
Various methods are known as a method of forming a transparent film as described in Patent Document 4. Patent Document 4 describes a method of sputtering a metal oxide and a method of transferring a curable resin layer formed on a temporary support onto a substrate. In Patent Document 4, by using a transfer film, a pressure-sensitive (pressing mechanical mechanism, not a capacitance change) switch is installed on a part of a front plate (a surface that is directly contacted with a finger). When the curable resin layer is formed, the resist component is not leaked or protruded from the opening, and the process of removing the exposed or protruding portion is eliminated. It is described that efficiency can be increased.

  Patent Document 5 has a temporary support, a curable resin layer, and a second resin layer disposed adjacent to the curable resin layer in this order, and the refractive index of the second resin layer. Discloses a transfer film having a refractive index higher than that of the curable resin layer and a refractive index of the second resin layer of 1.6 or more.

  Patent Document 6 discloses a method for forming a resin pattern having good developability using a photosensitive composition containing a resin having an acidic group in a side chain, a polymerizable compound, and a photopolymerization initiator. Have been described.

JP 2010-86684 A JP 2010-152809 A JP 2010-257492 A JP, 2014-010814, A JP 2014-108541 A JP 2012-078528 A

  In Patent Document 5, after forming a curable resin layer on a temporary support, a transfer film is formed by curing the curable resin layer by exposure and then laminating a second resin layer by coating. Yes.

  Here, the generally used capacitive input device is provided with a frame around the image display area. Therefore, the refractive index adjustment layer (layer for making the transparent electrode pattern difficult to see and improving the transparency of the transparent electrode pattern) and the transparent protective layer (overcoat layer) of the capacitive input device using the transfer film. In this case, the refractive index adjustment layer is laminated on the image display area to solve the problem of seeing the transparent electrode pattern, and at the same time, the refractive index adjustment layer and the transparent protective layer are not laminated on the frame portion. Thus, it is required to be easily formed into a desired pattern shape. As a method for forming a desired pattern, a method (die-cut method or half-cut method) in which the shape of the transfer film is cut according to the shape of the frame portion of the capacitive input device can be considered. However, from the viewpoint of further improving productivity, after transferring at least one of the refractive index adjustment layer and the transparent protective layer from the transfer film onto the transparent electrode pattern, the photo can be developed into a desired pattern using photolithography. It is desired to form a laminate having good lithographic properties (patterning properties using photolithography).

  Under such circumstances, the inventors of the present invention manufactured a transfer film provided with a protective film without curing the curable resin layer for the purpose of imparting photolithography properties. However, when the protective film is peeled off from the obtained transfer film, a part of the curable resin layer which is not cured is transferred to the protective film, and the transfer defect of the curable resin layer (a part of the curable resin layer is lost). In some cases, a problem that a lot of defects) occurs. This is because the curable resin layer that is not cured has high adhesiveness, and a part of the curable resin layer adheres to the protective film that should not be transferred.

The inventors of the present invention diligently studied to solve the transfer defects of the curable resin layer, and find out that the transfer defects of the curable resin layer can be reduced by increasing the surface roughness Ra of the protective film. It came.
However, it has been found that the transfer film having the surface roughness Ra of the protective film increased has a problem that many bubbles are generated at the interface between the protective film and the curable resin layer.

  That is, a transfer film that can be developed into a desired pattern by photolithography, has few bubbles, and has few transfer defects has not been known.

The present invention has been made in view of the present situation.
The problem to be solved by the present invention is to provide a transfer film having photolithographic properties, less bubbles and less transfer defects.
The problem to be solved by the present invention is to provide an electrode protective film for a capacitive input device in which a temporary support is removed from a transfer film having photolithographic properties, generating less bubbles, and having less transfer defects. It is an object of the present invention to provide a laminated body having an electrode protective film of a capacitive input device, an electrode protective film of the capacitive input device, or a capacitive input device including the laminated body.

The inventors of the present invention have found that the above-mentioned problems can be solved by combining a protective film whose surface roughness Ra and oxygen permeability coefficient are controlled in a specific range with a curable resin layer that has not been cured. It was.
The present invention, which is a specific means for solving the above problems, and preferred embodiments of the present invention are as follows.

[1] a temporary support;
A curable resin layer that is curable; and
A protective film;
In this order,
The oxygen permeability coefficient of the protective film is 100 cm ³ · 25 μm / m ² · 24 hours · atm or more,
The transfer film whose surface roughness Ra of the surface at the side of the curable resin layer of a protective film is 5-60 nm.
[2] The transfer film according to [1], wherein the protective film has an oxygen permeability coefficient of 5000 cm ³ · 25 μm / m ² · 24 hours · atm or less.
[3] The transfer film according to [1] or [2], wherein the protective film has a thickness of 10 to 75 μm.
[4] The transfer film according to any one of [1] to [3], wherein the protective film contains polyethylene terephthalate or polypropylene.
[5] Having a second resin layer between the protective film and the curable resin layer,
The transfer according to any one of [1] to [4], wherein the second resin layer contains particles having a refractive index of 1.50 or more in an amount of 60 to 90% by mass with respect to the total solid content of the second resin layer. the film.
[6] The transfer film according to [5], which satisfies the following formula 1:
Formula 1: n ₁ <n ₂
n ₁ represents the refractive index of the curable resin layer, and n ₂ represents the refractive index of the second resin layer.
[7] The transfer film according to any one of [5] or [6], wherein the second resin layer is curable.
[8] The transfer film according to any one of [5] to [7], wherein the particles having a refractive index of 1.50 or more are zirconium oxide particles or titanium oxide particles.
[9] The transfer film according to any one of [5] to [8], wherein the curable resin layer and the second resin layer are in direct contact.
[10] The transfer film according to any one of [5] to [9], wherein the curable resin layer and the second resin layer are alkali-soluble.
[11] The curable resin layer includes a polymerizable compound and a binder polymer,
The transfer film according to any one of [1] to [10], wherein the binder polymer is an alkali-soluble resin.
[12] The transfer film according to any one of [1] to [11], which has a roll shape.
[13] An electrode protective film for a capacitive input device, wherein the protective film is removed from the transfer film according to any one of [1] to [12].
[14] a substrate including an electrode of the capacitive input device;
A laminate comprising the electrode protective film of the capacitive input device according to [13].
[15] A capacitive input device having the electrode protective film of the capacitive input device according to [13] or the laminate according to [14].

  According to the present invention, it is possible to provide a transfer film that has photolithographic properties, generates less bubbles, and has few transfer defects. In addition, according to the present invention, it is possible to provide an electrode protective film, a laminate, a capacitive input device, and an image display device of a capacitive input device.

It is a section schematic diagram showing an example of composition of an electrostatic capacity type input device of the present invention. It is a cross-sectional schematic diagram which shows another example of a structure 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 relationship between the transparent electrode pattern in this invention, and a non-pattern area | region. It is a top view which shows an example of the front plate in which the opening part was formed. It is a top view which shows an example of the front board in which the mask 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 the 1st and 2nd transparent electrode pattern was formed. It is the schematic which shows an example of the desired pattern by which the curable resin layer and the 2nd resin layer were hardened. It is explanatory drawing which shows an example of the taper shape of the edge part of a transparent electrode pattern. It is a section schematic diagram showing an example of composition of a layered product of the present invention. It is a section schematic diagram showing an example of composition of a transfer film of the present invention. It is a top view which shows another example of a structure of the electrostatic capacitance type input device of this invention, and shows the aspect containing the terminal part (terminal part) of the routing wiring which is pattern-exposed and is not covered with the curable resin layer . Schematic showing an example of a state before a transfer film of the present invention having a curable resin layer and a second resin layer is laminated on a transparent electrode pattern of a capacitive input device and cured by exposure or the like FIG.

  Hereinafter, the transfer film of the present invention, the electrode protective film of the capacitive input device, the laminate, and the capacitive input device will be described. The description of the constituent elements described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Transfer film]
The transfer film of the present invention comprises a temporary support,
A curable resin layer that is curable; and
A protective film;
In this order,
The oxygen permeability coefficient of the protective film is 100 cm ³ · 25 μm / m ² · 24 hours · atm or more,
The surface roughness Ra of the surface of the protective film on the side of the curable resin layer is 5 to 60 nm.
With such a configuration, it is possible to provide a transfer film that has photolithography properties, generates less bubbles, and has few transfer defects.
By using a curable resin layer that is curable, after the curable resin layer is transferred from the transfer film, it can be developed into a desired pattern by photolithography.
By setting the oxygen permeability coefficient of the protective film to 100 cm ³ · 25 μm / m ² · 24 hours · atm or more, air bubbles are discharged out of the transfer film through the protective film. Further, by setting the surface roughness Ra of the surface of the protective film on the side of the curable resin layer to 60 nm or less, the amount of gas mixed when the protective film is laminated on the surface of the curable resin layer side can be reduced. Can be reduced.
By setting the surface roughness Ra of the protective film to 5 nm or more, the adhesion between the protective film and the curable resin layer can be lowered, and transfer defects can be reduced.
Herein, that the layer has a curing property, using a Fourier transform infrared spectrophotometer to measure the wavelength region of 400cm ^-1 ~4000cm ^-1 of the resin layer, C = C bond from the 810 cm ^-1 This can be detected by measuring the peak intensity. The peak at 810 cm ⁻¹ derived from the C═C bond of the layer after the layer is further subjected to a curing step (at least one of exposure and heating) than the peak intensity of 810 cm ⁻¹ derived from the C═C bond of the layer When the strength is small, it can be detected that the resin has curability. A layer that is not completely cured (for example, a semi-cured layer) may have curability.
It is preferable to determine that the layer has curability from the double bond consumption rate of the layer.
The curable resin layer that is curable is preferably a curable resin layer having a double bond consumption rate of less than 10%. In the state of the transfer film, the curable resin layer may not be cured. In this case, the double bond consumption rate of the curable resin layer is 0%. Further, in the state of the transfer film, the curable resin layer may be cured with a double bond consumption rate of less than 10%, in which case the double bond consumption rate of the curable resin layer exceeds 0%. Less than 10%. From the viewpoint of imparting photolithographic properties, the double bond consumption rate of the curable resin layer is more preferably 0%.
On the other hand, the transfer film of the present invention is curable by the curable resin layer (preferably has a double bond consumption rate of less than 10%) as long as it is satisfied before exposure for photolithography. Good. When photolithography is performed using the transfer film of the present invention, the curable resin layer is exposed to a curable resin layer (preferably the double bond consumption rate is less than 10%), and the double bond consumption rate of the curable resin layer is exposed. May be 10% or more. For example, in the transfer film of the present invention, the curable resin layer (and the second resin layer, if necessary) is processed into a desired pattern by photolithography before transferring it to the transfer object, thereby increasing the double bond consumption rate. After setting it to 10% or more, the curable resin layer (and the second resin layer as necessary) may be transferred to the transfer target. In addition, the transfer film of the present invention transfers the curable resin layer (and the second resin layer, if necessary) to the transfer object, and then transfers the curable resin layer (and the second resin if necessary) to a desired pattern. May be processed by photolithography to increase the double bond consumption rate to 10% or more.
Hereinafter, preferred embodiments of the transfer film of the present invention will be described.

<Configuration of transfer film>
The transfer film of the present invention has a temporary support, a curable resin layer, and a protective film in this order. The temporary support and the curable resin layer may be arranged in direct contact with each other, or may be arranged via another layer. Examples of the other layer include a second resin layer, a thermoplastic resin layer, and an intermediate layer described later. The temporary support and the curable resin layer are preferably disposed in direct contact with each other.
In FIG. 12, an example of the preferable layer structure of the transfer film of this invention is shown. FIG. 12 is a schematic view of the transfer film 30 of the present invention in which the temporary support 26, the curable resin layer 7, the second resin layer 12, and the protective film 29 are laminated in direct contact with each other in this order.
In the transfer film of the present invention, the curable resin layer and the second resin layer are preferably in direct contact with each other from the viewpoint of production simplicity.
In the transfer film of the present invention, it is preferable that the second resin layer and the protective film are in direct contact from the viewpoint of reducing transfer defects.

  The transfer film of the present invention is preferably in a roll shape. Here, when the transfer film is formed into a roll shape, the dent defect due to the foreign matter propagates and the dent defect tends to increase. In a preferred embodiment of the transfer film of the present invention, dent defects can be reduced. Therefore, even if the transfer film has a roll shape, dent defects can be reduced.

<Protective film>
The transfer film of the present invention has a protective film,
The oxygen permeability coefficient of the protective film is 100 cm ³ · 25 μm / m ² · 24 hours · atm or more,
The surface roughness Ra of the surface of the protective film on the side of the curable resin layer is 5 to 60 nm.

(Oxygen permeability coefficient)
In the present invention, the oxygen permeability coefficient of the protective film is 100 cm ³ · 25 μm / m ² · 24 hours · atm or more.
Oxygen permeability coefficient of the protective film is preferably ^{100~5000cm 3 · 25μm / m 2 ·} 24 hr · atm, particularly preferably ^{200~4500cm 3 · 25μm / m 2 ·} 24 hr · atm, 500~4000cm ³ · 25μm / More preferably, m ² · 24 hours · atm. Generation | occurrence | production of a bubble can be decreased by making oxygen permeability of a protective film more than the lower limit of a preferable range. From the viewpoint of obtaining the effect of reducing the generation of bubbles, there is no upper limit on the oxygen permeability of the protective film. By setting the oxygen permeability of the protective film to be equal to or less than the upper limit value of the preferable range, the strength of the protective film can be maintained and dent defects described later can be reduced.
The oxygen transmission coefficient of the protective film is measured by the method described later. The oxygen permeability coefficient of the protective film is the same value as that of the protective film alone before the production even when the protective film is peeled off from the state of the transfer film.

(Surface roughness Ra)
In this invention, surface roughness Ra of the surface at the side of the curable resin layer of a protective film is 5-60 nm, It is preferable that it is 10-50 nm, and it is more preferable that it is 15-45 nm.
The surface roughness Ra means arithmetic average roughness.
The surface roughness Ra of the protective film is measured by the method described later. The surface roughness Ra of the protective film is the same value as in the case of the protective film alone before the production even when the protective film is peeled off from the state of the transfer film.

(Thickness)
In this invention, it is preferable that the thickness of a protective film is 10-75 micrometers, It is more preferable that it is 20-65 micrometers, It is especially preferable that it is 25-35 micrometers.
Here, a protective film is formed after forming a curable resin layer having a curable property (preferably having a double bond consumption rate of less than 10%) (or by forming a second resin layer thereon). When the transfer film obtained by laminating is rolled up in a roll shape, the curable resin layer (and / or the second resin layer) is recessed, and a dent defect is likely to occur. Since the dust generated in the manufacturing process is wound in a state of adhering to the protective film, the winding pressure causes a mark through the dust, and the curable resin layer (and / or the second resin layer) is depressed. Presumed. It is preferable to reduce the dent defect in order to suppress image distortion or the like in the image display device. The curable resin layer (and / or the second resin layer preferably having a double bond consumption rate of less than 10%) that is curable (preferably having a double bond consumption rate of less than 10%) is soft, A dent defect is likely to occur.
The thickness of the protective film is preferably 10 μm or more from the viewpoint of reducing dent defects (defects in which the curable resin layer and / or the second resin layer are recessed).
The thickness of the protective film is preferably 25 to 35 μm from the viewpoint that all of bubbles, transfer defects and dent defects can be reduced.

(resin)
There is no restriction | limiting in particular as resin of a protective film. At least one of the oxygen permeability and the surface roughness of the protective film can be controlled by the type of resin. Examples of the resin for the protective film include polyester (preferably polyethylene terephthalate), polyolefin (preferably polypropylene), polyvinyl chloride, polycarbonate, and the like.
In this invention, it is preferable that a protective film contains a polyethylene terephthalate or a polypropylene, and it is more preferable that a protective film contains a polypropylene.

In particular, a polyester (preferably polyethylene terephthalate) film and a polyolefin (preferably polypropylene) film having a surface roughness Ra in the above-described preferable range have not been used as protective films for transfer films.
In this invention, it is preferable to use the polyester film and polyolefin film whose surface roughness Ra is said preferable range. Examples of the method for controlling the surface roughness Ra of the polyester film and the polyolefin film include a method of controlling the degree of orientation of the protective film, controlling the density, and performing smoothing or roughening. Particularly, a polyolefin (preferably polypropylene) film has conventionally had a large surface roughness Ra. In the present invention, the surface roughness Ra of the polyolefin (preferably polypropylene) film is reduced by controlling stretching conditions and cooling conditions after stretching, and controlling the crystal state, and is controlled within the above preferred range. It is preferable.
Examples of the method for controlling the oxygen permeability of the protective film include a method for controlling the degree of orientation of the protective film, controlling the density, and performing a smoothing or roughening treatment.

  As the protective film, among the protective films described in JP-A-2006-259138, paragraphs 0083 to 0087 and 0093, those having oxygen permeability and surface roughness within the above ranges can be appropriately used.

  A commercially available protective film may be used as the protective film. Examples of the commercially available protective film include Alphan E201F, Alphane FG201 (manufactured by Oji F-Tex Co., Ltd., polypropylene film), and NF-15 (manufactured by Tamapoly Co., Ltd.).

<Temporary support>
The transfer film of the present invention has a temporary support.
There is no restriction | limiting in particular as a temporary support body used for a transfer film.

(Thickness)
The thickness of the temporary support is not particularly limited, and is generally in the range of 5 to 200 μm, and particularly preferably in the range of 10 to 150 μm from the viewpoint of ease of handling and versatility.

(Material)
The temporary support is preferably a film, and more preferably a resin film.
As the film used as the temporary support, a flexible material that does not cause significant deformation, shrinkage, or elongation under pressure or under pressure and heat 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.

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 provided with conductivity by a method described in JP-A-2005-221726.

<Curable resin layer>
(Double bond consumption rate of curable resin layer)
The transfer film of the present invention has a curable curable resin layer.
The double bond consumption rate of the curable resin layer is preferably less than 10%, and more preferably 0%. The double bond consumption rate of a curable resin layer is calculated | required by the method as described in the below-mentioned Example.

  The curable resin layer may be thermosetting, photocurable, thermosetting and photocurable. It is preferable that the curable resin layer is at least thermosetting from the viewpoint that the film can be thermoset after transfer to impart film reliability. It is more preferable that the curable resin layer is thermosetting and photocurable from the viewpoint of being easy to be photocured and formed into a film after the transfer, and thermosetting after forming the film to impart the reliability of the film.

  The cured layer obtained by curing the curable resin layer may lose curability (thermosetting or photocuring). In the present specification, for convenience of explanation, a cured layer that has lost its curability is also referred to as a curable resin layer.

(Refractive index)
The refractive index n ₁ of the curable resin layer is preferably 1.45 ≦ n ₁ ≦ 1.59, more preferably 1.5 ≦ n ₁ ≦ 1.53, and 1.5 ≦ n ₁ ≦ 1.52 is particularly preferable, and 1.51 ≦ n ₁ ≦ 1.52 is more preferable.

  There is no particular limitation on the method for controlling the refractive index of the curable resin layer. For example, a curable resin layer having a desired refractive index is used alone, a curable resin layer to which particles such as metal oxide particles, metal particles, and metal oxide particles are added, or a metal salt and a polymer are used. A complex can be used.

