JPWO2016159043A1 - Transfer film, laminate, capacitance input device and image display device - Google Patents

Abstract

It has a temporary support, a transparent resin layer, and a high refractive index transparent resin layer disposed adjacently so as to be in direct contact with the transparent resin layer in this order, and the refractive index of the high refractive index transparent resin layer is a transparent resin. A transfer film having a refractive index higher than the refractive index of the two layers and having a swelling ratio of the transparent resin layer and the high refractive index transparent resin layer of 6.0% or less is a concealment of the transparent electrode pattern when laminated on the transparent electrode pattern. A laminate having excellent pattern end durability when a pattern is formed after transfer can be formed; however, the swelling rate of the two layers comprising a transparent resin layer and a high refractive index transparent resin layer is high. Before and after immersing the refractive index transparent resin layer and the transparent resin layer on the copper foil of the copper foil laminated film from the transfer film and exposing at a dose of 80 mJ / cm 2 for 55 seconds in a 1% by mass sodium carbonate aqueous solution at 33 ° C. Change in film thickness Is a value representing a ratio to the film thickness before the immersion of the amount in percentage; laminate; capacitive input device; image display device.

Description

  The present invention relates to a transfer film, a laminate, a capacitance type input device, and an image display 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.

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, when the electrode pattern extends in a direction crossing each other and a finger or the like comes into contact with the input surface of the capacitance-type input device, the capacitance between the electrodes changes. There is a type that detects this and detects the input position.
A transparent resin layer is provided by laminating the electrode pattern and the lead wiring for the purpose of protecting the electrode pattern of the capacitive input device and the lead wiring (for example, metal wiring such as copper wire) collected in the frame. It has been.

  Patent Document 1 includes a temporary support, a transparent resin layer, and a second curable transparent resin layer disposed adjacent to the transparent resin layer in this order, and a second curable transparent resin layer. Has a higher refractive index than the transparent resin layer, and the second curable transparent resin layer has a refractive index of 1.6 or more. According to Patent Document 1, it is described that a transparent laminate having no problem of visually recognizing a transparent electrode pattern can be formed with this configuration.

JP 2014-108541 A

  On the other hand, the transparent resin layer is required to be patterned, for example, so as not to cover the terminal portion of the routing wiring in order to connect the terminal portion of the routing wiring of the capacitive input device to other wiring. Yes. As a method for forming the pattern of the transparent resin layer, it is required to use a photolithography method from the viewpoint of productivity. However, when a transparent resin layer that can be patterned by the photolithography method is used, the wiring wiring arranged in the transparent electrode pattern and the frame portion of the capacitive input device for reducing the reflectance with reference to Patent Document 1 When the pattern of the transparent resin layer and the high refractive index transparent resin layer is provided on the surface, it is said that deterioration from the pattern end occurs after repeated use by touching the input surface of the capacitive input device with a finger. It was found that a new problem arises.

  The problem to be solved by the present invention is that the concealability of a transparent electrode pattern when laminated on a transparent electrode pattern is good, and a laminate having excellent pattern end durability when a pattern is formed after transfer can be formed. It is to provide a transfer film. The problems to be solved by the present invention include a laminate produced using this transfer film, a capacitive input device produced using this transfer film, or comprising this laminate, and this static An object of the present invention is to provide an image display device including a capacitive input device as a constituent element.

In order to solve the above-mentioned problems, the present inventors have intensively studied and analyzed. As a result, the inventors of the present invention between the undercut entering the pattern ends of the transparent resin layer and the high refractive index transparent resin layer patterned after being laminated on the transparent electrode pattern, and the deterioration of the pattern end durability Correlation was found. In particular, since the second curable transparent resin layer having the structure described in Patent Document 1 contains a large amount of inorganic particles, it has low adhesion to the substrate and the lead-out wiring, and undercut is likely to occur during pattern development processing. It was found that when the second curable transparent resin layer was undercut at the pattern edge, it was invaded by harmful substances from the pattern edge, and the internal wiring of the capacitive input device began to deteriorate. In the field of capacitive input devices, when a person tries to touch the input surface of the capacitive input device with his / her finger, the capacitive input device is often gripped, and harmful substances such as sweat Is often attached to the pattern edge existing in the frame portion of the capacitance-type input device. Therefore, the pattern edge durability of the transparent resin layer and the high refractive index transparent resin layer is a practically important performance.
Therefore, as a result of further studies, the present inventors have found that the swelling and shrinkage of the transparent resin layer and the high refractive index transparent resin layer greatly affect the occurrence of undercuts at the pattern edges of the transparent resin layer and the high refractive index transparent resin layer. It has been found that the occurrence of undercut at the pattern edge can be suppressed by reducing the swelling and shrinkage of the transparent resin layer and the high refractive index transparent resin layer. That is, the concealability of the transparent electrode pattern when the transfer film is laminated on the transparent electrode pattern is good by setting the swelling ratio of the two layers comprising the transparent resin layer and the high refractive index transparent resin layer within a specific range. And it came to discover that the transfer film excellent in pattern edge durability at the time of forming a pattern after transfer can be provided.
The present invention, which is a specific means for solving the above problems, is as follows.