(Thickness)
The thickness of the curable resin layer is preferably 1 to 20 μm, more preferably 2 to 15 μm, and particularly preferably 3 to 12 μm. The curable resin layer is preferably used for an image display portion of a capacitance type input device. In that case, high transparency and high transmittance are important. When the thickness of the curable resin layer is sufficiently thin, a decrease in transmittance due to the absorption of the curable resin layer is less likely to occur, and yellowing is also less likely to occur due to the difficulty of absorbing short waves.
In the present specification, T ₁ represents the average thickness of the curable resin layer. In the present specification, the term “thickness of the curable resin layer” refers to “average thickness T ₁ of the curable resin layer” unless otherwise specified.

(Alkali soluble)
In the transfer film of the present invention, the curable resin layer is preferably alkali-soluble. That the resin layer is alkali-soluble means that the resin layer is dissolved by a weak alkaline aqueous solution. The curable resin layer is more preferably developable with a weak alkaline aqueous solution.

(composition)
The curable resin layer of the transfer film may be a negative type material or a positive type material. The curable resin layer of the transfer film is preferably a negative material.
When the curable resin layer of the transfer film is a negative material, the curable resin layer preferably contains a binder polymer, a polymerizable compound, a polymerization initiator, and a compound that can react with an acid by heating. Further, the curable resin layer may include metal oxide particles. Furthermore, the curable resin layer may contain an additive.

-Binder polymer-
In the transfer film of the present invention, the curable resin layer preferably contains a binder polymer.
There is no restriction | limiting in particular as a binder polymer of a curable resin layer. In the transfer film of the present invention, the binder polymer of the curable resin layer is preferably an alkali-soluble resin.
There is no restriction | limiting in particular as alkali-soluble resin. The alkali-soluble resin is preferably a carboxyl group-containing resin. When the curable resin layer contains a carboxyl group-containing resin, the curable resin layer preferably further contains a compound (preferably a blocked isocyanate) that can react with an acid by heating. When the curable resin layer contains a carboxyl group-containing resin and a compound capable of reacting with an acid by heating (preferably a blocked isocyanate), the three-dimensional crosslinking density of the curable resin layer is increased by thermal crosslinking, so that the carboxyl group The carboxyl group of the containing resin can be dehydrated and hydrophobized. By hydrophobizing the curable resin layer, the wet heat resistance of the curable resin layer can be increased.
In addition, the detail of the compound which can react with an acid by heating is mentioned later.

  It is preferable that the binder polymer contained in the curable resin layer contains an acrylic resin. Here, the second resin layer described later preferably contains a resin having an acid group. Interlayer adhesion between the curable resin layer and the second resin layer is that the binder polymer contained in the curable resin layer and the resin having an acid group contained in the second resin layer both contain an acrylic resin. From the viewpoint of enhancing the ratio, it is more preferable.

  The binder polymer contained in the curable resin layer is particularly preferably a carboxyl group-containing resin and a binder polymer that is an acrylic resin.

The curable resin layer may contain a binder polymer other than the carboxyl group-containing resin. As the other binder polymer, any polymer component can be used without particular limitation. The other binder polymer is preferably a binder polymer having high surface hardness and high heat resistance from the viewpoint of use as a transparent protective layer of a capacitive input device.
The other binder polymer is more preferably an alkali-soluble resin.
Examples of other binder polymers include known photosensitive siloxane resin materials as alkali-soluble resins.

The binder polymer used in the curable resin layer is not particularly limited as long as it is not contrary to the gist of the present invention, and can be appropriately selected from known ones. The polymer described in paragraph 0025 of JP2011-95716A, It is preferable to use the polymers described in paragraphs 0033 to 0052 of Kai 2010-237589. Moreover, the following compound A is mentioned as a preferable example of the binder polymer which is carboxyl group-containing resin and is an acrylic resin.

The acid value of the binder polymer is preferably 60 to 200 mgKOH / g, more preferably 60 to 150 mgKOH / g, and particularly preferably 60 to 110 mgKOH / g.
As the acid value of the binder polymer, the value of the theoretical acid value calculated by the calculation method described in the following document or the like is used. JP 2004-149806 A [0063], JP 2012-211228 A [0070].

The curable resin layer may contain a polymer latex as a binder polymer. The polymer latex referred to here is one in which water-insoluble polymer particles are dispersed in water. The polymer latex is described, for example, in Soichi Muroi “Chemistry of Polymer Latex (published by Kobunshi Shuppankai (Showa 48))”.
Polymer particles that can be used include acrylic, vinyl acetate, rubber (for example, styrene-butadiene, chloroprene), olefin, polyester, polyurethane, polystyrene, and copolymers thereof. Particles are preferred.
It is preferable to increase the bonding force between the polymer chains constituting the polymer particles. Examples of means for strengthening the bonding force between polymer chains include a method using an interaction generated by hydrogen bonding and a method of generating a covalent bond.

As a means for imparting an interaction caused by hydrogen bonding, it is preferable to introduce a monomer having a polar group in the polymer chain by copolymerization or graft polymerization.
The polar groups of the binder polymer include carboxyl groups (contained in acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid, partially esterified maleic acid, etc.), primary, secondary and tertiary amino groups , Ammonium base, sulfonic acid group (such as styrene sulfonic acid group) and the like. The binder polymer preferably has at least a carboxyl group.
The preferable range of the copolymerization ratio of the monomer having these polar groups is 5 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 20 to 30% by mass with respect to 100% by mass of the polymer. is there.

  As a means for generating a covalent bond, an epoxy compound, a blocked isocyanate, an isocyanate, a vinyl sulfone compound, an aldehyde compound, a methylol compound, a carboxyl, a hydroxyl group, a carboxyl group, a primary, secondary amino group, an acetoacetyl group, a sulfonic acid group, etc. The method of making an acid anhydride etc. react is mentioned.

The polymer latex that can be used in the present invention may be obtained by emulsion polymerization or may be obtained by emulsification. The method for preparing these polymer latexes is described, for example, in “Emulsion Latex Handbook” (edited by Emulsion Latex Handbook Editorial Committee, published by Taiseisha Co., Ltd. (Showa 50)).
Examples of the polymer latex that can be used in the present invention include an aqueous dispersion of polyethylene ionomer (trade name: Chemipearl S120, manufactured by Mitsui Chemicals, Inc., solid content 27%) (trade name: Chemipearl S100, manufactured by Mitsui Chemicals, Inc.). (Product name: Chemipearl S111, Mitsui Chemicals Co., Ltd. Solid content 27%) (Product name: Chemipearl S200, Mitsui Chemicals Co., Ltd. Solid content 27%) (Trade name: Chemipearl S650, manufactured by Mitsui Chemicals, Inc., solid content 27%) (trade name: Chemipearl S75N, manufactured by Mitsui Chemicals, Inc., solid content 24%), polyether -Based polyurethane aqueous dispersion (trade name: Hydran WLS-201, manufactured by DIC Corporation. Solid content 35%, Tg-50 ° C., T Is a glass transition temperature (abbreviation of glass transition temperature) (trade name: Hydran WLS-202 manufactured by DIC Corp., solid content 35%, Tg-50 ° C.) (trade name: Hydran WLS-221 manufactured by DIC Corp.). (Trade name: Hydran WLS-210 manufactured by DIC Corporation. Solid content: 35%, Tg-15 ° C) (trade name: manufactured by Hydran WLS-213 DIC Co., Ltd., solid content 35) %, Tg-15 ° C.) (trade name: manufactured by Hydran WLI-602 DIC Corp., solid content: 39.5%, Tg-50 ° C.) (trade name: manufactured by Hydran WLI-611 DIC Corp., solid content 39) 0.5%, Tg-15 ° C.), ammonium acrylate copolymer (trade name: Jurimer AT-210, manufactured by Nippon Pure Chemical), alkyl acrylate Copolymer ammonium (trade name: Jurimer ET-410, manufactured by Nippon Pure Chemical), alkyl acrylate copolymer ammonium (trade name: Jurimer AT-510, manufactured by Nippon Pure Chemical), polyacrylic acid (trade name: Jurimer AC-10L, manufactured by Nippon Pure Chemical) ) Is neutralized with ammonia and emulsified.

  The weight average molecular weight of the binder polymer is preferably 10,000 or more, more preferably 20,000 to 100,000.

-Polymerizable compound-
In the transfer film of the present invention, the curable resin layer preferably contains a polymerizable compound, more preferably contains a polymerizable compound having an ethylenically unsaturated group, and the photopolymerizable compound has an ethylenically unsaturated group. It is particularly preferable that The polymerizable compound preferably has at least one ethylenically unsaturated group as a polymerizable group. The polymerizable compound may have an epoxy group in addition to the ethylenically unsaturated group. More preferably, the polymerizable compound of the curable resin layer includes a compound having a (meth) acryloyl group.
A polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type.

The polymerizable compound preferably includes a bifunctional polymerizable compound, more preferably includes a compound having two ethylenically unsaturated groups, and particularly preferably includes a compound having two (meth) acryloyl groups. .
The polymerizable compound having a bifunctional ethylenically unsaturated group is not particularly limited as long as it is a compound having two ethylenically unsaturated groups in the molecule, and a commercially available (meth) acrylate compound can be used. For example, tricyclodecane dimethanol diacrylate (A-DCP Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (DCP Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol di Acrylate (A-NOD-N, Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, Shin-Nakamura Chemical Co., Ltd.) and the like can be preferably used.
The content of the bifunctional polymerizable compound is preferably in the range of 20 to 90% by mass and preferably in the range of 30 to 80% by mass with respect to all the polymerizable compounds contained in the curable resin layer. More preferably, it is in the range of 35 to 75% by mass.

It is preferable that at least one of the polymerizable compounds contains a carboxyl group because the carboxyl group of the binder polymer and the carboxyl group of the polymerizable compound can form a carboxylic acid anhydride in the curable resin layer.
It does not specifically limit as a polymeric compound containing a carboxyl group, A commercially available compound can be used. For example, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M-520 (manufactured by Toagosei Co., Ltd.), Aronix M-510 (manufactured by Toagosei Co., Ltd.) and the like can be preferably used.
The content of the polymerizable compound containing a carboxyl group is preferably in the range of 1 to 50% by mass, and in the range of 1 to 30% by mass with respect to all the polymerizable compounds contained in the curable resin layer. It is more preferable, and it is especially preferable that it is the range of 5-15 mass%.

It is preferable that a urethane (meth) acrylate compound is included as a polymerizable compound.
In the urethane (meth) acrylate compound, the number of functional groups of the polymerizable group, that is, the number of (meth) acryloyl groups is preferably 3 or more, more preferably 4 or more.
It does not specifically limit as a urethane (meth) acrylate compound, A commercially available compound can be used. For example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.) can be preferably used.
The content of the urethane (meth) acrylate compound is preferably 10% by mass or more, and more preferably 20% by mass or more, based on all polymerizable compounds contained in the curable resin layer.

The polymerizable compound may contain a trifunctional or higher functional polymerizable compound.
The photopolymerizable compound having a trifunctional or higher functional ethylenically unsaturated group is not particularly limited as long as it is a compound having three or more ethylenically unsaturated groups in the molecule. For example, skeletons such as dipentaerythritol (tri / tetra / penta / hexa) acrylate, pentaerythritol (tri / tetra) acrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, isocyanuric acid acrylate, glycerin triacrylate, etc. ) Acrylate compounds can be used, and those having a long span length between (meth) acrylates are preferred. Specifically, the above-mentioned dipentaerythritol (tri / tetra / penta / hexa) acrylate, pentaerythritol (tri / tetra) acrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) AD-TMP, etc.), caprolactone-modified compounds of skeletal (meth) acrylate compounds such as isocyanuric acid acrylate (Nippon Kayaku KAYARAD DPCA, Shin-Nakamura Chemical A-9300-1CL, etc.), alkylene oxide-modified compounds (Nipponization) Pharmaceutical KAYARAD RP-1040, Shin-Nakamura Chemical Co., Ltd. ATM-35E, A-9300, Daicel Ornex EBECRYL 135, etc.), ethoxylated glycerin triacrylate (Shin Nakamura Chemical Co., Ltd. A-GLY) -9E etc.) can be preferably used. Moreover, it is preferable to use trifunctional or more urethane (meth) acrylate. As tri- or more functional urethane (meth) acrylates, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.) And the like can be preferably used.
The content of the tri- or higher functional polymerizable compound is preferably in the range of 3 to 50% by mass, and in the range of 5 to 30% by mass with respect to all the polymerizable compounds contained in the curable resin layer. Is more preferable, and the range of 7 to 20% by mass is particularly preferable.

The polymerizable compound used in the curable resin layer preferably has a weight average molecular weight of 200 to 3000, more preferably 250 to 2600, and particularly preferably 280 to 2200.
The transfer film preferably has a molecular weight of 250 or more, more preferably 280 or more, more preferably 300 or more, of the polymerizable compound, which is the minimum molecular weight among all the polymerizable compounds contained in the curable resin layer. It is particularly preferred.
In the transfer film, the curable resin layer contains a polymerizable compound, and the ratio of the content of the polymerizable compound having a molecular weight of 300 or less to the content of all the polymerizable compounds contained in the curable resin layer is 30% or less. Preferably, it is 25% or less, particularly preferably 20% or less.

-Polymerization initiator-
In the transfer film of the present invention, the curable resin layer preferably contains a polymerization initiator, and more preferably contains a photopolymerization initiator. When the curable resin layer contains a polymerizable compound and a polymerization initiator, it is possible to easily form a pattern of the curable resin layer.
There is no restriction | limiting in particular as a polymerization initiator used for a curable resin layer. As a polymerization initiator used for the curable resin layer, for example, the photopolymerization initiator described in paragraphs 0031 to 0042 described in JP 2011-95716 A can be used. For example, in addition to 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (trade name: IRGACURE OXE-01, manufactured by BASF), ethanone, 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), 2- (dimethylamino) -2 -[(4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE 379EG, manufactured by BASF), 2-methyl-1- (4-methylthiophenyl) 2-morpholinopropan-1-one (trade name: IRGACURE 907, manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydro Xyl-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (trade name: IRGACURE 127, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1 (trade name: IRGACURE 369, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: IRGACURE 1173, manufactured by BASF), 1-hydroxy-cyclohexyl -Phenyl-ketone (trade name: IRGACURE 184, manufactured by BASF), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: IRGACURE 651, manufactured by BASF), oxime ester type (trade name: Lunar 6 (manufactured by DKSH Japan Ltd.) is preferably used Door can be.
It is preferable that 1 mass% or more of polymerization initiators are contained with respect to the curable resin layer, and it is more preferable that 2 mass% or more is contained. The above-mentioned polymerization initiator is preferably contained in an amount of 10% by mass or less, more preferably 5% by mass or less, more preferably from the viewpoint of improving the patterning property with respect to the curable resin layer.

-Compound capable of reacting with acid by heating-
In the transfer film of the present invention, the curable resin layer preferably contains a compound capable of reacting with an acid by heating.

The compound capable of reacting with an acid by heating is not particularly limited as long as it is not contrary to the gist of the present invention. The compound capable of reacting with an acid by heating is preferably a compound having a high reactivity with an acid after heating at a temperature exceeding 25 ° C., compared with the reactivity with an acid at 25 ° C. The compound that can react with an acid by heating has a group that can react with an acid that is temporarily inactivated by a blocking agent, and the group derived from the blocking agent is dissociated at a predetermined dissociation temperature. preferable.
Examples of the compound capable of reacting with an acid by heating include a carboxylic acid compound, an alcohol compound, an amine compound, a blocked isocyanate (also referred to as blocked isocyanate), an epoxy compound, and the like, and is preferably a blocked isocyanate. .

The compound capable of reacting with an acid by heating having a hydrophilic group in the molecule is not particularly limited, and a known compound can be used. The method for preparing the compound capable of reacting with an acid by heating having a hydrophilic group in the molecule is not particularly limited, but for example, it can be prepared by synthesis.
The compound having a hydrophilic group in the molecule and capable of reacting with an acid by heating is preferably a blocked isocyanate having a hydrophilic group in the molecule. Details of the compound capable of reacting with an acid by heating having a hydrophilic group in the molecule will be described in the explanation of the blocked isocyanate described later.

  The blocked isocyanate means “a compound having a structure in which an isocyanate group of an isocyanate is protected (masked) with a blocking agent”.

  The initial Tg of the blocked isocyanate is preferably -40 ° C to 10 ° C, and more preferably -30 ° C to 0 ° C.

It is preferable that the dissociation temperature of block isocyanate is 100 to 160 degreeC, and it is more preferable that it is 130 to 150 degreeC.
The dissociation temperature of the blocked isocyanate in the present specification refers to “according to the deprotection reaction of the blocked isocyanate when measured by differential scanning calorimetry (DSC) with a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.). "Endothermic peak temperature".

  Examples of the blocking agent having a dissociation temperature of 100 ° C. to 160 ° C. include pyrazole compounds (3,5-dimethylpyrazole, 3-methylpyrazole, 4-bromo-3,5-dimethylpyrazole, 4-nitro-3,5-dimethyl. Pyrazole, etc.), active methylene compounds (malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate), etc.), triazole compounds (1,2,4-triazole, etc.) ), Oxime compounds (formal oxime, acetal oxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, etc., having a structure represented by —C (═N—OH) — in the molecule). Among these, from the viewpoint of storage stability, oxime compounds and pyrazole compounds are preferable, and oxime compounds are particularly preferable.

It is preferable that the blocked isocyanate has an isocyanurate structure from the viewpoint of film brittleness and substrate adhesion. A blocked isocyanate having an isocyanurate structure can be prepared, for example, by isocyanurating hexamethylene diisocyanate.
Among blocked isocyanates having an isocyanurate structure, compounds having an oxime structure using an oxime-based compound as a blocking agent are more likely to have a dissociation temperature within a preferable range than a compound having no oxime structure, resulting in less development residue. It is preferable from the viewpoint of easy handling.

  The number of blocked isocyanate groups of the blocked isocyanate is preferably 1 to 10, more preferably 2 to 6, and particularly preferably 3 to 4.

As the blocked isocyanate, a blocked isocyanate compound described in Japanese Patent Application Laid-Open No. 2006-208824, 0074 to 0085, may be used, and the contents of this publication are incorporated herein.
Specific examples of the blocked isocyanate used for the transfer film include the following compounds. However, the blocked isocyanate used in the present invention is not limited to the following specific examples.

  Commercially available blocked isocyanate can also be mentioned as blocked isocyanate used for a transfer film. For example, Takenate (registered trademark) B870N (made by Mitsui Chemicals, Inc.), which is a methyl ethyl ketone oxime blocked form of isophorone diisocyanate, Duranate (registered trademark) MF-K60B, TPA-B80E, X3071. 04 (all manufactured by Asahi Kasei Chemicals Corporation).

The blocked isocyanate having a hydrophilic group in the molecule is preferably a blocked isocyanate in which at least a part of the isocyanate group is an aqueous isocyanate group to which a hydrophilic group is added. By reacting the isocyanate group of the polyisocyanate with a blocking agent (sometimes referred to as an amine compound), a blocked isocyanate having a hydrophilic group in the molecule can be obtained. Examples of the reaction method include a method of adding a hydrophilic group to a part of the isocyanate group of the polyisocyanate by a chemical reaction.
The hydrophilic group of the compound capable of reacting with an acid by heating is not particularly limited, and specific examples include a nonionic hydrophilic group and a cationic hydrophilic group.

Although it does not specifically limit as a nonionic hydrophilic group, Specifically, the compound etc. which added ethylene oxide and propylene oxide to the hydroxyl group of alcohol, such as methanol, ethanol, butanol, ethylene glycol, or diethylene glycol, are mentioned. That is, the hydrophilic group of a compound that can react with an acid by heating having a hydrophilic group in the molecule is preferably an ethylene oxide chain or a propylene oxide chain. These compounds have active hydrogens that react with isocyanate groups and can thereby be added to isocyanate groups. Among these, monoalcohols that can be dispersed in water with a small amount of use are preferable.
Moreover, as addition number of an ethylene oxide chain or a propylene oxide chain, 4-30 are preferable and 4-20 are more preferable. If the addition number is 4 or more, the water dispersibility tends to be further improved. Moreover, if the addition number is 30 or less, the initial Tg of the obtained blocked isocyanate tends to be further improved.
The addition of a cationic hydrophilic group is a method using a compound having both a cationic hydrophilic group and an active hydrogen that reacts with an isocyanate group; for example, a functional group such as a glycidyl group is previously introduced into the polyisocyanate; Thereafter, for example, there is a method of reacting a specific compound such as sulfide or phosphine with this functional group. The former method is easy.
Although it does not specifically limit as active hydrogen which reacts with an isocyanate group, Specifically, a hydroxyl group, a thiol group, etc. are mentioned. The compound having both a cationic hydrophilic group and active hydrogen that reacts with an isocyanate group is not particularly limited, and specific examples include dimethylethanolamine, diethylethanolamine, diethanolamine, and methyldiethanolamine. The tertiary amino group thus introduced can be quaternized with dimethyl sulfate, diethyl sulfate or the like.

  The equivalent ratio of the isocyanate group to which a hydrophilic group is added and the blocked isocyanate group is preferably 1:99 to 80:20, more preferably 2:98 to 50:50, and 5:95 to 30. : 70 is particularly preferable. It is preferable to set it as the said preferable range from the point of coexistence with isocyanate reactivity and a development residue.

  As the blocked isocyanate having a hydrophilic group in the molecule and a synthesis method thereof, the aqueous blocked polyisocyanate described in JP-A-2014-065833, 0010 to 0045 can be preferably used. Embedded in.

When a blocked isocyanate having a hydrophilic group in the molecule is synthesized, the addition reaction of the hydrophilic group and the blocking reaction of the isocyanate group can be performed in the presence of a synthesis solvent. In this case, the synthesis solvent preferably contains no active hydrogen, and examples thereof include dipropylene glycol monomethyl ether and propylene glycol monomethyl ether acetate methoxypropyl acetate.
When synthesizing a blocked isocyanate having a hydrophilic group in the molecule, the compound having a hydrophilic group is preferably added in an amount of 2 to 80% by mass and more preferably 1 to 100% by mass with respect to the polyisocyanate. Is more preferable.
When synthesizing a blocked isocyanate having a hydrophilic group in the molecule, the blocking agent is preferably added in an amount of 20 to 99 mass%, more preferably 10 to 100 mass%, relative to the polyisocyanate.

  The blocked isocyanate used for the transfer film preferably has a weight average molecular weight of 200 to 3000, more preferably 250 to 2600, and particularly preferably 280 to 2200.

-Metal oxide particles-
The curable resin layer may or may not contain particles (preferably metal oxide particles) for the purpose of adjusting the refractive index and light transmittance. In order to control the refractive index of the curable resin layer, metal oxide particles can be included in an arbitrary ratio depending on the type of polymer or polymerizable compound used. In the curable resin layer, the metal oxide particles are preferably contained in an amount of 0 to 35% by mass, more preferably 0 to 10% by mass, and particularly preferably not contained, relative to the curable resin layer. . Although it is preferable that the curable resin layer does not include metal oxide particles, the case where the curable resin layer includes metal oxide particles is also included in the present invention. Examples of the metal oxide particles when the curable resin layer includes metal oxide particles include ZrO ₂ particles, Nb ₂ O ₅ particles, and TiO ₂ particles.
Since the metal oxide particles have high transparency and light transmittance, a curable resin layer having a high refractive index and excellent transparency can be obtained.
The refractive index of the aforementioned metal oxide particles is preferably higher than the refractive index of a composition made of a material obtained by removing the metal oxide particles from the curable resin layer. In other words, the refractive index of the metal oxide particles is preferably higher than the refractive index of the curable resin layer not including the metal oxide particles.

The metal of the metal oxide particles described above includes metalloids such as B, Si, Ge, As, Sb, and Te.
The light-transmitting and high refractive index metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb. Oxide particles containing atoms such as Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable. Titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / Tin oxide and antimony / tin oxide are more preferable, titanium oxide, titanium composite oxide, and zirconium oxide are more preferable, and titanium oxide and zirconium oxide are particularly preferable. Titanium oxide is particularly preferably a rutile type having a high refractive index. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.

  From the viewpoint of transparency of the curable resin layer, the average primary particle diameter of the metal oxide particles is preferably 1 to 200 nm, particularly preferably 3 to 80 nm. Here, the average primary particle diameter of the particles refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the longest side is the diameter.

  Moreover, the metal oxide particles described above may be used alone or in combination of two or more.

-Additives-
Furthermore, you may use an additive for the above-mentioned curable 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, known fluorosurfactants, and Japanese Patent No. 4502784. And the other additives described in paragraphs 0058 to 0071 of JP-A No. 2000-310706. Examples of the additive preferably used in the curable resin layer include Megafac F-551 (manufactured by DIC Corporation), which is a known fluorosurfactant.

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

<Second resin layer>
The transfer film may have a second resin layer.
From the viewpoint that the transfer film of the present invention has a second resin layer between the protective film and the curable resin layer, so that two or more resin layers can be laminated from the transfer film at one time, so that the productivity is improved. ,preferable.
The second resin layer preferably contains particles from the viewpoint of reducing transfer defects. The second resin layer is preferably formed by applying a second resin layer forming coating solution containing particles.

(Double bond consumption rate of the second resin layer)
In the transfer film of the present invention, the second resin layer is preferably curable. The double bond consumption rate of the second resin layer is determined by the method described in Examples described later.
Photolithography is practically required to be performed at least on a curable resin layer that is a layer closer to the outside than the second resin layer after transfer. The second resin layer that becomes a layer closer to the inside than the curable resin layer after the transfer may not have photolithographic properties. In the present invention, since the curable resin layer is curable in the state of a transfer film, the curable resin layer that becomes a layer closer to the outside than the second resin layer after transfer has photolithography.
The second resin layer may be thermosetting, photocurable, thermosetting and photocurable. Among these, it is preferable that the second resin layer is at least a thermosetting resin layer from the viewpoint of thermosetting after transfer and imparting film reliability, and is a thermosetting resin layer and a photocurable resin layer. It is more preferable from the viewpoint that it is easy to form a film by photocuring after the transfer, and can be thermally cured after the film formation to impart reliability of the film.
When the second resin layer is curable, the second resin layer may not be cured in the state of the transfer film, in which case the double bond consumption rate of the curable resin layer is 0%. . When the second resin layer is curable, the double resin consumption rate of the second resin layer may be cured in the state of the transfer film. The combined consumption rate is preferably more than 0% and less than 10%.
From the viewpoint of imparting photolithographic properties to the second resin layer, the double bond consumption rate of the second resin layer is preferably less than 10%, and more preferably 0%.

(Refractive index)
The transfer film of the present invention preferably satisfies the following formula 1.
Formula 1: n ₁ <n ₂
n ₁ represents the refractive index of the curable resin layer, and n ₂ represents the refractive index of the second resin layer.
The transparent electrode pattern (preferably Indium Tin Oxide; including a metal oxide such as ITO) generally has a higher refractive index than the resin layer. The transfer film satisfies Formula 1: n ₁ <n _2, and thus the difference in refractive index between the transparent electrode pattern and the second resin layer, and the second resin layer and the curable resin layer described above. Transfer film with a small refractive index difference can be obtained, and when the laminate is formed on the viewing side of the transparent electrode pattern, the light reflection is reduced and the transparent electrode pattern becomes difficult to see, concealing the transparent electrode pattern The sex can be improved.
Even when the second resin layer is laminated without curing the curable resin layer after the curable resin layer is laminated, the layer fraction is improved when the method for producing a transfer film described later is used. In this case, the concealability of the transparent electrode pattern can be improved by the above-described mechanism, and photolithography is performed after the refractive index adjustment layer (that is, the curable resin layer and the second resin layer) is transferred from the transfer film onto the transparent electrode pattern. Can be developed into a desired pattern. If the layer fraction of the curable resin layer and the second resin layer is good, the effect of adjusting the refractive index obtained by the above mechanism is easily obtained, and the transparent electrode pattern concealing property tends to be sufficiently improved. .
In the transfer film, the refractive index of the second resin layer is preferably higher than the refractive index of the curable resin layer. The value of n ₂ −n ₁ is preferably 0.03 to 0.30, and more preferably 0.05 to 0.20.
The refractive index n ₂ of the second resin layer is preferably 1.60 or more.
The refractive index of the second resin layer needs to be adjusted by the refractive index of the transparent electrode pattern, and the upper limit of the value is not particularly limited, but is preferably 2.1 or less, and is 1.78 or less. More preferably. The refractive index n ₂ of the second resin layer is preferably 1.60 ≦ n ₂ ≦ 1.75. The refractive index of the second resin layer described above may be 1.74 or less.
When the refractive index of the transparent electrode pattern exceeds 2.0, as in the case of In and Zn oxides (Indium Zinc Oxide; IZO), the refractive index n ₂ of the second resin layer is 1.7. It is preferable that it is 1.85 or more.

  The method for controlling the refractive index of the second resin layer is not particularly limited, but a resin layer having a desired refractive index is used alone, or a resin layer to which particles such as metal particles and metal oxide particles are added is used. Alternatively, a composite of a metal salt and a polymer can be used.

(The thickness of the second resin layer)
The thickness of the second resin layer is preferably 500 nm or less, and more preferably 110 nm or less. The thickness of the second resin layer is preferably 20 nm or more. The thickness of the second resin layer is particularly preferably from 55 to 100 nm, more preferably from 60 to 100 nm, and even more preferably from 70 to 100 nm.
In the present specification, T ₂ represents the average thickness of the second resin layer. In the present specification, the term “the thickness of the second resin layer” refers to “the average thickness T ₂ of the second resin layer” unless otherwise specified.

(Alkali soluble)
In the transfer film of the present invention, the second resin layer is preferably alkali-soluble.

(composition)
The second resin layer of the transfer film may be a negative type material or a positive type material. The second resin layer of the transfer film is preferably a negative material.
When the second resin layer of the transfer film is a negative material, the second resin layer preferably contains a resin having an acid group, a monomer having an acid group, particles, and a metal oxidation inhibitor. Furthermore, the second resin layer may contain another binder polymer, a polymerizable compound, and a polymerization initiator. Furthermore, the second resin layer may contain an additive.

-Resin having an acid group-
The resin having an acid group is preferably a resin having a monovalent acid group (such as a carboxyl group).
The resin having an acid group is preferably a resin having solubility in an aqueous solvent (preferably water or a mixed solvent of a lower alcohol having 1 to 3 carbon atoms and water). The resin having an acid group is not particularly limited as long as it does not contradict the gist of the present invention, and can be appropriately selected from known ones.
The resin having an acid group used for the second resin layer is preferably an alkali-soluble resin. The alkali-soluble resin is a linear organic polymer, and is a group that promotes at least one alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having an acid group (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.). Among these, more preferably, it is soluble in an organic solvent and can be developed using a weak alkaline aqueous solution.
As the acid group of the resin having an acid group, a carboxyl group is more preferable.

  For the production of the alkali-soluble resin, for example, a method using a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. You can also.

  As said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, JP 59-44615, JP-B 54-34327, JP-B 58-12777, JP-B 54-25957, JP-A 59-53836, JP-A 59-71048, JP Poly (meth) acrylic acid, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, croton as described in Japanese Patent Publication Nos. 46-2121 and 56-40824. Acid copolymers, maleic acid copolymers such as styrene / maleic acid, partially esterified maleic acid copolymers, etc., and acidic cellulose derivatives having a carboxylic acid in the side chain such as carboxyalkyl cellulose and carboxyalkyl starch, hydroxyl groups A polymer having an acid anhydride added to the polymer, and having a reactive functional group such as a (meth) acryloyl group in the side chain. Child polymers are also mentioned as preferred.

The resin having an acid group is preferably an acrylic resin.
As a specific structural unit of the resin having an acid group, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable.

Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) ) Acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, cyclohexyl acrylate and the like.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH ₂ = CR ¹ R ² , CH ₂ = C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic carbon atom having 6 to 10 carbon atoms. Represents a hydrogen ring, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. And the like.

These other copolymerizable monomers can be used alone or in combination of two or more. Other preferred copolymerizable monomers are selected from CH ₂ ═CR ¹ R ² , CH ₂ ═C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one, and particularly preferably CH ₂ = CR ¹ R ² and / or CH ₂ = C (R ¹ ) (COOR ³ ).

  In addition, a (meth) acrylic compound having a reactive functional group, cinnamic acid, or the like is allowed to react with a linear polymer having a substituent capable of reacting with the reactive functional group, thereby producing an ethylenically unsaturated double bond. Is a resin in which is introduced into the linear polymer. Examples of the reactive functional group include a hydroxyl group, a carboxyl group, and an amino group. Examples of the substituent capable of reacting with the reactive functional group include an isocyanate group, an aldehyde group, and an epoxy group.

The resin having an acid group is more preferably a benzyl (meth) acrylate / (meth) acrylic acid copolymer or a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers.
In addition, a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate is preferably used as the resin having an acid group.
Resins having an acid group can be mixed and used in an arbitrary amount.

  In addition to the above, the resin having an acid group may be a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-polymer described in JP-A-7-140654. Phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / Methacrylic acid copolymer.

  Among these, as the resin having an acid group, an acrylic resin having an acid group is preferable, a copolymer resin of (meth) acrylic acid / vinyl compound is preferable, and (meth) acrylic acid / (meta It is particularly preferable that it is a copolymer resin of allyl acrylate. In this specification, acrylic resin includes both methacrylic resin and acrylic resin, and (meth) acrylic similarly includes methacrylic and acrylic.

  The weight average molecular weight of the resin having an acid group is preferably 10,000 or more, more preferably 20,000 to 100,000.

  It is preferable that 10-80 mass% of resin which has an acid group is contained with respect to a 2nd resin layer, It is more preferable that 15-65 mass% is contained, It is especially preferable that 20-50 mass% is contained.

-Monomer having an acid group-
As the monomer having an acid group, acrylic monomers such as (meth) acrylic acid and derivatives thereof, and the following monomers can be preferably used.
For example, 3 to 4 functional radical polymerizable monomers (penterythritol tri and tetraacrylate skeleton introduced with a carboxylic acid group. Acid value = 80 to 120 mg KOH / g), 5 to 6 functional radical polymerizable monomers (dipenta A compound in which a carboxylic acid group is introduced into an erythritol penta and hexaacrylate skeleton, such as an acid value of 25 to 70 mgKOH / g). Although a specific name is not described, a bifunctional alkali-soluble radically polymerizable monomer may be used as necessary.
In addition, monomers having an acid group described in [0025] to [0030] of JP-A-2004-239842 can be preferably used, and the contents of this publication are incorporated in the present invention.
Moreover, the monomer which has an acid group among the polymeric compounds quoted as a polymeric compound used for a curable resin layer can also be used preferably.
Among these, a polymerizable compound containing a carboxyl group is preferable, and acrylic monomers such as (meth) acrylic acid and derivatives thereof can be more preferably used. Among them, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) is available. Particularly preferred. In the present specification, the acrylic monomer includes both a methacrylic monomer and an acrylic monomer.
In the second resin layer, the acid group-containing resin is preferably contained in an amount of 1 to 50% by mass of the monomer having an acid group, more preferably 3 to 20% by mass, and more preferably 6 to 15% by mass. Is particularly preferred.

-Particles-
The second resin layer preferably contains particles from the viewpoint of controlling adhesion with the protective film and reducing transfer defects.
The second resin layer preferably contains particles in an amount of 60 to 90% by mass with respect to the total solid content of the second resin layer, from the viewpoint of reducing transfer defects, and more preferably 65 to 90% by mass. More preferably, the content is 70% by mass or more and less than 85% by mass. The second resin layer contains particles in an amount of 60% by mass or more based on the total solid content of the second resin layer, and the second resin layer (and / or the curable resin layer) transfers to the protective film. From the viewpoint of reducing the adhesiveness to such an extent that transfer defects can be reduced, it is preferable. The second resin layer contains 90% by mass or less of particles with respect to the total solid content of the second resin layer, and the protective film is composed of the second resin layer (and / or the curable resin layer) and bubbles. From the viewpoint of increasing the adhesiveness to such an extent that generation can be suppressed, this is preferable.
The refractive index of the particles is preferably higher than the refractive index of a composition made of a material obtained by removing the particles from the second resin layer. In other words, the refractive index of the particles is preferably higher than the refractive index of the second resin layer that does not include particles. The particles contained in the second resin layer are preferably particles having a refractive index of 1.50 or more from the viewpoint of the concealability of the transparent electrode pattern. The second resin layer preferably contains particles having a refractive index of 1.55 or more, more preferably contains particles having a refractive index of 1.70 or more, and contains particles of 1.90 or more. It is particularly preferable that it contains particles of 2.00 or more.
The refractive index of the particles contained in the second resin layer is a refractive index in light having a wavelength of 400 nm to 750 nm. Here, that the refractive index in light having a wavelength of 400 nm to 750 nm is 1.50 or more means that the average refractive index in light having a wavelength in the above range is 1.50 or more. It is not necessary that the refractive index of all light having a wavelength is 1.50 or more. The average refractive index is a value obtained by dividing the sum of the measured values of the refractive index for each light having a wavelength in the above range by the number of measurement points.
In the transfer film of the present invention, the second resin layer preferably contains 60 to 90% by mass of particles having a refractive index of 1.50 or more based on the total solid content of the second resin layer.

The particles having a refractive index of 1.50 or more are more preferably metal oxide particles from the viewpoint of adjusting the refractive index and light transmittance.
The second resin layer can contain metal oxide particles at an arbitrary ratio depending on the resin used, the type and content of the polymerizable monomer, the type of metal oxide particles used, and the like.
There is no restriction | limiting in particular as a kind of metal oxide particle, A well-known metal oxide particle can be used. The metal oxide particles mentioned in the curable resin layer described above can also be used in the second resin layer.
In the present invention, the second resin layer has at least one of zirconium oxide particles (ZrO ₂ particles), Nb ₂ O ₅ particles, and titanium oxide particles (TiO ₂ particles). From the viewpoint of controlling the refractive index within the range of the refractive index. The metal oxide particles are more preferably zirconium oxide particles or titanium oxide particles, and particularly preferably zirconium oxide particles. Commercially available products may be used as the particles. For example, nano-use OZ-S30M (Nissan Chemical Industries, Ltd.) can be preferably used.
When zirconium oxide particles are used as the metal oxide particles, the content of the zirconium oxide particles is the total amount of the second resin layer from the viewpoint of providing appropriate adhesion to the protective film and reducing bubbles and transfer defects. The solid content is preferably 60% to 90% by mass, more preferably 65% to 90% by mass, and still more preferably 70% by mass to less than 85% by mass.
On the other hand, as a more preferable aspect in the case of using titanium oxide particles as the metal oxide particles, the metal oxide particles are preferably contained in an amount of 30 to 70% by mass, and 40% by mass or more with respect to the second resin layer. More preferably, the content is less than 60% by mass. By setting it as the said preferable range, the defect of the 2nd resin layer which has a metal oxide particle after transfer cannot be seen easily, and the laminated body with favorable concealability of a transparent electrode pattern can be produced.