[1] a temporary support;
A transparent resin layer;
It has a high refractive index transparent resin layer arranged adjacent to be in direct contact with the transparent resin layer in this order,
The refractive index of the high refractive index transparent resin layer is higher than the refractive index of the transparent resin layer,
A transfer film in which the swelling ratio of the two layers comprising the transparent resin layer and the high refractive index transparent resin layer is 6.0% or less;
However, the swelling rate of the two layers comprising the transparent resin layer and the high refractive index transparent resin layer is determined by transferring the high refractive index transparent resin layer and the transparent resin layer from the transfer film onto the copper foil of the PET film on which the copper foil is laminated. After exposure at an exposure amount of 80 mJ / cm ² , the ratio of the change in film thickness before and after immersing in a 1% by mass sodium carbonate aqueous solution at 33 ° C. for 55 seconds is a value expressed as a percentage. .
[2] In the transfer film according to [1], the transparent resin layer preferably has 2.50 × 10 ⁻³ pieces / g or more of a crosslinkable group.
[3] In the transfer film according to [1] or [2], the transparent resin layer preferably contains a photopolymerization initiator having a solid content ratio of 0.3% by mass or more.
[4] The transfer film according to any one of [1] to [3] preferably has an I / O value, which is a measure of hydrophilicity / hydrophobicity of the transparent resin layer, of 1.10 or less.
[5] The transfer film according to any one of [1] to [4] preferably has a C / H ratio of 0.68 or more, which is a ratio of carbon to hydrogen in the mass of the transparent resin layer. .
[6] In the transfer film according to any one of [1] to [5], the acid value of the transparent resin layer is preferably from 35 to 80 mgKOH / g.
[7] In the transfer film according to any one of [1] to [6], the transparent resin layer preferably contains a binder polymer having an acid value of 55 to 150 mgKOH / g.
[8] In the transfer film according to any one of [1] to [7], the transparent resin layer preferably has a thickness of 4 to 15 μm.
[9] In the transfer film according to any one of [1] to [8], the high refractive index transparent resin layer preferably contains a metal oxidation inhibitor.
[10] In the transfer film according to [9], the metal oxidation inhibitor preferably has an imidazole ring, a triazole ring, or a condensed ring of these with another aromatic ring in the molecule.
[11] In the transfer film according to any one of [1] to [10], the refractive index of the high refractive index transparent resin layer is preferably 1.60 or more.
[12] In the transfer film according to any one of [1] to [11], the high refractive index transparent resin layer preferably contains metal oxide particles having a solid content ratio of 40% by mass or more.
[13] In the transfer film according to any one of [1] to [12], the thickness of the high refractive index transparent resin layer is preferably 0.20 μm or less.
[14] In the transfer film according to any one of [1] to [13], it is preferable that the swelling ratio of the two layers including the transparent resin layer and the high refractive index transparent resin layer is 1.5% or more. .
[15] The transfer film according to any one of [1] to [14] is preferably a dry resist film.
[16] an electrode pattern;
A high refractive index transparent resin layer disposed adjacent to the electrode pattern;
A transparent resin layer disposed adjacent to the high refractive index transparent resin layer,
The refractive index of the high refractive index transparent resin layer is higher than the refractive index of the transparent resin layer,
High refractive index transparent resin layer and transparent resin layer are patterned,
A laminate in which the undercut depth of the pattern end of the two layers comprising the high refractive index transparent resin layer and the transparent resin layer is 5.0 μm or less;
However, the undercut depth of the pattern end of the two layers composed of the high refractive index transparent resin layer and the transparent resin layer is an upper portion of more than half of the total film thickness of the two layers composed of the high refractive index transparent resin layer and the transparent resin layer. This is the value of the component in the direction parallel to the interface between the high refractive index transparent resin layer and the electrode pattern, which is the distance between the pattern extreme end point and the contact point between the pattern end of the high refractive index transparent resin layer and the electrode pattern.
[17] The laminate according to [16] preferably has a C / H ratio of 0.68 or more, which is a ratio of carbon and hydrogen in the mass of the transparent resin layer.
[18] In the laminate according to [16] or [17], the high refractive index transparent resin layer preferably contains a metal oxidation inhibitor.
[19] In the laminate according to [18], the metal oxidation inhibitor preferably has an imidazole ring, a triazole ring, or a condensed ring of these and another aromatic ring in the molecule.
[20] In the laminate according to any one of [16] to [19], the high refractive index transparent resin layer preferably contains metal oxide particles having a solid content ratio of 40% by mass or more.
[21] The laminate according to any one of [16] to [20] is a high refractive index transparent resin for a transfer film according to any one of [1] to [15] on an electrode pattern. It is preferable to have a layer and a transparent resin layer in this order.
[22] In the laminate according to any one of [16] to [21], the electrode pattern is preferably an electrode pattern positioned on the transparent film substrate.
[23] The laminate according to [22] preferably has an electrode pattern, a high refractive index transparent resin layer, and a transparent resin layer on both surfaces of the transparent film substrate, respectively.
[24] A capacitance-type input device manufactured using the transfer film according to any one of [1] to [15].
[25] A capacitance-type input device including the laminate according to any one of [16] to [23].
[26] An image display device comprising the capacitive input device according to [24] or [25] as a constituent element.

  According to the present invention, there is provided a transfer film capable of forming a laminate that has good concealability of a transparent electrode pattern when laminated on a transparent electrode pattern and excellent pattern end durability when a pattern is formed after transfer. can do.

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 board | substrate 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 board | substrate with which the opening part was formed. It is a top view which shows an example of the board | substrate with which the mask layer was formed. It is a top view which shows an example of the board | substrate with which the 1st transparent electrode pattern was formed. It is a top view which shows an example of the board | substrate with which the 1st and 2nd transparent electrode pattern was formed. It is a top view which shows an example of the board | substrate with which the electroconductive element different from the 1st and 2nd transparent electrode pattern was formed. It is the cross-sectional schematic which shows another example of the structure of the capacitance-type input device of this invention, and is a cross-sectional schematic which shows the preferable structure of the capacitance-type input device which is a front plate integrated sensor using a film sensor. is there. 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 transparent resin layer. Schematic showing an example of a state before a transfer film of the present invention having a transparent resin layer and a high refractive index transparent resin layer is laminated on a transparent electrode pattern of a capacitive input device and cured by exposure or the like FIG. It is the schematic which shows an example of the desired pattern by which the transparent resin layer and the high refractive index transparent resin layer were hardened. 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 the schematic which shows an example of the cross section of the laminated body of this invention, FIG.17 (A) represents the aspect of undercut depth U> 0, FIG.17 (B) shows the aspect of undercut depth U = 0. FIG. 17C shows a mode in which the undercut depth U <0.

  Hereinafter, the transfer film, laminate, capacitance-type input device and image display device of the present invention will be described. The description of the constituent requirements described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is not limited to the 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 has a temporary support, a transparent resin layer, and a high refractive index transparent resin layer disposed adjacently so as to be in direct contact with the transparent resin layer. In this transfer film, the refractive index of the layer is higher than the refractive index of the transparent resin layer, and the swelling ratio of the two layers comprising the transparent resin layer and the high refractive index transparent resin layer is 6.0% or less.
However, the swelling rate of the two layers comprising the transparent resin layer and the high refractive index transparent resin layer is determined by transferring the high refractive index transparent resin layer and the transparent resin layer from the transfer film onto the copper foil of the PET film on which the copper foil is laminated. After exposure at an exposure amount of 80 mJ / cm ² , the ratio of the change in film thickness before and after immersing in a 1% by mass sodium carbonate aqueous solution at 33 ° C. for 55 seconds is a value expressed as a percentage. .
With this configuration, the transfer film of the present invention forms a laminate that has excellent concealability of the transparent electrode pattern when laminated on the transparent electrode pattern, and excellent pattern end durability when the pattern is formed after transfer. it can.
Without being bound by any theory, the configuration of the present invention does not cause much shrinkage at the pattern ends of the transparent resin layer and the high refractive index transparent resin layer after irradiation with light (ultraviolet rays) and heating, and is harmful to salt water and the like. It is presumed that the undercut can be suppressed to a depth that can sufficiently block the substance, and the pattern end durability can be improved when a pattern is formed after transfer.
In the present specification, transparent means that the average transmittance of visible light having a wavelength of 400 nm to 700 nm is 80% or more. Therefore, the transparent layer refers to a layer having an average transmittance of visible light having a wavelength of 400 nm to 700 nm of 80% or more. The average transmittance of visible light having a wavelength of 400 nm to 700 nm of the transparent layer is preferably 90% or more.
The average transmittance of visible light having a wavelength of 400 nm to 700 nm of the transfer film of the present invention or the transparent layer of the transfer film is measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

  In a preferred embodiment of the present invention, the durability of the central portion of the transparent resin layer and the high refractive index transparent resin layer can be increased, and more preferably, the wet heat durability after the salt water is applied to the central portion can be increased. The wet heat durability after the application of salt water in the center is an important performance in practical use. Sweat that adheres when a human touches the input surface of the capacitive input device with a finger may penetrate into the capacitive input device. If the capacitive input device is subsequently used or charged in a humid and hot environment, the inside of the capacitive input device becomes a high temperature and high humidity environment. Therefore, the transparent resin layer and the high refractive index transparent resin It is preferable that the wet heat durability after the salt water provision of the center part of a layer is high.

Hereinafter, preferred embodiments of the transfer film of the present invention will be described.
The transfer film of the present invention is preferably for a transparent insulating layer or a transparent protective layer of a capacitive input device. In the transfer film of the present invention, the transparent resin layer is preferably in an uncured state. In that case, a laminated pattern of a protective film for an electrode of a capacitive input device is formed on the transparent electrode pattern by a photolithography method. And a transfer film for forming a laminated pattern of a refractive index adjusting layer and an overcoat layer (transparent protective layer).