  Further, the metal oxide particles may be used alone or in combination of two or more.

-Metal oxidation inhibitor-
The second resin layer preferably contains a metal oxidation inhibitor. When the second resin layer contains a metal oxidation inhibitor, the second resin layer is laminated on a transparent substrate (the transparent substrate preferably includes a transparent electrode pattern, a metal wiring portion, etc.) It becomes possible to surface-treat the metal wiring portion that is in direct contact with the second resin layer. It is considered that the protection of the metal wiring portion provided by the surface treatment is effective even after the second resin layer (and the support-side functional layer) is removed.
The metal oxidation inhibitor used in the present invention is preferably a compound having an aromatic ring containing a nitrogen atom in the molecule.
In addition, as the metal oxidation inhibitor, the aromatic ring containing a nitrogen atom is at least selected from the group consisting of an imidazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, and a condensed ring of these and another aromatic ring. One ring is preferable, and the aromatic ring containing the nitrogen atom is more preferably an imidazole ring or a condensed ring of an imidazole ring and another aromatic ring.
The other aromatic ring may be a monocyclic ring or a heterocyclic ring, but is preferably a monocyclic ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.
Preferable metal oxidation inhibitors include imidazole, benzimidazole, tetrazole, mercaptothiadiazole, and benzotriazole, and imidazole, benzimidazole, and benzotriazole are more preferable. Commercially available products may be used as the metal oxidation inhibitor, and for example, BT120 manufactured by Johoku Chemical Industry Co., Ltd. containing benzotriazole can be preferably used.
Moreover, it is preferable that it is 0.1-20 mass% with respect to the total mass of a 2nd resin layer, and, as for content of a metal oxidation inhibitor, it is more preferable that it is 0.5-10 mass%. More preferably, it is -5 mass%.

その他の水系樹脂組成物に用いられる光重合性化合物としては、メタノールなどの炭素原子数１乃至３の低級アルコールと水との混合溶媒にも溶解性を有することが、金属酸化物粒子のアルコール分散液を水系樹脂組成物に併用する場合に好ましい。水もしくは炭素原子数１乃至３の低級アルコールと水との混合溶媒に対して溶解性を有する重合性化合物としては、水酸基を有するモノマー、分子内にエチレンオキサイドやポリプロピレンオキサイド、およびリン酸基を有するモノマーが使用できる。炭素原子数１乃至３の低級アルコールと水との混合溶媒にも溶解性を有する重合性化合物としては、カヤラッドＲＰ−１０４０（日本化薬（株）製）、アロニックスＴＯ−２３４９（東亞合成社製）、重合性モノマー Ａ−９３００（新中村化学工業（社）製）、Ａ−ＧＬＹ−２０Ｅ（新中村化学工業（社）製）などが好ましい。なお、重合性化合物が炭素原子数１乃至３の低級アルコールと水との混合溶媒にも溶解性を有するとは、アルコールと水との混合溶媒に０．１質量％以上溶解することを言う。
また、重合性化合物の含有量は、第二の樹脂層の全固形分に対し、０〜２０質量％であることが好ましく、０〜１０質量％であることがより好ましく、０〜５質量％であることが更に好ましい。 -Polymerizable compound-
The second resin layer described above preferably contains a polymerizable compound such as a photopolymerizable compound or a thermopolymerizable compound from the viewpoint of curing and increasing the strength of the film. The second resin layer may contain only the above-mentioned monomer having an acid group as a polymerizable compound, or may contain other polymerizable compound other than the above-mentioned monomer having an acid group.
As the polymerizable compound used in the second resin layer, the polymerizable compounds described in paragraphs 0023 to 0024 of Japanese Patent No. 4098550 can be used. Among these, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and tetraacrylate of pentaerythritol ethylene oxide adduct can be preferably used. These polymerizable compounds may be used alone or in combination. When a mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate is used, the ratio of pentaerythritol triacrylate to the entire mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate is preferably 0 to 80% by mass, More preferably, it is 60%.
Specifically, as the polymerizable compound used in the second resin layer, a water-soluble polymerizable compound represented by the following structural formula 1 and a pentaerythritol tetraacrylate mixture (NK ester A-TMMT Shin-Nakamura Chemical Co., Ltd.) ), Containing about 10% triacrylate as an impurity), a mixture of pentaerythritol tetraacrylate and triacrylate (NK ester A-TMM3LM-N, Shin-Nakamura Chemical Co., Ltd., triacrylate 37%), pentaerythritol tetraacrylate and Mixture of triacrylate (NK Ester A-TMM-3L made by Shin-Nakamura Chemical Co., Ltd., triacrylate 55%), mixture of pentaerythritol tetraacrylate and triacrylate (NK Ester A-TMM3 made by Shin-Nakamura Chemical Co., Ltd.) , Triacrylate 5 7%), tetraacrylate of pentaerythritol ethylene oxide adduct (Kayarad RP-1040 manufactured by Nippon Kayaku Co., Ltd.), and the like.

As the photopolymerizable compound used in other aqueous resin compositions, the alcohol dispersion of the metal oxide particles may be soluble in a mixed solvent of lower alcohol having 1 to 3 carbon atoms such as methanol and water. It is preferable when the liquid is used in combination with an aqueous resin composition. Examples of the polymerizable compound having solubility in water or a mixed solvent of a lower alcohol having 1 to 3 carbon atoms and water include a monomer having a hydroxyl group, an ethylene oxide, a polypropylene oxide, and a phosphate group in the molecule. Monomers can be used. Examples of polymerizable compounds having solubility in a mixed solvent of a lower alcohol having 1 to 3 carbon atoms and water include Kayarad RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.). ), Polymerizable monomer A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.), A-GLY-20E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like are preferable. In addition, that the polymerizable compound is soluble in a mixed solvent of a lower alcohol having 1 to 3 carbon atoms and water means that the polymerizable compound is dissolved in a mixed solvent of alcohol and water by 0.1% by mass or more.
Moreover, it is preferable that it is 0-20 mass% with respect to the total solid of a 2nd resin layer, as for content of a polymeric compound, it is more preferable that it is 0-10 mass%, and 0-5 mass%. More preferably.

-Polymerization initiator-
There is no restriction | limiting in particular as a polymerization initiator used for a 2nd resin layer. The polymerization initiator used for the second resin layer preferably has solubility in water or a mixed solvent of water and a lower alcohol having 1 to 3 carbon atoms and water.
As a polymerization initiator used for the second resin layer, IRGACURE 2959 or a polymerization initiator represented by the following structural formula 2 can be used.
Moreover, it is preferable that it is 0-5 mass% with respect to the total solid of the resin composition used for formation of a 2nd resin layer, and, as for content of a polymerization initiator, it is 0-1 mass%. More preferably, it is still more preferably 0 to 0.5% by mass.

-Other binder polymers-
The second resin layer may contain another binder polymer having no acid group. There is no restriction | limiting in particular as another binder polymer. As another binder polymer, the binder polymer used for the above-mentioned curable resin layer can be used.

-Additives-
The second resin layer may contain an additive. Examples of the additive include surfactants described in paragraph 0017 of Japanese Patent No. 4502784, paragraphs 0060-0071 of JP-A-2009-237362, and thermal polymerization described in paragraph 0018 of Japanese Patent No. 4502784. In addition, other additives described in paragraphs 0058 to 0071 of JP-A No. 2000-310706 may be used. Examples of the additive preferably used for the second resin layer include Megafac F-444 (manufactured by DIC Corporation), which is a known fluorosurfactant.

  As described above, the case where the second resin layer of the transfer film is a negative type material has been mainly described, but the second resin layer of the transfer film may be a positive type material. When the second resin layer of the transfer film is a positive type material, for example, a material described in JP-A-2005-221726 is used for the second resin layer.

<Any resin layer>
In addition to the temporary support, the curable resin layer, the second resin layer, and the protective film, the transfer film may have any other layer as long as the effects of the present invention are not impaired. Other optional layers may include a thermoplastic resin layer and an intermediate layer.

(Thermoplastic resin layer)
In the transfer film of the present invention, a thermoplastic resin layer can be provided between the temporary support and the curable resin layer. As the thermoplastic resin layer, reference can be made to the thermoplastic resin layers described in [0041] to [0047] of JP-A-2014-108541. The contents of this publication are incorporated herein.

(Middle layer)
In the transfer film of the present invention, an intermediate layer can be provided between the thermoplastic resin layer and the curable resin layer. The intermediate layer is described as “separation layer” in JP-A-5-72724.

<Production method of transfer film>
The manufacturing method of the transfer film of this invention is not specifically limited, It can manufacture by a well-known method.
When producing a transfer film having a curable resin layer and a protective film on a temporary support, a step of forming the curable resin layer on the temporary support and a protective film on the curable resin layer described above It is preferable to have a process.

Further, when producing a transfer film having a second resin layer, a step of forming a curable resin layer on a temporary support, a step of forming a second resin layer on the curable resin layer, And a step of forming a protective film on the second resin layer.
The step of forming the curable resin layer is preferably a step of applying the organic solvent-based resin composition onto the temporary support described above.
From the viewpoint of interlayer adhesion between the curable resin layer and the second resin layer, the step of forming the second resin layer is a step of forming the second resin layer directly on the curable resin layer. preferable.
The step of forming the second resin layer is preferably a step of applying an aqueous resin composition from the viewpoint of improving the layer fraction. By applying the aqueous resin composition on the curable resin layer obtained by the organic solvent-based resin composition to form the second resin layer, the second resin without curing the curable resin layer. Even when the layers are formed, interlayer mixing does not occur, and the layer fraction is improved.

In addition, the second resin layer is formed by applying the aqueous resin composition used for forming the second resin layer without exposing the curable resin layer obtained by coating and drying. However, it is preferable from a viewpoint which can provide sclerosis | hardenability to a curable resin layer in the state of the film for dry resists. From the viewpoint of imparting photolithographic properties, it is preferable to provide a second resin layer or a protective film without curing after applying the curable resin layer. In this case, the double bond consumption rate of the curable resin layer is 0%.
On the other hand, the second resin layer may be formed after the curable resin layer is cured. After applying the curable resin layer, the double bond consumption rate is cured within a range of less than 10%, and after the adhesiveness of the curable resin layer is reduced within a range in which photolithography can be sufficiently maintained, A resin layer or a protective film may be provided. In this case, the double bond consumption rate of the curable resin layer is more than 0% and less than 10%.
From the viewpoint of imparting photolithographic properties, it is preferable to provide the second resin layer or the protective film without curing after applying the curable resin layer.
As a method for curing the curable resin layer, a method similar to the method for curing the curable resin layer after transfer in the method for producing a laminate described later can be used.
Hereinafter, preferred embodiments of each step will be described.

(Process of forming a curable resin layer on a temporary support)
It is preferable that the manufacturing method of a transfer film includes the process of forming a curable resin layer on a temporary support body.

-Organic solvent resin composition-
The step of forming the curable resin layer is preferably a step of applying the organic solvent-based resin composition onto the temporary support described above.
The organic solvent-based resin composition refers to a resin composition that can be dissolved in an organic solvent.
A common organic solvent can be used as the organic solvent. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (1-methoxy-2-propyl acetate), cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.
Moreover, an organic solvent may be used individually by 1 type and can also use 2 or more types together.

In the method for producing a transfer film, the organic solvent-based resin composition used for forming the curable resin layer preferably includes a binder polymer, a polymerizable compound, and a polymerization initiator.
Furthermore, since the organic solvent-based resin composition used for forming the curable resin layer contains a surfactant containing fluorine atoms (also referred to as a fluorine-based surfactant), the curable resin layer is cured without being cured. Even if the second resin layer is formed, interlayer mixing does not occur, and the thickness uniformity of the second resin layer is improved. Moreover, by adjusting the content of the surfactant in the organic solvent-based resin composition so that the content of the surfactant with respect to the total solid content of the curable resin layer is 0.01 to 0.50% by mass. When manufacturing the laminated body mentioned later, the adhesiveness of a 2nd resin layer and a transparent electrode pattern becomes favorable.

(Step of forming the second resin layer)
It is preferable that the manufacturing method of a transfer film includes the process of forming a 2nd resin layer.

-Aqueous resin composition-
The step of forming the second resin layer is preferably a step of applying the aqueous resin composition.
Since the second resin layer obtained using the aqueous resin composition is easily dissolved in water, it is preferable that the second resin layer has a composition that does not easily cause a problem of wet heat resistance of the transfer film. Specifically, an aqueous resin composition containing an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group is preferably used as the aqueous resin composition. When the second resin layer obtained using such an aqueous resin composition is dried, ammonia having a lower boiling point than water is obtained from the ammonium salt of the monomer having an acid group or the ammonium salt of the resin having an acid group. Is easy to volatilize. Therefore, an acid group can be generated (regenerated) from the ammonia salt state and can be present in the second resin layer as a monomer having an acid group or a resin having an acid group. Since the monomer having an acid group or the resin having an acid group constituting the second resin layer in which the acid group has been generated does not dissolve in water, the moisture resistance of the transfer film can be improved.

The aqueous resin composition refers to a resin composition that can be dissolved in an aqueous solvent.
As the aqueous solvent, water or a mixed solvent of water and a lower alcohol having 1 to 3 carbon atoms and water is preferable. In the preferable aspect of the manufacturing method of a transfer film, it is preferable that the solvent of the water-system resin composition used for formation of a 2nd resin layer contains water and C1-C3 alcohol, More preferably, it contains water or a mixed solvent having an alcohol / water mass ratio of 20/80 to 80/20.
A mixed solvent of water, water and methanol, and a mixed solvent of water and ethanol are preferable, and a mixed solvent of water and methanol is more preferable from the viewpoint of drying and coating properties.
In particular, when a mixed solvent of water and methanol is used in forming the second resin layer, the mass ratio (mass% ratio) of methanol / water is preferably 20/80 to 80/20, and 30/70 More preferably, it is -70/30, and it is especially preferable that it is 40 / 60-70 / 30. By controlling to the said range, a curable resin layer and a 2nd resin layer can implement | achieve application | coating and quick drying without interlayer mixing. As a result, defects in the second resin layer having metal oxide particles are hardly visible after transfer, and it is easy to produce a transfer film that can produce a laminate with good concealment of the transparent electrode pattern.

The aqueous resin composition has a pH (Power of Hydrogen) at 25 ° C. of preferably 7.0 or more and 12.0 or less, more preferably 7.0 to 10.0, and more preferably 7.0 to 8. 5 is particularly preferred. For example, an excess amount of ammonia with respect to the acid group can be used, and a monomer having an acid group or a resin having an acid group can be added to adjust the pH of the aqueous resin composition to the above preferred range.
Moreover, as for the manufacturing method of a transfer film, it is preferable that the water-system resin composition used for formation of a 2nd resin layer is at least one among thermosetting and photocurability. When the curable resin layer is curable, according to the method for producing a transfer film, even if the second resin layer is laminated without being cured after the curable resin layer is laminated, the layer fraction is improved and the transparent electrode Pattern concealment can be improved. In this case, the laminated body described later further transfers the curable resin layer and the second resin layer from the obtained transfer film onto the transparent electrode pattern simultaneously, and then at least after the transfer by photolithography, the second resin layer. The curable resin layer that becomes a layer closer to the outside can be developed into a desired pattern. An embodiment in which the second resin layer is curable is more preferable. In this embodiment, the curable resin layer and the second resin layer are simultaneously transferred onto the transparent electrode pattern, and then developed into a desired pattern by photolithography at the same time. it can.
Providing a protective film without curing the second resin layer is preferable from the viewpoint of imparting photolithographic properties. In this case, the double bond consumption rate of the second resin layer is 0%.
In addition, the second resin layer is cured within a range where the double bond consumption rate is less than 10%, and the adhesiveness of the curable resin layer is reduced within a range where the photolithography property can be sufficiently maintained, and then a protective film is provided. May be. In this case, the double bond consumption rate of the second resin layer is more than 0% and less than 10%.

-Resin having an acid group or monomer having an acid group-
It is particularly preferable that the aqueous resin composition used for forming the second resin layer contains an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group.
The ammonium salt of the monomer having an acid group or the ammonium salt of a resin having an acid group is not particularly limited.
The ammonium salt of the monomer having an acid group or the ammonium salt of a resin having an acid group in the second resin layer is preferably an acrylic monomer having an acid group or an ammonium salt of an acrylic resin.

The step of forming the second resin layer comprises dissolving a monomer having an acid group or a resin having an acid group in an aqueous ammonia solution, and including a monomer or a resin in which at least a part of the acid group is ammonium chlorided. It is preferable to include the process of preparing.
In the method for producing a transfer film, the aqueous resin composition used for forming the second resin layer contains an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group, a binder polymer, and light or heat. It preferably contains a polymerizable compound and a light or thermal polymerization initiator. Only the ammonium salt of the resin having an acid group may be a binder polymer, or in addition to the ammonium salt of a resin having an acid group, another binder polymer may be used in combination. The ammonium salt of the monomer having an acid group may be a photo or thermopolymerizable compound, and in addition to the ammonium salt of the monomer having an acid group, a photo or thermopolymerizable compound may be used in combination.

(Volatilization of ammonia)
The method for producing a transfer film preferably includes a step of generating an acid group by volatilizing ammonia from an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group. The step of generating an acid group by volatilizing ammonia from the ammonium salt of the monomer having an acid group or the ammonium salt of a resin having an acid group is a step of heating the applied aqueous resin composition. Preferably there is.
The preferable range of the detailed conditions of the process of heating the applied aqueous resin composition is described below.
As a heating and drying method, it can be carried out by passing through a furnace equipped with a heating device, or by blowing air. The heating and drying conditions may be appropriately set according to the organic solvent to be used, and examples thereof include a method of heating to a temperature of 40 to 150 ° C. Among these conditions, heating at a temperature of 50 to 120 ° C is particularly preferable, and heating to a temperature of 60 to 100 ° C is more preferable. As the composition after heating and drying, the moisture content on a wet basis is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less.

(Process for forming protective film)
It is preferable that the manufacturing method of a transfer film includes the process of forming a protective film. There is no restriction | limiting in particular as a process of forming a protective film, A well-known method can be used. For example, the method of crimping | bonding a protective film with respect to a curable resin layer or a 2nd resin layer can be mentioned.

(Step of forming a roll)
It is preferable that the manufacturing method of a transfer film includes the process of forming a roll. There is no restriction | limiting in particular as a process of forming a protective film, A well-known method can be used. For example, the transfer film which formed the protective film can mention the method of winding up in roll shape so that a protective film may become an outer side.