<Swelling rate>
In the transfer film of the present invention, the swelling ratio of the two layers comprising the transparent resin layer and the high refractive index transparent resin layer is 6.0% or less, and preferably 4.5% or less from the viewpoint of pattern end durability. . On the other hand, in the transfer film of the present invention, the swelling ratio of the two layers comprising the transparent resin layer and the high refractive index transparent resin layer is preferably 1.5% or more from the viewpoint of developability. When the swelling ratio is 1.5% or more, the penetration of the developer at the time of development becomes sufficient, and dissolution of the unexposed portion proceeds, which is preferable from the viewpoint of developability. In addition, in the case of a transfer film obtained by curing a transparent resin layer on a temporary support and then laminating a high refractive index transparent resin layer, it cannot be patterned by a photolithography method, and developability by the photolithography method is poor.
The swelling ratio of the two layers consisting of the transparent resin layer and the high refractive index transparent resin layer is as follows. The value which expressed the ratio with respect to the film thickness before immersing of the variation | change_quantity of the film thickness before and behind being immersed in 1 mass% sodium carbonate aqueous solution of 33 degreeC after transcribe | transferring and exposing with the exposure amount of 80 mJ / cm < ² >. It is.
The “swelling ratio” referred to in the present invention is a value expressed as a percentage of the film thickness before immersion of the amount of change in film thickness before and after the target layer is immersed in a specific liquid. The swelling rate is positive when the layer swells and takes a negative value when the layer shrinks. The film thickness of the layer can be measured with, for example, a stylus film thickness meter.

<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 the temporary support satisfying this property 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.

<Configuration and characteristics of transparent resin layer>
The transparent resin layer is arranged adjacent to be in direct contact with the high refractive index transparent resin layer. On the other hand, the transparent resin layer may be disposed adjacent to the temporary support so as to be in direct contact with each other, or may be laminated via the temporary support with another layer, but is adjacent to the temporary support so as to be in direct contact with the temporary support. Are preferably arranged.
The transparent resin layer may be thermosetting, photocurable, thermosetting and photocurable. Among them, the transparent resin layer and the high refractive index transparent resin layer described later are a thermosetting transparent resin layer and a photocurable transparent resin layer, and are easily photocured after transfer and can be formed into a film. It is preferable from the viewpoint of thermosetting and imparting wet heat durability after application of salt water.

(Acid value of transparent resin layer)
In the transfer film of the present invention, the acid value of the transparent resin layer is preferably 35 to 80 mgKOH / g, more preferably 35 to 70 mgKOH / g, and particularly preferably 40 to 60 mgKOH / g. The acid value of the transparent resin layer is preferably 35 mgKOH / g or more from the viewpoint that the undercut depth does not become too small and developability can be improved.
The “acid value” as used in the present invention refers to the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids, etc. contained in 1 g of the target sample.
The acid value of the transparent resin layer can be determined according to a method shown in JIS (Japan Industrial Standards) K 0070: 1992.

(Thickness)
The thickness of the transparent resin layer can be set to 1 to 20 μm, for example. In the transfer film of the present invention, the thickness of the transparent resin layer is preferably 4 to 15 μm, and more preferably 5 to 12 μm. When the thickness of the transparent resin layer is 4 μm or more, the wet heat durability of the transparent resin layer after transfer (especially after exposure, development, and heating) after applying salt water can be improved, and the durability of the center is improved. can do. The developability can be improved when the thickness of the transparent resin layer is 15 μm or less. The above-mentioned transparent resin layer is preferably used in the image display portion of the capacitance-type input device. In that case, it is important to increase the transparency and the transmittance, and the thickness of the transparent resin layer is sufficiently thin. Therefore, a decrease in transmittance due to absorption of the transparent resin layer is less likely to occur, and yellow coloration is also less likely to occur because short waves are less likely to be absorbed.
The thickness of the transparent resin layer is determined by the method described in Examples below using a reflection spectral film thickness meter.

(Amount of crosslinkable group)
In the transfer film of the present invention, the transparent resin layer preferably has 2.50 × 10 ⁻³ pieces / g or more of a crosslinkable group from the viewpoint that the swelling ratio can be reduced and the pattern end durability can be improved. It is more preferable to have a crosslinkable group of × 10 ⁻³ / g or more and 1.00 × 10 ⁻² / g or less.
The amount of the crosslinkable group can be calculated by dissolving the transparent resin layer sample in a suitable solvent, and quantifying the various crosslinkable groups by analysis such as NMR (Nuclear Magnetic Resonance) or FT-IR (Fourier Transform Infrared Spectrometer). Moreover, you may obtain | require by calculation based on the material composition of a transparent resin layer.
The amount of the crosslinkable group can be adjusted by changing the type of the photopolymerizable compound or binder polymer.