<Other processes>
Before forming the above-mentioned curable resin layer on the above-mentioned temporary support, it may further include a step of forming a thermoplastic resin layer.

  After the step of forming the thermoplastic resin layer, a step of forming an intermediate layer between the thermoplastic resin layer and the curable resin layer may be included. In the case of forming a transfer film having an intermediate layer, a solution (addition solution for thermoplastic resin layer) in which an additive is dissolved together with a thermoplastic organic polymer is applied on a temporary support, dried, and heated. It is preferable to provide a plastic resin layer. Applying a prepared liquid (intermediate layer coating liquid) prepared by adding a resin or an additive to a solvent that does not dissolve the thermoplastic resin layer on the obtained thermoplastic resin layer, and drying to laminate the intermediate layer preferable. It is preferable that a coating resin for a curable resin layer prepared by using a solvent that does not dissolve the intermediate layer is further applied on the intermediate layer and dried to laminate the curable resin layer.

  As another method for producing the curable resin layer or the second resin layer, the method for producing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138 can be employed.

<Application>
The transfer film of the present invention is preferably used for an electrode protective film of a capacitive input device, and is preferably used for a transparent insulating layer or a transparent protective layer among electrode protective films. In the transfer film, the curable resin layer may be in an uncured state. In that case, transfer to form a laminated pattern of the electrode protective film of the capacitive input device on the transparent electrode pattern by photolithography. It can be used as a transfer film for forming a laminated pattern of a film, more preferably a refractive index adjusting layer and an overcoat layer (transparent protective layer).
The transfer film of the present invention is preferably a dry resist film. In the present specification, the dry resist refers to a product in which a transfer film takes a film form.

[Electrode protective film of capacitive input device]
The electrode protective film of the capacitive input device of the present invention is obtained by removing the protective film from the transfer film of the present invention.
The electrode protective film of the capacitive input device of the present invention is preferably one obtained by removing the protective film and the temporary support from the transfer film of the present invention.
More preferably, the electrode protective film of the capacitive input device of the present invention is obtained by transferring the curable resin layer from the transfer film of the present invention onto the transparent electrode pattern and curing the curable resin layer.
An electrode protective film is a film | membrane which has a function which protects the electrode (transparent electrode pattern etc.) of an electrostatic capacitance type input device.
The electrode protective film of the capacitive input device is preferably photocured on the curable resin layer, and more preferably photocured and heat-treated.

[Laminate]
The laminated body of this invention has the board | substrate containing the electrode of an electrostatic capacitance type input device, and the electrode protective film of the electrostatic capacitance type input device of this invention.

  The electrode of the capacitive input device may be a transparent electrode pattern or a lead wiring. In the laminate, the electrode of the capacitive input device is preferably an electrode pattern, and more preferably a transparent electrode pattern.

The laminate has a substrate including electrodes of the capacitive input device and a curable resin layer formed on the substrate, and preferably includes at least a substrate, a transparent electrode pattern, and a curable resin layer. And a transparent electrode pattern, a second resin layer disposed adjacent to the transparent electrode pattern, and a curable resin layer disposed adjacent to the second resin layer.
The laminate has a substrate, a transparent electrode pattern, a second resin layer disposed adjacent to the transparent electrode pattern, and a curable resin layer disposed adjacent to the second resin layer. The refractive index of the second resin layer is particularly preferably higher than the refractive index of the curable resin layer, and the refractive index of the second resin layer is more preferably 1.6 or more. preferable. By setting it as such a structure, the problem that a transparent electrode pattern is visually recognized can be solved.

<Configuration of laminate>
The laminate of the present invention is a transparent film having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm on the side of the transparent electrode pattern opposite to the side on which the second resin layer is formed. It is preferable from the viewpoint of further improving the concealing property of the transparent electrode pattern. In addition, in this specification, when there is no notice in particular and it describes as a "transparent film | membrane", it points out said "transparent film | membrane whose refractive index is 1.6-1.78 and thickness is 55-110 nm."
The laminate of the present invention further has a transparent substrate on the opposite side of the transparent film having the refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm on which the transparent electrode pattern is formed. It is preferable.

FIG. 11 shows an example of the configuration of the laminate of the present invention.
In FIG. 11, the transparent substrate 1 has a transparent film 11 having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm, and further includes a transparent electrode pattern 4, a second resin layer 12, and a curable resin layer. 7 has an in-plane region 21 laminated in this order. In addition, in FIG. 11, in addition to the above-described region, the above-described laminate includes a region in which the transparent substrate 1 and the transparent film 11 are laminated in this order (in the configuration of FIG. 11, the second resin layer 12 and the curable resin). It is shown that the layer 7 includes a region 22 (that is, a non-pattern region 22 where a transparent electrode pattern is not formed) stacked in this order.
In other words, the above-described laminate includes a region 21 in which the transparent substrate 1, the transparent film 11, the transparent electrode pattern 4, the second resin layer 12, and the curable resin layer 7 are laminated in this order in the in-plane direction.
The in-plane direction means a direction substantially parallel to a plane parallel to the transparent substrate of the laminate. Therefore, the transparent electrode pattern 4, the second resin layer 12, and the curable resin layer 7 include in the plane the region in which the transparent electrode pattern 4, the second resin layer 12, and the curable resin layer 7 are laminated in this order. This means that an orthographic projection of the region 7 in this order on the plane parallel to the transparent substrate of the laminate exists in the plane parallel to the transparent substrate of the laminate.
Here, when the laminate of the present invention is used in a capacitance-type input device to be described later, the transparent electrode pattern has a first transparent electrode pattern and a second transparent electrode in two directions substantially orthogonal to the row direction and the column direction, respectively. It may be provided as an electrode pattern (see, for example, FIG. 3). For example, in the configuration of FIG. 3, the transparent electrode pattern in the laminate of the present invention may be the second transparent electrode pattern 4 or the pad portion 3 a of the first transparent electrode pattern 3. In other words, in the following description of the laminate of the present invention, the reference numeral of the transparent electrode pattern may be represented by “4”. The transparent electrode pattern in the laminate of the present invention is not limited to use for the second transparent electrode pattern 4 in the capacitive input device of the present invention, and is used as, for example, the pad portion 3a of the first transparent electrode pattern 3. May be.

It is preferable that the laminated body of this invention contains the non-pattern area | region in which the above-mentioned transparent electrode pattern is not formed. In the present specification, the non-pattern region means a region where the transparent electrode pattern 4 is not formed.
FIG. 11 shows a mode in which the laminate of the present invention includes a non-pattern region 22.
In the laminate of the present invention, the transparent substrate, the transparent film, and the second resin layer described above are stacked in this order on at least a part of the non-pattern region 22 where the transparent electrode pattern is not formed. The region is preferably included in the plane.
In the laminated body of the present invention, the transparent film and the second resin layer are adjacent to each other in a region where the transparent substrate, the transparent film, and the second resin layer are stacked in this order. Preferably it is.
However, in the other areas of the non-pattern area 22 described above, other members may be disposed at arbitrary positions as long as they do not contradict the spirit of the present invention. When used in a mold input device, the mask layer 2 in FIG. 1A, the insulating layer 5, another conductive element 6 and the like can be laminated.

In the laminate of the present invention, the transparent substrate and the transparent film are preferably adjacent to each other.
FIG. 11 shows a mode in which the above-described transparent film 11 is laminated adjacently on the above-described transparent substrate 1.
However, a third transparent film may be laminated between the above-mentioned transparent substrate and the above-described transparent film as long as it does not contradict the gist of the present invention. For example, it is preferable to include a third transparent film (not shown in FIG. 11) having a refractive index of 1.5 to 1.52 between the transparent substrate and the transparent film.

In the laminate, the thickness of the transparent film is preferably 55 to 110 nm, more preferably 60 to 110 nm, and particularly preferably 70 to 90 nm.
Here, the transparent film described above may have a single layer structure or a laminated structure of two or more layers. When the above-mentioned transparent film has a laminated structure of two or more layers, the thickness of the above-mentioned transparent film means the total thickness of all layers.

In the laminate, it is preferable that the transparent film and the transparent electrode pattern are adjacent to each other.
FIG. 11 shows an aspect in which the transparent electrode pattern 4 is laminated adjacently on a partial region of the transparent film 11.
The shape of the end portion of the transparent electrode pattern 4 is not particularly limited. However, the end portion of the transparent electrode pattern 4 may have a tapered shape as shown in FIG. It may have a taper shape wider than the surface opposite to the transparent substrate.
Here, the angle of the end portion of the transparent electrode pattern (hereinafter also referred to as a taper angle) when the end portion of the transparent electrode pattern has a tapered shape is preferably 30 ° or less, 0.1 to 15 More preferably, it is 0.5 to 5 °.
The method for measuring the taper angle in this specification can be obtained by taking a photomicrograph of the end of the transparent electrode pattern described above, approximating the taper portion of the photomicrograph to a triangle, and directly measuring the taper angle. .
FIG. 10 shows an example in which the end portion of the transparent electrode pattern is tapered. The triangle that approximates the tapered portion in FIG. 10 has a bottom surface of 800 nm and a height (thickness at the upper base portion substantially parallel to the bottom surface) of 40 nm, and the taper angle α at this time is about 3 °. The triangular bottom surface approximating the tapered portion is preferably 10 to 3000 nm, more preferably 100 to 1500 nm, and particularly preferably 300 to 1000 nm.
In addition, the preferable range of the height of the triangle which approximated the taper part is the same as the preferable range of the thickness of the transparent electrode pattern.

The laminate of the present invention preferably includes a region in which the transparent electrode pattern and the second resin layer are adjacent to each other.
FIG. 11 shows the above-mentioned transparent electrode pattern, the above-mentioned second resin layer, and the curable resin in the region 21 in which the above-mentioned transparent electrode pattern, the above-mentioned second resin layer, and the curable resin layer are laminated in this order. An embodiment is shown in which the layers are adjacent to each other.

In the laminate of the present invention, both the transparent electrode pattern and the non-pattern region 22 where the transparent electrode pattern is not formed are continuously and directly formed by the transparent film and the second resin layer. Or it is preferable to coat | cover through another layer.
Here, “continuously” means that the transparent film and the second resin layer are not a pattern film but a continuous film. That is, it is preferable that the transparent film and the second resin layer have no opening from the viewpoint of making the transparent electrode pattern difficult to be visually recognized.
Further, it is preferable that the transparent electrode pattern and the non-pattern region 22 are directly covered with the transparent film and the second resin layer, rather than being covered with another layer. As the “other layer” in the case of being covered through another layer, the insulating layer 5 included in the capacitive input device of the present invention described later, or the capacitive input device of the present invention described later is used. Thus, when two or more layers of transparent electrode patterns are included, a second layer of transparent electrode patterns can be exemplified.
FIG. 11 shows an aspect in which the second resin layer 12 is laminated. The above-mentioned second resin layer 12 is laminated over a region where the transparent electrode pattern 4 on the transparent film 11 is not laminated and a region where the transparent electrode pattern 4 is laminated. That is, the aforementioned second resin layer 12 is adjacent to the aforementioned transparent film 11, and further, the aforementioned second resin layer 12 is adjacent to the transparent electrode pattern 4.
Moreover, when the edge part of the transparent electrode pattern 4 is a taper shape, it is preferable that the above-mentioned 2nd resin layer 12 is laminated | stacked along the taper shape (with the same inclination as a taper angle).

  FIG. 11 shows an aspect in which the curable resin layer 7 is laminated on the surface of the second resin layer 12 opposite to the surface on which the transparent electrode pattern is formed. Yes.

<Material of laminate>
(Transparent substrate)
The laminated body of this invention has a board | substrate containing the electrode of an electrostatic capacitance type input device. The substrate including the electrode of the capacitive input device is preferably a member different from the substrate.
In the laminate of the present invention, the transparent substrate is preferably a glass substrate or a transparent film substrate, and more preferably a transparent film substrate. The refractive index of the transparent substrate is preferably 1.5 to 1.55, and particularly preferably 1.5 to 1.52.
The above-mentioned transparent substrate may be comprised by translucent substrates, such as a glass substrate, and can use the tempered glass represented by the gorilla glass of Corning, etc. Moreover, as the above-mentioned transparent substrate, the materials used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used.
When a transparent film substrate is used as the transparent substrate, it is more preferable to use one that is not optically distorted or one that has high transparency. Specific examples of the transparent film substrate include a transparent film substrate containing polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, or cycloolefin resin.

(Transparent electrode pattern)
The refractive index of the transparent electrode pattern is preferably 1.75 to 2.1.
The material for the transparent electrode pattern is not particularly limited, and a known material can be used. For example, it can be manufactured using a light-transmitting conductive metal oxide film such as ITO or IZO, or a metal film. Examples of such metal oxide films and metal films include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as SiO ₂ . At this time, the thickness of each element can be 10 to 200 nm. Further, since the amorphous ITO film is made into a polycrystalline ITO film by firing, the electrical resistance can be reduced. The first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 described later are photosensitive having a conductive photocurable resin layer using conductive fibers. It can also be produced using a film. In addition, when the first conductive pattern or the like is formed of ITO or the like, paragraphs 0014 to 0016 of Japanese Patent No. 4506785 can be referred to. Among these, the transparent electrode pattern described above is preferably an ITO film.
In the laminate of the present invention, the transparent electrode pattern is preferably an ITO film having a refractive index of 1.75 to 2.1.

(Curable resin layer and second resin layer)
Preferred ranges of the curable resin layer and the second resin layer included in the laminate of the present invention are the same as the preferred ranges of the curable resin layer and the second resin layer in the transfer film of the present invention. .
Among them, the laminate preferably includes the curable resin layer containing a carboxylic acid anhydride from the viewpoint of forming an electrode protective film for a capacitive input device with excellent wet heat resistance. By adding blocked isocyanate to the carboxyl group-containing resin of the curable resin layer and thermally crosslinking, the three-dimensional crosslinking density is increased, the carboxyl group of the carboxyl group-containing resin is dehydrated and hydrophobized, etc. It is estimated that it contributes to improvement of wet heat resistance.
Although there is no restriction | limiting in particular as a method of including a carboxylic acid anhydride in a curable resin layer, The curable resin layer after transcription | transfer is heat-processed, and at least one part of carboxyl group-containing acrylic resin is used as a carboxylic acid anhydride. The method is preferred. Further, when at least one of the polymerizable compounds contains a carboxyl group, the carboxyl group-containing acrylic resin and the polymerizable compound containing a carboxyl group may form a carboxylic acid anhydride, and contain a carboxyl group. A carboxylic acid anhydride may be formed between the polymerizable compounds.

(Transparent film)
In the laminate of the present invention, the refractive index of the transparent film is 1.6 to 1.78, and preferably 1.65 to 1.74. Here, the transparent film described above may have a single layer structure or a laminated structure of two or more layers. When the aforementioned transparent film has a laminated structure of two or more layers, the refractive index of the aforementioned transparent film means the refractive index of all layers.
As long as the refractive index range is satisfied, the material for the transparent film is not particularly limited.

The preferred range of the material for the transparent film and the preferred range for the physical properties such as the refractive index are the same as those for the second resin layer.
In the laminate of the present invention, it is preferable from the viewpoint of optical homogeneity that the transparent film and the second resin layer are made of the same material.

In the laminate of the present invention, the transparent film is preferably a transparent resin film.
The metal oxide particles, resin (binder) and other additives used for the transparent resin film are not particularly limited as long as they do not contradict the gist of the present invention, and the second resin layer in the transfer film of the present invention is not limited. Resins used and other additives can be preferably used.
In the laminate of the present invention, the transparent film may be an inorganic film. Examples of the material used for the inorganic film include the materials used for the second resin layer described above.

(Third transparent film)
The refractive index of the above-mentioned third transparent film is preferably 1.5 to 1.55 from the viewpoint of improving the concealing property of the transparent electrode pattern by approaching the refractive index of the above-mentioned transparent substrate, More preferably, it is -1.52.

<Method for producing laminate>
The method for producing the laminate of the present invention is not limited and can be produced by a known method.
Among them, the laminate of the present invention is produced by a production method including a step of laminating the second resin layer and the curable resin layer of the transfer film of the present invention in this order on a transparent electrode pattern. It is preferable. With such a configuration, the second resin layer of the laminate and the above-described curable resin layer can be collectively transferred, and the laminate having no problem of visually recognizing the transparent electrode pattern can be easily produced with high productivity. Can be manufactured.
The second resin layer in the method for producing a laminate is formed on the transparent electrode pattern and on the transparent film in the non-pattern region, or directly or via another layer. Is done.

(Surface treatment of transparent substrate)
Further, in order to improve the adhesion of each layer after lamination in the subsequent transfer step, the non-contact surface of the transparent substrate (front plate) in advance (of the surface of the transparent substrate constituting the capacitive input device, Surface treatment can be performed on the surface opposite to the surface on which the input means such as a finger is brought into contact. As the aforementioned surface treatment, it is preferable to carry out a surface treatment (silane coupling treatment) using a silane compound. As the silane coupling agent, those having a functional group that interacts with the photosensitive resin are preferable. For example, a liquid containing a silane coupling agent (0.3 mass% aqueous solution of N-β (aminoethyl) γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) is sprayed for 20 seconds with a shower, Wash with pure water shower. Thereafter, the reaction is carried out by heating. A heating tank may be used, and the reaction can be promoted by preheating the substrate of the laminator.

(Transparent electrode pattern film formation)
The above-mentioned transparent electrode pattern uses the method of forming the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 in the description of the capacitive input device of the present invention described later. Thus, it is possible to form a film on a transparent substrate or a transparent film having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm, and a method using a photosensitive film described later is preferable.

(Filming of curable resin layer and second resin layer)
The method for forming the curable resin layer includes a protective film removing step for removing the protective film from the transfer film of the present invention, and a transfer step for transferring the curable resin layer of the transfer film from which the protective film has been removed onto the transparent electrode pattern. And an exposure step of exposing the curable resin layer transferred onto the transparent electrode pattern, and a developing step of developing the exposed curable resin layer.
When the transfer film of the present invention has the second resin layer, it is preferable that the curable resin layer and the second resin layer are simultaneously transferred, exposed and developed in the transfer step, the exposure step and the development step.

-Transfer process-
The aforementioned transfer step is a step of transferring the curable resin layer (preferably the curable resin layer and the second resin layer) of the transfer film from which the protective film has been removed onto the transparent electrode pattern.
At this time, a method including a step of removing the temporary support after laminating the curable resin layer (preferably the curable resin layer and the second resin layer) of the transfer film on the transparent electrode pattern is preferable.
The transfer (bonding) of the curable resin layer (preferably the curable resin layer and the second resin layer) to the surface of the transparent electrode pattern is performed by the curable resin layer (preferably the curable resin layer and the second resin layer). Is performed on the surface of the transparent electrode pattern by 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 described above, the method described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present invention.