(I / O value)
The transfer film of the present invention has an I / O value of 1.10 or less, which is a measure of the hydrophilicity / hydrophobicity of the transparent resin layer, from the viewpoint that the swelling rate can be reduced, the pattern end durability can be improved, and the central portion durability can also be improved. It is preferable that it is 0.80-0.99.
The “I / O value” referred to in the present invention means the degree of hydrophilicity / hydrophobicity exhibited by a compound by integrating the organic degree and inorganic degree determined for each functional group according to the number of functional groups and taking the ratio. It is a parameter that serves as an index representing the scale. “I” represents inorganicity, “O” represents organicity, and the larger the I / O value, the higher the inorganicity. I / O values are described in detail in “Organic Conceptual Diagram” (by Yoshio Koda, Sankyo Publishing, 1984).
The I / O value can be adjusted by changing the type of the photopolymerizable compound or binder polymer.

(C / H ratio)
In the transfer film of the present invention, the C / H ratio, which is the ratio of carbon to hydrogen in the mass of the transparent resin layer, can be reduced from the viewpoint that the swelling ratio can be reduced, the pattern end durability can be improved, and the central portion durability can also be improved. .68 or more is preferable, and 0.69 to 0.75 is more preferable.
The “C / H ratio” in the present invention refers to the ratio of the mass of carbon atoms and hydrogen atoms to the total mass of the target layer. Various elemental analysis methods are used as a method for measuring the ratio of carbon atoms and hydrogen atoms. As a typical means, for example, a method of burning a predetermined amount of sample and measuring the weight of generated water and carbon dioxide can be mentioned. The higher the C / H ratio, the lower the I / O value.

(Refractive index)
In the transfer film of the present invention, the refractive index of the high refractive index transparent resin layer is higher than the refractive index of the transparent resin layer.
The refractive index of the transparent resin layer is preferably 1.50 to 1.53, more preferably 1.50 to 1.52, and particularly preferably 1.51 to 1.52. . The refractive index is measured by comparing the spectral reflectance spectrum calculated assuming the thickness and refractive index of the target layer with the measured spectral reflectance spectrum, and minimizing the difference between the two by the curve fitting method. Find the thickness and refractive index. In the present invention, a spectral reflection film thickness meter FE-3000 manufactured by Otsuka Electronics Co., Ltd. is used as an apparatus that can perform both the measurement and the calculation.

(composition)
The transfer film of the present invention may be a negative type material or a positive type material.
The transfer film of the present invention is preferably a negative material.

  The method for controlling the refractive index of the transparent resin layer is not particularly limited, but a transparent resin layer having a desired refractive index is used alone, or a transparent 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.

  Furthermore, you may use an additive for the above-mentioned transparent resin layer. 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.

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

-Binder polymer-
The transfer film of the present invention preferably contains a binder polymer in the transparent resin layer. Although there is no restriction | limiting in particular as a binder polymer used for a transparent resin layer, It is preferable that it is resin which has an acid group. The resin having an acid group that can be used 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 also includes a resin in a salt state in which the acid group is neutralized.
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 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.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. As the acid group, a carboxyl group is preferable.
The binder polymer used for the transparent resin layer is preferably an acrylic resin, and more preferably a carboxyl group-containing acrylic resin.
In addition, you may contain other binder polymers other than resin which has an acid group. As the other binder polymer contained in the transparent resin layer, any polymer component can be used without particular limitation, but from the viewpoint of use as a protective film for a transparent electrode of a capacitive input device, surface hardness, heat resistance Highly preferred are alkali-soluble resins, and among the alkali-soluble resins, there can be mentioned known photosensitive siloxane resin materials.
In the transfer film of the present invention, the binder polymer contained in the transparent resin layer is preferably an acrylic resin. Both the binder polymer contained in the transparent resin layer and the resin or binder polymer having an acid group contained in the high refractive index transparent resin layer described later contain an acrylic resin, so that the transparent resin layer and the high refractive index transparent resin layer It is preferable from the viewpoint of improving interlayer adhesion before and after transfer. The preferable range of the above-mentioned binder polymer of the transparent resin layer will be specifically described.

The binder polymer (also referred to as “binder” or “polymer”) used in the transparent resin layer 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. Polymers described in paragraph 0025 of 2011-95716 and polymers described in paragraphs 0033 to 0052 of JP 2010-237589 can be used.
In the transfer film of the present invention, the transparent resin layer preferably contains a binder polymer having an acid value of 55 to 150 mgKOH / g, the acid value of the binder polymer is more preferably 60 to 150 mgKOH / g, and 70 to 120 mgKOH / g. Particularly preferred is g.
The “acid value” as used in the present invention refers to the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids, etc. contained in 1 g of the target sample. Examples of the method for measuring the acid value of the binder polymer include the same method as the method for measuring the acid value of the transparent resin layer. In addition, when the acid value of the binder polymer used for the transparent resin layer cannot be directly measured, the acid value of the binder polymer may be a theoretical acid value calculated by a calculation method described in the following literature or the like. . JP 2004-149806 A [0063], JP 2012-211228 A [0070].