The aforementioned exposure step is a step of exposing the curable resin layer (preferably the curable resin layer and the second resin layer) transferred onto the transparent electrode pattern.
Specifically, a predetermined mask is disposed above the curable resin layer (preferably the curable resin layer and the second resin layer) formed on the transparent electrode pattern and the temporary support, and then the upper part of the mask. And a method of exposing the curable resin layer (preferably the curable resin layer and the second resin layer) from the light source (via a mask and a temporary support).
Here, the light source for the exposure can be irradiated with light (for example, 365 nm, 405 nm, etc.) in a wavelength region capable of curing the curable resin layer (preferably the curable resin layer and the second resin layer). If there are, they can be appropriately selected and used. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is about 5-200 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.

The development step described above is a step of developing the exposed curable resin layer (preferably the curable resin layer and the second resin layer).
In the present invention, the development step described above is a development step in a narrow sense that pattern-develops the pattern-exposed curable resin layer (preferably the curable resin layer and the second resin layer) with a developer.
The development described above can be performed using a developer. The developer is not particularly limited, and a known developer such as the developer described in JP-A-5-72724 can be used. The developing solution is preferably a developing solution in which the photocurable resin layer has a developing type development behavior. For example, pKa (The negative logic of the acid dissociation constant); Ka is a compound of 0 to 13 in acid dissociation constant. A developer containing 0.05 to 5 mol / L is preferable. On the other hand, when the curable resin layer (preferably the curable resin layer and the second resin layer) itself does not form a pattern, the developer exhibits a development behavior that does not dissolve the non-alkali development type colored composition layer. A developer is preferable, for example, a developer containing a compound having pKa = 7 to 13 at a concentration of 0.05 to 5 mol / L. A small amount of an organic solvent miscible with water may be added to the developer. 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, and benzyl alcohol. , 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.

  As the development method described above, any of paddle development, shower development, shower & spin development, dip development, and the like may be used. Here, the above-described shower development will be described. The uncured portion can be removed by spraying a developer onto the above-described curable resin layer and the above-described second resin layer after exposure. When a thermoplastic resin layer or an intermediate layer is provided, an alkaline solution having a low solubility of the photocurable resin layer is sprayed by a shower or the like before development to remove the thermoplastic resin layer or the intermediate layer. It is preferable to keep it. 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.

  The above-described method for manufacturing a capacitive input device may have other steps such as a post-exposure step and a post-bake step. When the curable resin layer (preferably the curable resin layer and the second resin layer) is thermosetting, it is preferable to perform a post-bake process.

  The patterning exposure and the entire surface exposure may be performed after peeling the temporary support, or may be performed before peeling the temporary support, and then the temporary support may be peeled off. Exposure through a mask or digital exposure using a laser or the like may be used.

-Heating process-
The method for producing a laminate preferably includes a step of heat-treating the curable resin layer after transfer, and heat-treating the curable resin layer after transfer to convert at least a part of the carboxyl group-containing acrylic resin to carboxylic acid. It is more preferable to include a step of making an anhydride. The heat treatment to the curable resin layer after transfer is preferably after exposure and development, that is, a post-baking step after exposure and development. When the above-mentioned curable resin layer and the above-mentioned second resin layer are thermosetting, it is particularly preferable to perform a post-bake process. Moreover, it is preferable to perform a post-baking process also from a viewpoint of adjusting the resistance value of transparent electrodes, such as ITO.
The film substrate is used as the substrate at a heating temperature in the step of heat-treating the curable resin layer after the transfer so that at least a part of the carboxyl group-containing acrylic resin is a carboxylic anhydride. In some cases, more preferably 140-150 ° C.

(Transparent film formation)
The laminate of the present invention is a transparent film having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm on the opposite side of the transparent electrode pattern on which the second resin layer is formed. In addition, it is preferable that the transparent film is formed directly on the transparent electrode pattern or via another layer such as the third transparent film.
The method for forming the transparent film is not particularly limited, but is preferably formed by transfer or sputtering.
Among them, the laminate is preferably formed by transferring the transparent film-forming curable resin layer formed on the temporary support onto the transparent substrate. More preferably, the film is cured later to form a film. As a transfer and curing method, the photosensitive film in the description of the capacitance-type input device of the present invention described later is used, and the above-described curable resin layer and the above-described second resin layer in the laminate manufacturing method are transferred. The method of performing a transfer, exposure, development, and other processes similarly to the method of performing can be mentioned. In that case, it is preferable to adjust the refractive index of the transparent film in the above range by dispersing the metal oxide particles in the photocurable resin layer in the photosensitive film.

On the other hand, when the transparent film is an inorganic film, it is preferably formed by sputtering.
As the sputtering method, the methods used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used.

(Third transparent film formation)
The third transparent film forming method is the same as the method of forming a transparent film having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm on a transparent substrate.

The method for producing a laminate preferably includes a step of simultaneously curing the curable resin layer and the second resin layer, and more preferably includes a step of pattern curing at the same time. In the transfer film of the present invention, the second resin layer is preferably laminated without curing the curable resin layer after the curable resin layer is laminated. The curable resin layer and the second resin layer transferred from the transfer film of the present invention thus obtained can be simultaneously cured. Thereby, after transferring the curable resin layer and the second resin layer from the transfer film of the present invention onto the transparent electrode pattern, it can be developed into a desired pattern by photolithography.
The method for producing a laminate includes an uncured portion of the curable resin layer and the second resin layer after the step of simultaneously curing the curable resin layer and the second resin layer (in the case of photocuring, only the unexposed portion). It is more preferable to include a step of developing and removing only the exposed portion).

[Capacitance type input device]
The capacitive input device of the present invention includes the electrode protective film of the capacitive input device of the present invention or the laminate of the present invention.
In the capacitive input device, it is preferable that the above-described curable resin layer of the transfer film is laminated on the transparent substrate including the transparent electrode pattern using the transfer film of the present invention. More preferably, the above-mentioned second resin layer and the above-mentioned curable resin layer of the transfer film are laminated in this order on the transparent substrate including the transparent electrode pattern. The second resin layer and the curable resin layer disposed adjacent to the second resin layer were transferred from the transfer film of the present invention onto the transparent electrode pattern of the capacitive input device. Is particularly preferred.
In the capacitive input device of the present invention, it is preferable that the curable resin layer and the second resin layer transferred from the transfer film are simultaneously cured, and the curable resin layer and the second resin layer are simultaneously pattern cured. More preferably. In addition, when hardening | curing simultaneously the curable resin layer and 2nd resin layer which were transcribe | transferred from the transfer film, it is preferable not to peel a temporary support body from a transfer film.
The capacitance-type input device of the present invention may be developed by removing the uncured portion of the curable resin layer and the second resin layer that are transferred from the transfer film of the present invention and simultaneously pattern-cured, and removed. preferable. In addition, it is preferable to peel the protective film from the transfer film of the present invention after simultaneously curing the curable resin layer and the second resin layer transferred from the transfer film of the present invention and before developing. Since the capacitance-type input device of the present invention needs to be connected to the flexible wiring formed on the polyimide film at the terminal portion of the routing wiring, it is covered with the curable resin layer (and the second resin layer). Preferably not.
This aspect is shown in FIG. FIG. 13 shows a capacitance-type input device having the following configuration including a lead wire (another conductive element 6) of a transparent electrode pattern and a terminal portion 31 of the lead wire.
Since the curable resin layer on the terminal portion 31 of the routing wiring is an uncured portion (unexposed portion), it is removed by development, and the terminal portion 31 of the routing wiring is exposed.
Specific exposure and development modes are shown in FIGS. FIG. 14 shows a state before the transfer film 30 of the present invention having a curable resin layer and a second resin layer is laminated on the transparent electrode pattern of the capacitive input device and cured by exposure or the like. Indicates. When photolithography is used, that is, when cured by exposure, the curable resin layer having the shape shown in FIG. 9 and the cured portion (exposed portion) 33 of the second resin layer are subjected to pattern exposure and non-patterning using a mask. It can be obtained by developing the exposed area. Specifically, in FIG. 9, the opening 34 corresponding to the terminal portion of the routing wiring as the uncured portion of the curable resin layer and the second resin layer, and the outside of the outline of the frame portion of the capacitive input device The end of the transfer film of the present invention having the curable resin layer and the second resin layer that protruded is removed, and the curable resin layer for not covering the terminal portion (lead-out wiring portion) of the routing wiring and A cured portion (desired pattern) of the second resin layer is obtained.
Thereby, the flexible wiring produced on the polyimide film can be directly connected to the terminal portion 31 of the routing wiring, and the sensor signal can be sent to the electric circuit.
The capacitance type input device of the present invention includes a transparent electrode pattern, a second resin layer disposed adjacent to the transparent electrode pattern, and a curable resin disposed adjacent to the second resin layer. And a refractive index of the second resin layer is higher than a refractive index of the curable resin layer, and a refractive index of the second resin layer is 1.6 or more. It is preferable to have.
Hereinafter, the detail of the preferable aspect of the electrostatic capacitance type input device of this invention is demonstrated.

The capacitance type input device of the present invention includes at least the following (3) to (5) on the front plate (corresponding to the transparent substrate in the laminate of the present invention) and the non-contact surface side of the front plate. It has elements (7) and (8) and preferably has the laminate of the present invention.
(3) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in the first direction via the connection portions;
(4) A plurality of second electrode patterns comprising a plurality of pad portions that are electrically insulated from the first transparent electrode pattern and extend in a direction intersecting the first direction.
(5) An insulating layer for electrically insulating the first transparent electrode pattern and the second electrode pattern described above;
(7) a second resin layer formed so as to cover all or part of the elements of (3) to (5) described above;
(8) A curable resin layer formed so as to cover the element (7) described above.
Here, the above-mentioned (7) second resin layer corresponds to the above-mentioned second resin layer in the laminate of the present invention. Moreover, the above-mentioned (8) curable resin layer corresponds to the above-mentioned curable resin layer in the laminate of the present invention. In addition, it is preferable that the above-mentioned curable resin layer is a so-called transparent protective layer in a generally known capacitance-type input device.

In the capacitive input device of the present invention, the above-mentioned (4) second electrode pattern may be a transparent electrode pattern or a transparent electrode pattern, but is preferably a transparent electrode pattern.
The capacitance-type input device of the present invention further includes (6) the first transparent electrode described above that is electrically connected to at least one of the first transparent electrode pattern and the second electrode pattern described above. The conductive element may be different from the pattern and the second electrode pattern described above.
Here, when the above-mentioned (4) second electrode pattern is not a transparent electrode pattern and does not have the above-mentioned (6) another conductive element, the above-mentioned (3) first transparent electrode pattern is This corresponds to the transparent electrode pattern in the laminate of the present invention.
When the above-mentioned (4) second electrode pattern is a transparent electrode pattern and does not have the above-mentioned (6) another conductive element, the above-mentioned (3) first transparent electrode pattern and the above-mentioned (4 ) At least one of the second electrode patterns corresponds to the transparent electrode pattern in the laminate of the present invention.
When the above-mentioned (4) second electrode pattern is not a transparent electrode pattern but has the above-mentioned (6) another conductive element, the above-mentioned (3) the first transparent electrode pattern and the above-mentioned (6) another At least one of the conductive elements corresponds to the transparent electrode pattern in the laminate of the present invention.
When the above-mentioned (4) second electrode pattern is a transparent electrode pattern and has the above-mentioned (6) another conductive element, the above-mentioned (3) first transparent electrode pattern, the above-mentioned (4) first At least one of the two electrode patterns and the above-described another conductive element (6) corresponds to the transparent electrode pattern in the laminate of the present invention.

  The capacitance-type input device of the present invention further comprises (2) a transparent film, (3) the first transparent electrode pattern and the front plate, (4) the second electrode pattern and the front surface. It is preferable to have between board | substrates or between the above-mentioned (6) another electroconductive element and the above-mentioned front board. Here, it is concealed of the transparent electrode pattern that the above-mentioned (2) transparent film corresponds to a transparent film having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm in the laminate of the present invention. From the viewpoint of further improving the properties.

The capacitance-type input device of the present invention preferably further has (1) a mask layer and / or a decoration layer as necessary. The mask layer described above is provided as a black frame around the area touched by a finger or a touch pen so that the transparent electrode pattern routing wiring cannot be visually recognized from the contact side or is decorated. The above-mentioned decoration layer is provided for decoration as a frame around the area touched with a finger or a touch pen. For example, it is preferable to provide a white decoration layer.
The above-mentioned (1) mask layer and / or decorative layer are the above-mentioned (2) between the transparent film and the above-mentioned front plate, (3) between the above-mentioned (3) first transparent electrode pattern and the above-mentioned front plate, and (4) above-mentioned. It is preferable to have between a 2nd transparent electrode pattern and the above-mentioned front board, or between the above-mentioned (6) another electroconductive element and the above-mentioned front board. The aforementioned (1) mask layer and / or decorative layer is more preferably provided adjacent to the aforementioned front plate.

  Even if the capacitance-type input device of the present invention includes such various members, the above-described second resin layer disposed adjacent to the transparent electrode pattern and the above-described second resin By including the above-mentioned curable resin layer disposed adjacent to the layer, the transparent electrode pattern can be made inconspicuous, and the concealment problem of the transparent electrode pattern can be improved. Furthermore, as described above, the transparent electrode pattern is sandwiched between the transparent film having the refractive index of 1.6 to 1.78 and the thickness of 55 to 110 nm and the second resin layer. Therefore, the concealment problem of the transparent electrode pattern can be improved.

<Configuration of capacitance type input device>
First, a preferable configuration of the capacitive input device of the present invention will be described together with a method for manufacturing each member constituting the device. FIG. 1A is a cross-sectional view showing a preferred configuration of the capacitive input device of the present invention. 1A, a capacitive input device 10 includes a transparent substrate (front plate) 1, a mask layer 2, a transparent film 11 having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm, One transparent electrode pattern (shown is a connection portion 3b of the first transparent electrode pattern), a second transparent electrode pattern 4, an insulating layer 5, another conductive element 6, and a second The aspect comprised from the resin layer 12 and the curable resin layer 7 is shown.
Moreover, FIG. 1B showing the XY cross section in FIG. 3 mentioned later is also sectional drawing which shows the preferable structure of the electrostatic capacitance type input device of this invention. 1B, the capacitive input device 10 includes a transparent substrate (front plate) 1, a transparent film 11 having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm, and a first transparent electrode pattern. 3, the aspect comprised from the 2nd transparent electrode pattern 4, the 2nd resin layer 12, and the curable resin layer 7 is shown.

  For the transparent substrate (front plate) 1, the materials listed as materials for the transparent electrode pattern in the laminate of the present invention can be used. Moreover, in FIG. 1A, the side in which each element of the transparent substrate 1 which is a front plate is provided is called a non-contact surface side. In the capacitive input device 10 of the present invention, input is performed by bringing a finger or the like into contact with the contact surface (the surface opposite to the non-contact surface) of the transparent substrate 1 that is the front plate.

A mask layer 2 is provided on the non-contact surface of the transparent substrate 1 that is the front plate. The mask layer 2 is a frame-shaped pattern around the display area formed on the non-contact surface side of the front panel of the touch panel, and is formed so as not to show the lead wiring and the like.
As shown in FIG. 2, the capacitive input device 10 of the present invention has a mask layer 2 so as to cover a part of the transparent substrate 1 as a front plate (a region other than the input surface in FIG. 2). Is provided. Further, the transparent substrate 1 as the front plate can be provided with an opening 8 in a part thereof as shown in FIG. A pressing mechanical switch can be installed in the opening 8.

  On the non-contact surface of the transparent substrate 1 which is the front plate, a plurality of first transparent electrode patterns 3 formed with a plurality of pad portions extending in the first direction via the connection portions, and the first 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 intersecting the first direction; and a first transparent electrode pattern 3 and an insulating layer 5 that electrically insulates the second transparent electrode pattern 4 are formed. As the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 described later, those mentioned as the material for the transparent electrode pattern in the laminate of the present invention may be used. An ITO film is preferable.

Further, at least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4 is opposite to the non-contact surface of the transparent substrate 1 that is the front plate and the transparent substrate 1 that is the front plate of the mask layer 2. It can be installed across both areas of the surface. In FIG. 1A, the second transparent electrode pattern 4 extends over both regions of the non-contact surface of the transparent substrate 1 that is the front plate and the surface opposite to the transparent substrate 1 that is the front plate of the mask layer 2. The installed figure is shown.
Thus, even when a photosensitive film is laminated across a mask layer that requires a certain thickness and the non-contact surface of the front plate, a vacuum laminator or the like can be obtained by using a photosensitive film having a specific layer configuration described later. Even without using expensive equipment, it is possible to perform lamination without generating bubbles at the boundary of the mask portion with a simple process.

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 from the first transparent electrode pattern 3 by the insulating layer 5, and is in a direction intersecting the first direction C (second direction D in FIG. 3). ) To be formed by a plurality of pad portions. Here, when the first transparent electrode pattern 3 is formed, the pad portion 3a and the connection portion 3b described above may be manufactured as one body, or only the connection portion 3b is manufactured, 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 produced (patterned) as a single body (patterning), as shown in FIG. 3, a part of the connection part 3b and a part of the pad part 3a are connected, and an insulating layer is formed. Each layer is formed so that the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are electrically insulated by 5.
Moreover, the area | region in which the 1st transparent electrode pattern 3 in FIG. 3, the 2nd transparent electrode pattern 4, and another electroconductive element 6 mentioned later is not formed is equivalent to the non-pattern area | region 22 in the laminated body of this invention. .

In FIG. 1A, another conductive element 6 is installed on the surface side opposite to the transparent substrate 1 which is the front plate of the mask layer 2. Another 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 the first transparent electrode pattern 3 and the second transparent electrode pattern 4. Is a different element.
In FIG. 1A, an embodiment in which another conductive element 6 is connected to the second transparent electrode pattern 4 is shown.

  Moreover, in FIG. 1A, the curable resin layer 7 is installed so that all of each component may be covered. The curable resin layer 7 may be configured to cover only a part of each component. The insulating layer 5 and the curable resin layer 7 may be the same material or different materials. As a material which comprises the insulating layer 5, what was mentioned as a material of the curable resin layer in the laminated body of this invention or the 2nd resin layer can be used preferably.

<Method for Manufacturing Capacitive Input Device>
Examples of the embodiment formed in the process of manufacturing the capacitive input device of the present invention include the embodiments shown in FIGS. FIG. 4 is a top view showing an example of the transparent substrate 1 in which the opening 8 is formed. FIG. 5 is a top view showing an example of the front plate on which the mask 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 the first transparent electrode pattern 3 and the 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 the example which actualized the following description, and the scope of the present invention is not limitedly interpreted by these drawings.

  In the method of manufacturing a capacitance-type input device, when the second resin layer 12 and the curable resin layer 7 are formed, the elements are arbitrarily formed using the transfer film of the present invention. It can be formed by transferring the above-mentioned second resin layer and the above-mentioned curable resin layer to the surface of the transparent substrate 1 which is the front plate.

In the manufacturing method of the capacitance type input device, at least one element of the mask layer 2, the first transparent electrode pattern 3, the second transparent electrode pattern 4, the insulating layer 5, and another conductive element 6. However, it is preferable to form using the photosensitive film which has a temporary base material and a photocurable resin layer in this order.
When each of the above-described elements is formed using the transfer film of the present invention or the above-described photosensitive film, the resist component does not leak or protrude from the opening even in the transparent substrate (front plate) having the opening. Especially in the mask layer where it is necessary to form a light-shielding pattern just above the boundary line of the edge of the front plate, the resist component does not leak or protrude from the edge of the transparent substrate, so that the non-contact surface of the transparent substrate is not contaminated. With a simple process, it is possible to manufacture a touch panel that is thin and lightweight.