The transparent 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. As means for strengthening the bonding force between polymer chains, there are a method using an interaction caused 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 (styrene sulfonic acid group and the like), and the like. The binder polymer which is a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more 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 still more preferably 20 to 35% by mass with respect to 100% by mass of the polymer. is there. In the binder polymer which is a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more, the preferable range of the copolymerization ratio of the monomer having a carboxyl group is 5 to 50% by mass, more preferably 5 to 50% by mass with respect to 100% by mass of the polymer. It is 40 mass%, More preferably, it exists in the range of 20-35 mass%.
On the other hand, as means for generating a covalent bond, an epoxy compound, a blocked isocyanate, an isocyanate, at least one of a hydroxyl group, a carboxyl group, a primary or secondary amino group, an acetoacetyl group and a sulfonic acid group, Examples include a method of reacting at least one of a vinyl sulfone compound, an aldehyde compound, a methylol compound, a carboxylic acid anhydride, and the like.
The weight average molecular weight of the polymer is preferably 10,000 or more, more preferably 20,000 to 100,000.

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 alkyl acrylate copolymer ammonium (trade name: Jurimer AT-210, manufactured by Toagosei Co., Ltd.) and an alkyl acrylate copolymer ammonium (trade name: Jurimer ET-410, Toagosei Co., Ltd.). Co., Ltd.), alkyl acrylate copolymer ammonium (trade name: Jurimer AT-510, manufactured by Toagosei Co., Ltd.), and polyacrylic acid (product name: Jurimer AC-10L, manufactured by Toagosei Co., Ltd.) with neutralized ammonia. And an emulsified product.

-Photopolymerizable compound-
In the transfer film of the present invention, the transparent resin layer preferably contains a photopolymerizable compound having an ethylenically unsaturated group. The photopolymerizable compound having an ethylenically unsaturated group only needs to have at least one ethylenically unsaturated group as a photopolymerizable group, and has an epoxy group in addition to the ethylenically unsaturated group. Also good. More preferably, the photopolymerizable compound of the transparent resin layer includes a compound having a (meth) acryloyl group.
The photopolymerizable compound used for the transfer film may be used alone or in combination of two or more, but it is possible to use a combination of two or more transparent resin layers after transfer. From the viewpoint of improving the wet heat durability after the application of salt water after exposure. The photopolymerizable compound used for the transfer film of the present invention is a combination of a tri- or higher functional photopolymerizable compound and a bifunctional photopolymerizable compound. Brine after exposure of the transparent resin layer after transfer From the viewpoint of improving wet heat durability after application, it is preferable. The bifunctional photopolymerizable compound is preferably used in the range of 10 to 90% by mass, more preferably in the range of 20 to 85% by mass with respect to all the photopolymerizable compounds, and 30 to 80% by mass. It is particularly preferable to use in the range of%. The trifunctional or higher functional photopolymerizable compound is preferably used in the range of 10 to 90% by mass, more preferably in the range of 15 to 80% by mass with respect to all the photopolymerizable compounds. It is particularly preferable to use in the range of mass%. The transfer film preferably contains at least a compound having two ethylenically unsaturated groups and a compound having at least three ethylenically unsaturated groups as the photopolymerizable compound, and has two (meth) acryloyl groups. More preferably, it comprises at least a compound and a compound having at least three (meth) acryloyl groups.
The transfer film of the present invention is such that at least one of the photopolymerizable compounds having an ethylenically unsaturated group contains a carboxyl group, the photopolymerizability having a carboxyl group of the binder polymer and an ethylenically unsaturated group. It is preferable from the viewpoint of forming a carboxylic acid anhydride with the carboxyl group of the compound and further enhancing the wet heat durability after application of salt water. It does not specifically limit as a photopolymerizable compound which has an ethylenically unsaturated group 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 photopolymerizable compound having an ethylenically unsaturated group containing a carboxyl group is preferably used in the range of 1 to 50% by mass, and used in the range of 1 to 30% by mass with respect to all the photopolymerizable compounds. It is more preferable to use in the range of 5 to 15% by mass.
It is preferable that a urethane (meth) acrylate compound is included as the above-mentioned photopolymerizable compound. The mixing amount of the urethane (meth) acrylate compound is preferably 10% by mass or more, and more preferably 20% by mass or more with respect to all the photopolymerizable compounds. In the urethane (meth) acrylate compound, the number of functional groups of the photopolymerizable group, that is, the number of (meth) acryloyl groups is preferably 3 or more, and more preferably 4 or more.
The photopolymerizable 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 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, dipentaerythritol (tri / tetra / penta / (Hexa) acrylate, pentaerythritol (tri / tetra) acrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, isocyanuric acid acrylate and other (meth) acrylate compounds can be used, but span between (meth) acrylates Longer lengths are preferred. Specifically, skeletons such as the aforementioned dipentaerythritol (tri / tetra / penta / hexa) acrylate, pentaerythritol (tri / tetra) acrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, isocyanuric acid acrylate ( Caprolactone-modified compounds of meth) acrylate compounds (KAYARAD DPCA manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified compounds (KAYARAD RP-produced by Nippon Kayaku Co., Ltd.) 1040, Shin-Nakamura Chemical Co., Ltd. ATM-35E, A-9300, Daicel Ornex EBECRYL 135, 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 photopolymerizable compound used for the transfer film preferably has a molecular weight of 200 to 3000, more preferably 250 to 2600, and particularly preferably 280 to 2200.