  Using the above-mentioned photosensitive film as a permanent material such as the first transparent electrode pattern, the second transparent electrode pattern and the conductive element when the mask layer, the insulating layer, and the conductive photocurable resin layer are used. In the case of forming the photosensitive film, the photosensitive film may be laminated on a transparent substrate or the like and then subjected to pattern exposure as necessary. The aforementioned photosensitive film may be a negative type material or a positive type material. When the above-mentioned photosensitive film is a negative material, a pattern can be obtained by developing and removing the unexposed portion and when the positive film is a positive material. In the development, the thermoplastic resin layer and the photocurable resin layer may be developed and removed with separate liquids, or may be removed 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.

(Photosensitive film)
The photosensitive film other than the transfer film of the present invention, which is preferably used when manufacturing the capacitance type input device of the present invention, is described in [0222] to [0255] of JP-A No. 2014-178922. The contents of this publication are incorporated herein.

<Image display device>
The capacitive input device of the present invention and an image display device including the capacitive input device as constituent elements are “latest touch panel technology” (Techno Times, issued July 6, 2009), Mitani. The structure disclosed in Yuji's supervision, “Touch Panel Technology and Development”, CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. can be applied. .

  The present invention will be described more specifically with reference to the following 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 is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

[Example 1]
<Production of transfer film>
(Formation of curable resin layer)
Using a slit nozzle on a 75 μm thick polyethylene terephthalate film (temporary support), adjust the coating liquid for the curable resin layer having the following formulation 101 so that the thickness after drying is 10 μm. After applying and drying at 100 ° C. for 2 minutes, the coating was further dried at 120 ° C. for 1 minute to form a curable resin layer.

-Coating liquid for curable resin layer: Formula 101 (organic solvent-based resin composition)-
(Polymerizable compound)
Tricyclodecanedimethanol diacrylate 5.63 parts A-DCP: Shin-Nakamura Chemical Co., Ltd. Carboxylic acid-containing monomer 0.93 parts Aronix TO2349: Toagosei Co., Ltd. Urethane acrylate 2.81 parts 8UX -015A: Taisei Fine Chemical Co., Ltd.

(Binder polymer)
-The following compound A (acid value 95 mgKOH / g) 15.63 parts

(Polymerization initiator)
・ Irgacure OXE-02: 0.11 part of photopolymerization initiator manufactured by BASF ・ Irgacure 907: 0.11 part of photopolymerization initiator manufactured by BASF

(Compound capable of reacting with acid by heating)
・ Duranate X3071.04: Block isocyanate manufactured by Asahi Kasei Chemicals Corporation
3.63 parts

(Additive)
・ Mega Fuck F551: DIC Corporation 0.02 part

(Organic solvent)
・ 31.03 parts of 1-methoxy-2-propyl acetate ・ 40.00 parts of methyl ethyl ketone

(Formation of second resin layer)
Next, on the curable resin layer, a second resin layer coating liquid having the following formulation 201 was applied so that the thickness after drying was 100 nm, and dried at 80 ° C. for 1 minute. Thereafter, it was further dried at 110 ° C. for 1 minute to form a second resin layer disposed in direct contact with the curable resin layer. Here, the formulation 201 is prepared using a resin having an acid group and an aqueous ammonia solution, and the resin having an acid group is neutralized with an aqueous ammonia solution and contains an ammonium salt of the resin having an acid group. A second coating solution for the resin layer is prepared.

-Second coating solution for resin layer: Formulation 201 (aqueous resin composition)-
(Resin having an acid group)
-Acrylic resin 0.47 parts Methacrylic acid / Allyl methacrylate copolymer resin Weight average molecular weight 25,000, Composition ratio (molar ratio) = 40/60, Solid content 99.8%

(Monomer having an acid group)
・ Aronix TO-2349: Carboxylic acid-containing monomer 0.04 part, manufactured by Toagosei Co., Ltd.

(particle)
・ Nanouse OZ-S30M: Nissan Chemical Industries Co., Ltd. 4.28 parts Solid content 30.5%, methanol 69.5%, refractive index 2.2, ZrO ₂ particles having an average particle size of about 12 nm is there.

(Metal oxidation inhibitor)
・ BT120: Benzotriazole 0.04 parts, manufactured by Johoku Chemical Industry Co., Ltd.

(Additive)
・ Megafuck F444 0.01 part DIC Corporation

(solvent)
・ Ammonia aqueous solution (2.5%) 7.84 parts ・ Distilled water 29.50 parts ・ Methanol 65.70 parts

(Formation of protective film)
The laminate obtained as described above on the temporary support with the curable resin layer and the second resin layer arranged in direct contact with the curable resin layer in this order, the laminate A protective film A1 shown below was finally bonded onto the second resin layer to produce a transfer film of Example 1.
-Protective film A1-
Name: Alphan FG201 (manufactured by Oji F-Tex Co., Ltd., polypropylene film)
Oxygen permeability coefficient: 2500cm ³ · 25μm / m ² · 24 hours · atm
Thickness: 30μm
Surface roughness Ra: 40 nm

(Roll formation)
The obtained transfer film of Example 1 was wound into a roll shape so that the protective film was on the outside, and a roll was formed. It was stored in a roll state at 40 ° C. and a relative humidity of 80% for 7 days.
In the transfer film evaluation described below, a transfer film unwound from a roll was used.

[Example 2]
In Example 1, the transfer film of Example 2 was produced like Example 1 except having replaced protective film A1 with protective film A2 shown below.
-Protective film A2-
Name: Alphan E201F (manufactured by Oji F-Tex Co., Ltd., polypropylene film)
Oxygen transmission coefficient: 2700 cm ³ · 25 μm / m ² · 24 hours · atm
Thickness: 30μm
Surface roughness Ra: 50 nm

[Example 3]
In Example 1, the transfer film of Example 3 was produced like Example 1 except having replaced protective film A1 with protective film A3 shown below.
-Protective film A3-
Name: GF-8 (polyethylene film, NF-15 similar product made by Tamapoli described in Example 1 of Japanese Patent No. 5257648)
Oxygen permeability coefficient: 2600cm ³ · 25μm / m ² · 24 hours · atm
Thickness: 30μm
Surface roughness Ra: 60 nm

[Examples 4 to 14 and Comparative Examples 1 to 3]
In Example 1, transfer films of Examples 4 to 14 and Comparative Examples 1 to 3 were produced in the same manner as in Example 1 except that the protective film A1 was replaced with the protective films A4 to A17 shown in the following table, respectively.
The characteristics of the protective films A4 to A17 are shown below.
The protective film A4 is a PET film.
The protective film A5 is a polyvinyl chloride film.
The protective film A6 is a polycarbonate film.
The protective film A7 is a highly oriented PET film.
The protective film A8 is a low density polyethylene film.
The protective film A9 is a smooth PET film.
The protective film A10 is a polypropylene film.
The protective film A11 is an ultra-smooth PET film.
The protective film A12 is a roughened polypropylene film.
The protective film A13 is a 12 μm-thick polypropylene film.
The protective film A14 is a 15 μm-thick polypropylene film.
The protective film A15 is a 20 μm thick polypropylene film.
The protective film A16 is a 70 μm thick polypropylene film.
The protective film A17 is an 80 μm thick polypropylene film.

[Examples 15 to 19]
In Example 1, the transfer of Examples 15 to 19 was performed in the same manner as Example 1 except that the ZrO ₂ particles added to the _second coating solution for the resin layer were replaced with the contents shown in the following table. A film was prepared.

[Characteristics of transfer film]
<Double bond consumption rate>
The double bond consumption rate of the curable resin layer and the second resin layer was measured by the following method.
(1) Double bond consumption rate of curable resin layer When the curable resin layer was applied and dried on the temporary support, a section of this curable resin layer was cut from the surface using a microtome. To 0.1 mg of this slice, 2 mg of KBr powder was added and mixed well under a yellow light to obtain a UV (ultraviolet) uncured product measurement sample of the curable resin layer in the measurement of the double bond consumption rate.
FT-IR apparatus (Thermo Nicolet Japan Ltd., Nicolet 710) was used to measure the wavelength region of 400cm ^-1 ~4000cm ^-1, it was determined peak intensity of 810 cm ^-1 derived from C = C bond. FT-IR is a Fourier Transform Infrared Spectroscopy (Fourier Transform Infrared Spectroscopy). The peak intensity (double bond residual amount) A ₁ of the UV uncured product of the curable resin layer only applied and dried, and the peak intensity B ₁ of the film section of the curable resin layer in the transfer film of each Example and Comparative Example Asked. The double bond consumption rate of the curable resin layer was calculated according to the following formula.
formula:
Double bond consumption rate of curable resin layer = {1- (B ₁ / A ₁ )} × 100%
In the transfer films of Examples and Comparative Examples, the curable resin layer was not exposed after the curable resin layer was applied and dried on the temporary support. However, when manufacturing a transfer film of a reference example in which a second resin layer or a protective film is laminated after applying and drying a curable resin layer on a temporary support and exposing the curable resin layer, reference The peak intensity C ₁ of the film section of the curable resin layer in the example transfer film is obtained. Then, the double bond consumption rate of the curable resin layer in the transfer film of the reference example is calculated according to the following formula.
formula:
Double bond consumption rate of curable resin layer in transfer film of reference example = {1- (C ₁ / A ₁ )} × 100%
Further, the peak intensity A ₁ of the UV uncured product of the curable resin layer may be obtained by separately preparing a UV uncured product sample of the curable resin layer for A ₁ measurement. Specifically, the composition of the curable resin layer of the transfer film is analyzed and specified, a UV uncured product sample of the curable resin layer for A ₁ measurement is prepared, and A ₁ can be obtained from this sample. .

(2) Double bond consumption rate of the second resin layer When the second resin layer is applied and dried on the curable resin layer, the second resin layer is cut from the surface using a microtome. Cut. To 0.1 mg of this slice, 2 mg of KBr powder was added and mixed well under a yellow light to obtain a UV uncured product measurement sample of the second resin layer in the measurement of the double bond consumption rate.
FT-IR apparatus (Thermo Nicolet Japan Ltd., Nicolet 710) was used to measure the wavelength region of 400cm ^-1 ~4000cm ^-1, it was determined peak intensity of 810 cm ^-1 derived from C = C bond. Peak intensity (double bond residual amount) A ₂ of the UV uncured product of the second resin layer only by coating and drying, and peak intensity of the film section of the second resin layer in the transfer films of each Example and Comparative Example B ₂ was determined. The double bond consumption rate was calculated according to the following formula for the second resin layer.
formula:
Double bond consumption rate of second resin layer = {1− (B ₂ / A ₂ )} × 100%
In the transfer films of Examples and Comparative Examples, the second resin layer was not exposed after the second resin layer was applied and dried on the curable resin layer. However, when manufacturing a transfer film of a reference example in which a protective film is laminated after applying and drying the second resin layer on the curable resin layer and exposing the second resin layer, transfer the reference example. the peak intensity C ₂ of film sections of the second resin layer in the film determined. Then, the double bond consumption rate of the 2nd resin layer in the transfer film of a reference example is calculated according to a following formula.
formula:
Consumption rate of double bond of second resin layer in transfer film of reference example = {1- (C ₂ / A ₂ )} × 100%
Further, the peak intensity A ₂ of the UV uncured product of the second resin layer may be obtained by separately preparing a UV uncured product sample of the curable resin layer for A ₂ measurement. Specifically, the composition of the second resin layer of the transfer film is analyzed and specified, a UV uncured product sample of the second resin layer for A ₂ measurement is prepared, and A ₂ is obtained from this sample. Can do.

  The double bond consumption rates of the obtained curable resin layer and second resin layer are shown in the following table.

<Refractive index and thickness>
The refractive index n ₁ and thickness T _{1 of} the curable resin layer and the refractive index n ₂ and thickness T ₂ of the second resin layer were measured using a reflection spectral film thickness meter FE-3000 (manufactured by Otsuka Electronics Co., Ltd.). And determined as follows.
(1) On one surface of a temporary support used in each example and comparative example, cut into a length of 5 cm × 5 cm in length and breadth, via a transparent adhesive tape (OCA tape 8171CL: manufactured by 3M Co., Ltd.) Then, a laminate in which PT100 NB (manufactured by Lintec Co., Ltd.), which is a black polyethylene terephthalate (PET) material, was bonded was prepared. Using a reflection spectral film thickness meter FE-3000, the reflection spectrum (wavelength: 430 to 800 nm) of the laminate of the temporary support and black PET was evaluated, and the refractive index n ₀ of the temporary support at each wavelength was determined.
(2) Transparent adhesive tape on the temporary support surface of a sample in which only the curable resin layer was formed on the temporary support in the same manner as in each of the Examples and Comparative Examples, which was cut out to a length of 5 cm × 5 cm. The laminated body which made the black PET material contact through (OCA tape 8171CL: 3M Co., Ltd. product) was produced. Using a transmission electron microscope (TEM: HT7700, Hitachi High-Tech Fielding Co., Ltd.), the laminate of the curable resin layer, the temporary support, and the black PET was structurally analyzed. The thickness of the curable resin layer was measured at 10 points to determine an average value, and a first expected value T ₁ (I) of the average value of the thickness of the curable resin layer was determined. Using a reflection spectral film thickness meter FE-3000 manufactured by Otsuka Electronics Co., Ltd., the reflection spectrum (wavelength: 430 to 800 nm) of a laminate of a curable resin layer, a temporary support, and black PET was evaluated, and cured at each wavelength. The second expected value T ₁ (II) of the refractive index n ₁ of the curable resin layer and the average value of the thickness of the curable resin layer was determined, and the refractive index n ₁ of the curable resin layer at a wavelength of 550 nm was described in the following table. . At this time, in order to consider the reflection at the interface between the curable resin layer and the temporary support, the value of the refractive index n ₀ of the temporary support obtained in the above (1) and the average value of the average thickness of the curable resin layer The expected value T ₁ (I) of ₁ is input to the thickness calculation software attached to the FE 3000, and then the refractive index n ₁ of the curable resin layer is calculated from the reflection spectrum of the laminate of the curable resin layer, the temporary support, and the black PET. The second expected value T ₁ (II) of the average value of the thickness of the curable resin layer was obtained by fitting by simulation calculation.
(3) A transparent adhesive tape (OCA) tape is applied to the surface of the temporary support of the transfer film of each Example and Comparative Example, which was cut into a length of 5 cm × 5 cm, and the protective film was peeled off. 8171CL: manufactured by 3M Co., Ltd.), a sample piece in which a black PET material was contacted was produced. The sample piece is structurally analyzed using a transmission electron microscope (TEM), the thickness of the second resin layer is measured at 10 points, the average value is obtained, and the expected value T of the average value of the thickness of the second resin layer. ₂ (I) was determined. Reflection spectrum of 200 measurement points (that is, 4 cm length) on a straight line in an arbitrary direction at a measurement spot of 40 μm in diameter and at intervals of 0.2 mm using a reflection spectral film thickness meter FE-3000. Was repeated for a total of 1000 points in 5 rows every 1 cm in the direction orthogonal to the linear direction described above. At this time, the reflection at the interface between the curable resin layer and the temporary support and the interface between the curable resin layer and the second resin layer is taken into consideration. Therefore, the second expected value of the average value of the refractive index n ₀ of the temporary support obtained in (1), the refractive index n ₁ of the curable resin layer obtained in (2) and the thickness of the curable resin layer. In a state where T ₁ (II) and the expected value T ₂ (I) of the average value of the thickness of the second resin layer are substituted into the calculation formula, the second resin layer, the curable resin layer, the temporary support, From the reflection spectrum of the black PET laminate, the refractive index n _{2 of} the second resin layer and the thicknesses of the curable resin layer and the second resin layer at 1000 measurement points were obtained by fitting by simulation calculation. Furthermore, the average value of the thickness of the curable resin layer and the second resin layer was calculated to obtain n ₁ , n ₂ , T ₁ , and T ₂ .
With respect to the thickness of the curable resin layer and the thickness of the second resin layer, the fitting value of the simulation can be improved by inputting the expected value obtained by conducting the structural analysis with TEM to the reflection spectral film thickness meter.
The refractive index n ₂ of the refractive index n ₁ and a second resin layer of the cured resin layer described in the following Table.

<Oxygen permeability coefficient of protective film>
The oxygen permeability coefficient of the protective film was measured using GTR-31A (GTR Tech Co., Ltd.), which is a gas permeability measuring device, in accordance with the differential pressure method described in JIS K7126-1.
The oxygen permeability coefficient of the obtained protective film is shown in the following table. JIS is Japan Industrial Standards.

<Surface roughness Ra of protective film>
Using a fine shape measuring instrument ET-350K (manufactured by Kosaka Laboratory Ltd.), the unevenness of the surface of the protective film was measured under the following conditions. The obtained measurement result was calculated using the following three-dimensional analysis software based on JIS B 0601-2001, and the surface roughness Ra of the protective film was obtained.
Three-dimensional analysis software: TDA-22 (manufactured by Kosaka Laboratory)
・ Contact pressure: 0.04mN
・ Measurement length: 0.5mm
・ Feeding speed: 0.1 mm / second ・ Line pitch: 5 μm
-Number of lines: 40-Height magnification: x 50000
・ Measurement direction: MD direction (MD is Machine Direction)
The surface roughness Ra of the obtained protective film is shown in the following table.

[Evaluation of transfer film]
<Bubble>
The protective film of the obtained transfer film is not peeled off, and is visually observed under illumination of a fluorescent lamp, and bubbles having a diameter of 100 μm or more are extracted. The area of 1 m ² of the transfer film is observed three times, and the average number of bubbles per 1 m ^{2 of} the transfer film is calculated.
The number of bubbles per 1 m ^{2 of the} transfer film was scored according to the following criteria.
5 points: 0 / m ²
4 points: 1 piece / m ^{2 or} less 3 points: 1 piece / m ² or more, 2 pieces / m ^{2 or} less 2 points: 2 pieces / m ² or more, less than 10 pieces / m ² 1 point: 10 pieces / m ² or more The results obtained are listed in the table below. The evaluation of bubbles is practically required to be 3 to 5 points, preferably 4 or 5 points, and more preferably 5 points.

<Transfer defects>
The protective film of the obtained transfer film was peeled off. The surface of the peeled protective film was visually observed under the illumination of a fluorescent lamp, and was transferred from the layer (second resin layer or curable resin layer) in contact with the protective film to the surface of the protective film with a diameter of 100 μm or more. Extract transcripts. The area of 1 m ² of the protective film is observed three times, and the average number of transferred products per 1 m ^{2 of} the protective film is calculated. The number of transferred products per 1 m ² of the surface of the protective film was defined as the number of transfer defects per 1 m ^{2 of} the transfer film.
The number of transfer defects per 1 m ^{2 of the} transfer film was scored according to the following criteria.
5 points: 0 / m ²
4 points: 1 piece / m ^{2 or} less 3 points: 1 piece / m ² or more, 2 pieces / m ^{2 or} less 2 points: 2 pieces / m ² or more, less than 10 pieces / m ² 1 point: 10 pieces / m ² or more The results obtained are listed in the table below. The evaluation of the transfer defect is practically required to be 3 to 5 points, preferably 4 or 5 points, and more preferably 5 points.