-Photopolymerization initiator-
When the above-mentioned transparent resin layer contains the above-mentioned photopolymerizable compound and the above-mentioned photopolymerization initiator, the pattern of the transparent resin layer can be easily formed.
As a photoinitiator used for a transparent resin layer, the photoinitiator of Paragraphs 0031-0042 of Unexamined-Japanese-Patent No. 2011-95716 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- (0-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-hydroxy) Cy-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 photopolymerization initiator (Product name: Lunar 6, manufactured by DKSH Japan Ltd.) Ku can be used.
In the transfer film of the present invention, the transparent resin layer preferably contains a photopolymerization initiator having a solid content ratio of 0.3% by mass or more from the viewpoint of suppressing the expansion rate and improving the pattern end durability. It is more preferable that the transparent resin layer contains a photopolymerization initiator of 0.6% by mass or more in terms of the solid content ratio, and particularly preferably 0.7% by mass or more. The transparent resin layer preferably contains a photopolymerization initiator of 10% by mass or less in terms of the solid content ratio, and more preferably 5% by mass or less from the viewpoint of improving the patterning property of the laminate of the present invention.

-Block isocyanate-
In the transfer film of the present invention, the transparent resin layer preferably has a blocked isocyanate. The blocked isocyanate means “a compound having a structure in which an isocyanate group of an isocyanate is protected (masked) with a blocking agent”.

In the transfer film of the present invention, the dissociation temperature of the blocked isocyanate is preferably 100 ° C to 160 ° C, and particularly preferably 130 to 150 ° C.
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 (formald oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime) and the like. Among these, from the viewpoint of storage stability, oxime compounds and pyrazole compounds are preferable, and oxime compounds are particularly preferable.

In the transfer film of the present invention, it is preferable that the blocked isocyanate has an isocyanurate structure from the viewpoint of film brittleness and substrate adhesion.
Among the blocked isocyanates having an isocyanurate structure, the oxime compound A is preferable from the viewpoint of easily making the dissociation temperature within a preferable range and improving the developability compared to the compound B having no oxime structure.

  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.

  Specific examples of the blocked isocyanate used in the transfer film of the present invention include the following compounds. However, the blocked isocyanate used in the present invention is not limited to the following specific examples.

  Commercially available block isocyanate can also be mentioned as block isocyanate used for the transfer film of this invention. For example, Takenate (registered trademark) B870N (made by Mitsui Chemicals), which is a methyl ethyl ketone oxime blocked form of isophorone diisocyanate, Duranate (registered trademark) MF-K60B, TPA-B80E (Asahi Kasei Chemicals) which is a hexamethylene diisocyanate-based blocked isocyanate compound For example).

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

-Surfactant containing fluorine atoms-
The transparent resin layer preferably contains a surfactant containing fluorine atoms in an amount of 0.01 to 0.5% by mass based on the solid content of the transparent resin layer. When the transparent resin layer contains a surfactant containing fluorine atoms, the conventional effect of the surfactant, “Suppressing surface tension and smoothing the surface of the wet coated film after coating” is obtained. It is done. In addition, if the transparent resin layer contains a surfactant containing fluorine atoms, when the transparent resin layer is applied and dried, a thin layer of surfactant containing fluorine atoms is formed on the surface of the transparent resin layer, It was newly found that when this becomes a protective layer and a high refractive index transparent resin layer is applied, interlayer mixing with the transparent resin layer can be suppressed. By including a surfactant containing 0.01% by mass or more of fluorine atoms relative to the solid content of the transparent resin layer, this effect is remarkably obtained, and a surface activity containing 0.02% by mass or more of fluorine atoms is obtained. By including the agent, this effect can be obtained more remarkably.
More preferably, the transparent resin layer contains a fluorine atom-containing surfactant in an amount of 0.01 to 0.5% by mass, and 0.02 to 0.4% by mass, based on the solid content of the transparent resin layer. Particularly preferred. In order to maintain good adhesion between the high refractive index transparent resin layer and the transparent electrode pattern, it is preferable to contain a surfactant containing fluorine atoms in an amount of 0.5% by mass or less based on the solid content of the transparent resin layer. More preferably, the content is 0.4% by mass or less.
Furthermore, when an acrylic resin is selected as the resin of the transparent resin layer and a surfactant containing a fluorine atom is used in combination, this effect can be obtained more remarkably.
Examples of the surfactant containing a fluorine atom preferably used for the transparent resin layer include the surfactants described in paragraph No. 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362. it can. Moreover, as a surfactant containing a fluorine atom preferably used for the transparent resin layer, a commercially available surfactant containing a fluorine atom can be used. In particular, the following surfactants containing fluorine atoms are preferred.
DIC Corporation Mega Fuck F251, Mega Fuck F253, Mega Fuck F281, Mega Fuck F444, Mega Fuck F477, Mega Fuck F551, Mega Fuck F552, Mega Fuck F553, Mega Fuck F554, Mega Fuck F555, Mega Fuck F556, Megafuck F557, Megafuck F558, Megafuck F559, Megafuck F560, Megafuck F561, Megafuck F562, Megafuck F563, Megafuck F565, Megafuck F568, Megafuck F569, Megafuck F570, Megafuck F571, Megafuck R40, Megafuck R41, Megafuck R43, Megafuck R94, Megafuck RS-55, Megafuck RS56 Megafac RS72-K, Megafac RS75, Megafac RS76-E, Megafac RS76-NS, Megafac RS78, mega fuck RS90, mega fuck F780F.
A compound represented by the following formula (3) (weight average molecular weight 15,000, solid content 30% by mass, methyl ethyl ketone 70%) is also preferable and can be used.
Formula (3)