<Dent>
(Number of dent defects)
The protective film of the obtained transfer film was peeled off. After the protective film is peeled off, the transfer film is visually observed under illumination of a fluorescent lamp, and a dent having a diameter of 100 μm or more is extracted. At this time, the area of 1 m ² of the transfer film is observed three times, and the number of dent defects per 1 m ^{2 of} the transfer film is calculated on average.
The number of dent defects per 1 m ^{2 of the} transfer film was scored according to the following criteria.
5 points: 0 / m ²
4 points: 1 piece / m ^{2 or} less 3 points: 1 piece / m ² or more, 2 pieces / m ^{2 or} less 2 points: 2 pieces / m ² or more, less than 10 pieces / m ² 1 point: 10 pieces / m ² or more The results obtained are listed in the table below. The evaluation of the number of dent defects is preferably 3 to 5 points, more preferably 4 or 5 points, and particularly preferably 5 points.

(Simple evaluation of dents)
30 sheets of the obtained transfer film are cut out at 10 cm square, overlapped, and placed on a smooth aluminum plate. From above the transfer film, a sapphire needle having a diameter of 0.7 mm is pressed with a load of 400 g for 10 minutes.
Thereafter, the needle is removed and left to stand for 5 minutes, and then the number of transfer films on which a mark pressed by the needle is visually observed is counted. The number of transfer films in which the marks pressed by the needles were recognized was used as a simple evaluation of dents.
The results obtained are listed in the table below. It is a transfer film in which the occurrence of dents is prevented as the number of simple evaluations of dents (the number of transfer films on which the marks pressed by the needles are recognized) is smaller. The simple evaluation of the dent is preferably 10 sheets or less, more preferably 5 sheets or less.

[Evaluation of laminate]
<Production of laminate>
(Production of transparent electrode pattern film used for production of laminate)
-Formation of transparent film-
A cycloolefin resin film having a thickness of 38 μm and a refractive index of 1.53, using a high-frequency oscillator, an output voltage of 100%, an output of 250 W, a wire electrode having a diameter of 1.2 mm, an electrode length of 240 mm, and a work electrode of 1.5 mm The surface modification was performed by performing a corona discharge treatment for 3 seconds under the above conditions. The obtained film was used as a transparent film substrate.
Next, the material of the material-C shown in the following table is coated on a transparent film substrate using a slit-like nozzle, and then irradiated with ultraviolet rays (integrated light amount 300 mJ / cm ² ) and dried at about 110 ° C. As a result, a transparent film having a refractive index of 1.60 and a thickness of 80 nm was formed.

構造式（３）

なお、本明細書中の「ｗｔ％」は「質量％」と同義である。

Structural formula (3)

In the present specification, “wt%” is synonymous with “mass%”.

-Formation of transparent electrode layer-
A transparent film substrate on which a transparent film is formed is introduced into a vacuum chamber, and DC magnetron sputtering is performed using an ITO target (indium: tin = 95: 5 (molar ratio)) with a SnO ₂ content of 10% by mass. (Condition: Transparent film substrate temperature 150 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), an ITO thin film having a thickness of 40 nm and a refractive index of 1.82 was formed, and the transparent film and the transparent electrode were formed on the transparent film substrate. A layered film was obtained. The surface resistance of the ITO thin film was 80Ω / □ (Ω per square). DC is direct current.

-Preparation of photosensitive film E1 for etching-
On a polyethylene terephthalate film temporary base material having a thickness of 75 μm, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Further, a coating liquid for photocurable resin layer for etching having the following formulation E1 was applied and dried. In this way, a laminate comprising a thermoplastic resin layer having a dry thickness of 15.1 μm, an intermediate layer having a dry thickness of 1.6 μm, and a photocurable resin layer for etching having a thickness of 2.0 μm is formed on the temporary base material. Finally, a protective film (thickness 12 μm polypropylene film) was pressure-bonded. In this way, a photosensitive film E1 for etching, which is a transfer material in which the temporary base material, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the etching photocurable resin layer are integrated, was produced.

-Coating liquid for etching photocurable resin layer: Formulation E1--
Methyl methacrylate / styrene / methacrylic acid copolymer (copolymer composition (mass%): 31/40/29, weight average molecular weight 60,000,
Acid value: 163 mgKOH / g): 16.0 parts by mass / monomer 1 (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.): 5.6 parts by mass / tetramethylene oxide monomethacrylate of hexamethylene diisocyanate 0.5 Mole adduct
: 7.0 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 · 2,2-bis (orthochlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole
: 2.17 parts by mass · Malachite green oxalate: 0.02 parts by mass · Leuco Crystal Violet: 0.26 parts by mass · Phenothiazine: 0.013 parts by mass · Surfactant (trade name: Megafax F-780F, (Dainippon Ink Co., Ltd.)
: 0.03 parts by mass · Methyl ethyl ketone: 40 parts by mass · 1-methoxy-2-propanol: 20 parts by mass The viscosity at 100 ° C after removing the solvent of the coating liquid E1 for photocurable resin layer for etching is 2,500 Pa.・ It was second.

--- 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≈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 (Brand name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.): 9.1 parts by mass / Fluoropolymer: 0.54 parts by mass The above fluoropolymer is C ₆ F ₁₃ CH ₂ CH ₂ OCOCH═CH ₂ 40 parts, H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH═CH ₂ 55 parts and H (OCH ₂ CH ₂ ) ₇ OCOCH═CH ₂ 5 parts It is a polymer and has a weight average molecular weight of 30,000 and a 30% by mass solution of methyl ethyl ketone (trade name: MegaFac F780F, manufactured by Dainippon Ink & Chemicals, Inc.).

-Intermediate layer coating solution: Formulation 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 ISP Japan Co., Ltd.)
-Distilled water: 524 parts by mass-Methanol: 429 parts by mass

-Formation of transparent electrode pattern-
A film having a transparent film and a transparent electrode layer formed on a transparent film substrate is washed, and the protective photosensitive film E1 is removed. The surface of the transparent electrode layer is opposite to the surface of the photocurable resin layer for etching. (Transparent film substrate temperature: 130 ° C., rubber roller temperature 120 ° C., linear pressure 100 N / cm, conveyance speed 2.2 m / min). After peeling off the temporary base material, the thermoplastic resin layer and the intermediate layer were transferred to the surface of the transparent electrode layer together with the photocurable resin layer for etching. The distance between the surface of the exposure mask (quartz exposure mask having a transparent electrode pattern) and the photocurable resin layer for etching is set to 200 μm, and the photocurable property for etching is set via the thermoplastic resin layer and the intermediate layer. The resin layer was subjected to pattern exposure at an exposure amount of 50 mJ / cm ² (i-line).
Next, using a triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water) at 25 ° C., 100 Development process for 2 seconds, the thermoplastic resin layer and the intermediate layer are dissolved, and a surfactant-containing cleaning solution (trade name: T-SD3 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water) is used. Washing was performed at 33 ° C. for 20 seconds. Pure water is sprayed from an ultra-high pressure washing nozzle, the residue on the thermoplastic resin layer is removed with a rotating brush, and further post-baking treatment is performed at 130 ° C. for 30 minutes, and a transparent film and a transparent electrode layer are formed on the transparent film substrate. A film in which a photocurable resin layer pattern for etching was formed was obtained.
A film in which a transparent film, a transparent electrode layer, and a photocurable resin layer pattern for etching are formed on a transparent film substrate is immersed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), Processed for 100 seconds (etching process), dissolved and removed the transparent electrode layer in the exposed region not covered with the photocurable resin layer for etching, and a film with a transparent electrode pattern with the photocurable resin layer pattern for etching Got.
Next, a film with a transparent electrode pattern having a photocurable resin layer pattern for etching was applied to a resist stripping solution (N-methyl-2-pyrrolidone, monoethanolamine, surfactant (trade name: Surfynol 465, air (Products Co., Ltd.) immersed in a resist stripping tank containing a liquid temperature of 45 ° C.) and treated for 200 seconds (peeling treatment) to remove the photocurable resin layer for etching, and a transparent film and a transparent film on the transparent film substrate. A transparent electrode pattern film in which an electrode pattern was formed was obtained.

(Formation of electrode protection film for capacitive input device)
The protective film was peeled from the transfer film of each Example and Comparative Example, and the electrode protective film of the capacitance type input device of each Example and Comparative Example was obtained.

(Production of laminate)
-Transcription-
A transparent electrode pattern in which a transparent film and a transparent electrode pattern are formed on a transparent film substrate using the transfer films (electrode protective film of a capacitive input device) of Examples 1 to 18 and comparative examples from which the protective film has been peeled off The second resin layer, the curable resin layer, and the temporary support from the transfer film of each Example and Comparative Example to the transparent electrode pattern film so that the second resin layer covers the transparent film and the transparent electrode pattern of the film. Were transferred in this order to obtain a laminate before exposure. The transfer was performed at a temperature of the transparent film substrate: 40 ° C., a rubber roller temperature of 110 ° C., a linear pressure of 3 N / cm, and a conveyance speed of 2 m / min.
When the transfer film of Example 19 from which the protective film was peeled was used, the curable resin layer covered the transparent film and the transparent electrode pattern of the transparent electrode pattern film in which the transparent film and the transparent electrode pattern were formed on the transparent film substrate. Then, the curable resin layer and the temporary support were transferred in this order from the transfer film of Example 19 to the transparent electrode pattern film to obtain a laminate before exposure.

-Photolithography-
Then, using the proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp on the obtained pre-exposure laminate, an exposure mask (quartz exposure mask having an overcoat formation pattern) ) The distance between the surface and the temporary support was set to 125 μm, and pattern exposure was performed through the temporary support with an exposure amount of 100 mJ / cm ² (i-line). After peeling off the temporary support, the laminate (transparent film substrate) after pattern exposure was washed for 60 seconds at 32 ° C. with a 2% aqueous solution of sodium carbonate. Residues were removed by spraying ultrapure water from the ultra-high pressure cleaning nozzle onto the transparent film substrate after the cleaning treatment. Subsequently, air was blown to remove moisture on the transparent film substrate, and post-baking treatment was performed at 145 ° C. for 30 minutes. When the transfer films of Examples 1 to 18 and Comparative Examples were used, a transparent film, a transparent electrode pattern, a second resin layer disposed in direct contact with the transparent electrode pattern, and a second film The laminated body of Examples 1-18 and each comparative example which have continuously the curable resin layer arrange | positioned in contact with this resin layer in this order was obtained. In the region where the transparent electrode pattern does not exist, the second resin layer was disposed in direct contact with the transparent film.
In the case where the transfer film of Example 19 was used, Example 19 having a transparent film, a transparent electrode pattern, and a curable resin layer disposed in direct contact with the transparent electrode pattern in this order on the transparent film substrate. A laminate was obtained.
From the above steps, it was confirmed that the transfer film of the present invention has photolithographic properties.

<Evaluation of laminate>
(Concealment of transparent electrode pattern)
The laminated body of each Example and Comparative Example and the black PET material are placed so that the black PET material and the curable resin layer are adjacent to each other through a transparent adhesive tape (trade name, OCA tape 8171CL, manufactured by 3M Corporation). A substrate for evaluation was produced in which the entire substrate was shielded from light.
In a dark room, using a fluorescent lamp (light source) and the produced evaluation substrate, light is incident from the transparent film substrate surface side of the evaluation substrate, and reflected light from the surface of the transparent film substrate on which light is incident is reflected. The sample was visually observed from an oblique direction.
Based on the following evaluation criteria, the concealability of the transparent electrode pattern was evaluated.
-Evaluation criteria-
A: A transparent electrode pattern is not visually recognized.
B: A transparent electrode pattern is visually recognized.
The obtained results are shown in Table 2 below. The concealability of the transparent electrode pattern is preferably A.

From the obtained results, it was found that the transfer film of the present invention has photolithographic properties, generates less bubbles, and has few transfer defects.
On the other hand, the transfer film of Comparative Example 1 in which the oxygen permeability of the protective film was lower than the lower limit specified in the present invention had many bubbles. The transfer film of Comparative Example 2 in which the surface roughness of the protective film was lower than the lower limit specified in the present invention had many transfer defects. In the transfer film of Comparative Example 3 in which the surface roughness of the protective film exceeded the upper limit defined in the present invention, many bubbles were generated.

N _1, n _2, T ₁ and T ₂ in the laminate of the Examples and Comparative Examples were respectively n _1, n _2, T ₁ and T ₂ coincide in the transfer films of Examples and Comparative Examples.
For n ₁ , n ₂ , T ₁ and T ₂ in the obtained laminate, the same method as the calculation of n ₁ , n ₂ , T ₁ and T ₂ in the transfer films of each Example and Comparative Example is used for each layer. It repeated and calculated | required using the reflective spectral film thickness meter FE-3000 (made by Otsuka Electronics Co., Ltd.). The outline is shown below.
(1) About the laminated body of an Example and a comparative example, the sample which laminated | stacked the transparent film substrate, transparent film, and transparent electrode pattern which were used in each Example and comparative example in order, a transparent film substrate, a transparent film, a transparent electrode pattern, and About the sample etc. which laminated | stacked the 2nd resin layer in order, the expected value of the refractive index of each layer and the thickness of each layer was measured previously.
(2) In the laminated body, a transparent film substrate / transparent film / transparent electrode pattern / second resin layer / curable resin layer having a five-layer configuration is cut into a length and width of 5 cm × 5 cm and transparent. The sample piece which made the black PET material contact was produced through the adhesive tape (OCA tape 8171CL: product made from 3M Co., Ltd.). The sample piece was subjected to structural analysis using a transmission electron microscope (TEM), and the expected value of the thickness of each layer was determined. About sample piece, using FE-3000 (manufactured by Otsuka Electronics Co., Ltd.), measurement spot: reflection spectrum at 100 measurement points on a straight line in an arbitrary direction at intervals of 0.2 mm at a diameter of 40 μm. evaluated. At this time, in order to consider the interface between the second resin layer and the transparent electrode pattern and the interface between the curable resin layer and the second resin layer, the second resin layer, the transparent film substrate, the transparent film, and the transparent electrode pattern Transparent film substrate / transparent film / transparent electrode pattern with the expected value of the average value of the refractive index and the thickness of the curable resin layer and the expected value of the average value of the thickness of the second resin layer substituted in the calculation formula curable in / the second resin layer / cured resin layer 5 layer component measurement point of the refractive index n ₂ and 100 points of refractive index n ₁ and the second resin layer of the cured resin layer from the reflection spectra of the The thicknesses of the resin layer and the second resin layer were obtained by fitting by simulation calculation. Further, the average value, maximum value, minimum value, and standard deviation of the thicknesses of the curable resin layer and the second resin layer were calculated, and n ₁ , n ₂ , T _1, and T ₂ were calculated. In the present specification, an arbitrary direction is defined as a direction parallel to one side of the sample piece, and 100 measurement points (that is, 2 cm length) are equally set to a range of 1 cm from the center of one side of the sample piece.

Furthermore, when the content of the metal oxide particles in the curable resin layer and the second resin layer of the laminates of each Example and Comparative Example was measured by the following method, it was the value described in the above table.
After cutting the cross section of the laminate, the cross section is observed with a TEM (transmission electron microscope). The proportion of the area occupied by the metal oxide particles in the film cross-sectional area of the curable resin layer or the second resin layer of the laminate is measured at any three locations in the layer, and the average value is the volume fraction (VR). Is considered.
The volume fraction (VR) and the weight fraction (WR) are converted by the following formula to obtain the weight fraction (WR) of the metal oxide particles in the curable resin layer or the second resin layer of the laminate. Is calculated.
WR = D * VR / (1.1 * (1-VR) + D * VR)
D: Specific gravity of metal oxide particles The metal oxide particles can be calculated as D = 4.0 when titanium oxide is used, and D = 6.0 when zirconium oxide is used.
In addition, the content of the metal oxide particles in the curable resin layer or the second resin layer of the laminates of the examples and comparative examples can also be calculated from the composition of the curable resin layer or the second resin layer. .

  The transfer film of the present invention can be preferably used as a material for a touch panel (particularly a capacitive input device) or an image display device provided with a touch panel (particularly a capacitive input device) as a constituent element. . Since the transfer film of the present invention has photolithographic properties, when it is desired to form a desired pattern using the transfer film of the present invention, the pattern can be formed by photolithography, which has better productivity than the cutting method.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Mask layer 3 1st transparent electrode pattern 3a Pad part 3b Connection part 4 Transparent electrode pattern (2nd transparent electrode pattern)
5 Insulating Layer 6 Another Conductive Element 7 Curable Resin Layer 8 Opening 10 Capacitive Input Device 11 Transparent Film 12 Second Resin Layer 13 Laminate 21 Transparent Electrode Pattern, Second Resin Layer, and Curable Resin Layer 22 layered in this order Non-pattern region α Taper angle 26 Temporary support 29 Protective film 30 Transfer film 31 Leading wire terminal portion 33 Curing resin layer and second resin layer hardening portion 34 Leading wire end Opening corresponding to the part (uncured part of the curable resin layer and the second resin layer)
C First direction D Second direction

Claims (15)

A temporary support;
A curable resin layer that is curable; and
A protective film;
In this order,
The oxygen permeability coefficient of the protective film is 100 cm ³ · 25 μm / m ² · 24 hours · atm or more,
The transfer film whose surface roughness Ra of the surface at the side of the said curable resin layer of the said protective film is 5-60 nm. The transfer film according to claim 1, wherein the protective film has an oxygen permeability coefficient of 5000 cm ³ · 25 μm / m ² · 24 hours · atm or less.   The transfer film according to claim 1, wherein the protective film has a thickness of 10 to 75 μm.   The transfer film according to claim 1, wherein the protective film contains polyethylene terephthalate or polypropylene. Having a second resin layer between the protective film and the curable resin layer;
The second resin layer according to any one of claims 1 to 4, wherein the second resin layer contains particles having a refractive index of 1.50 or more in an amount of 60 to 90 mass% with respect to the total solid content of the second resin layer. Transfer film. The transfer film according to claim 5, which satisfies the following formula 1:
Formula 1: n ₁ <n ₂
n ₁ represents the refractive index of the curable resin layer, and n ₂ represents the refractive index of the second resin layer.   The transfer film according to claim 5, wherein the second resin layer is curable.   The transfer film according to any one of claims 5 to 7, wherein the particles having a refractive index of 1.50 or more are zirconium oxide particles or titanium oxide particles.   The transfer film according to claim 5, wherein the curable resin layer and the second resin layer are in direct contact with each other.   The transfer film according to claim 5, wherein the curable resin layer and the second resin layer are alkali-soluble. The curable resin layer contains a polymerizable compound and a binder polymer,
The transfer film according to any one of claims 1 to 10, wherein the binder polymer is an alkali-soluble resin.   The transfer film according to claim 1, which has a roll shape.   The electrode protective film of the electrostatic capacitance type input device by which the said protective film was removed from the transfer film as described in any one of Claims 1-12. A substrate including an electrode of a capacitive input device;
A laminate comprising the electrode protective film of the capacitive input device according to claim 13.   A capacitance-type input device comprising the electrode protective film of the capacitance-type input device according to claim 13 or the laminate according to claim 14.

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