-Metal oxide particles-
The aforementioned transparent 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 above-mentioned transparent resin layer within the above-mentioned range, metal oxide particles can be included in an arbitrary ratio depending on the type of polymer or photopolymerizable compound used. In the transparent resin layer, the metal oxide particles described above are preferably included in an amount of 0 to 35% by mass, more preferably 0 to 10% by mass with respect to the transparent resin layer. It is particularly preferred.
Since the metal oxide particles have high transparency and light transmittance, a transparent resin layer having a high refractive index and excellent transparency can be obtained.
The refractive index of the metal oxide particles is preferably higher than the refractive index of the transparent resin layer not including the metal oxide particles. That is, the above-described metal oxide particles preferably have a refractive index higher than that of a composition made of a material obtained by removing the particles from the transparent resin layer.

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.

Moreover, the metal oxide particles described above may be used alone or in combination of two or more.
The transparent resin layer preferably does not contain metal oxide particles, but the case where metal oxide particles are included is also included in the present invention. Examples of the metal oxide particles when the transparent resin layer includes metal oxide particles include ZrO ₂ particles, Nb ₂ O ₅ particles, and TiO ₂ particles.

<Configuration of high refractive index transparent resin layer>
The transfer film of the present invention has a high refractive index transparent resin layer disposed adjacent to the transparent resin layer.

  The high refractive index transparent resin layer may be thermosetting, photocurable, thermosetting and photocurable. Among them, the high refractive index transparent resin layer is preferably at least a thermosetting transparent resin layer, from the viewpoint that it can be thermoset after transfer to impart wet heat durability of the film, and the thermosetting transparent resin layer and photocurable The transparent resin layer is more preferable from the viewpoint that it can be easily photocured after transfer to form a film and can be thermoset after film formation to impart wet heat durability of the film.

(Refractive index)
The transfer film of the present invention has a high refractive index transparent resin layer disposed adjacently so as to be in direct contact with the transparent resin layer, and the refractive index of the high refractive index transparent resin layer is higher than the refractive index of the transparent resin layer described above. Is also expensive. The fact that the refractive index of the high refractive index transparent resin layer is higher than the refractive index of the transparent resin layer can also be confirmed by actually measuring the refractive index of each layer. It can also be confirmed based on the fact that a high refractive index substance such as fine particles is contained.
The difference in refractive index between the transparent electrode pattern (preferably Indium Tin Oxide; ITO) and the above-described high refractive index transparent resin layer and the difference in refractive index between the above high refractive index transparent resin layer and the above transparent resin layer are small. As a result, when the high refractive index transparent resin layer and the transparent resin layer are formed on the viewer side of the transparent electrode pattern, the light reflection is reduced and the transparent electrode pattern becomes difficult to see, and the transparent electrode pattern concealing property is improved. Can do.
In the transfer film, the difference between the refractive index of the high refractive index transparent resin layer and the refractive index of the transparent resin layer is preferably 0.03 to 0.30, and more preferably 0.05 to 0.20.
In addition, when the transparent resin layer is curable, even if the high refractive index transparent resin layer is laminated without curing the transparent resin layer after laminating the transparent resin layer, the layer fraction becomes good and the above The transparent electrode pattern concealing property can be improved by this mechanism. Furthermore, in this case, after transferring the refractive index adjusting layer (that is, the transparent resin layer and the high refractive index transparent resin layer) from the transfer film onto the transparent electrode pattern, the refractive index adjusting layer (preferably a transparent resin layer, more preferably transparent). The resin layer and the high refractive index transparent resin layer) can be developed into a desired pattern by photolithography.
In addition, if the layer fraction of the transparent resin layer and the high refractive index transparent resin layer is good, it is easy to sufficiently obtain the effect of adjusting the refractive index obtained by the above mechanism, and the transparent electrode pattern hiding property is sufficiently improved. There is a tendency to improve. Photolithography is preferably performed at least on the transparent resin layer that is closer to the outside than the high refractive index transparent resin layer after transfer. The high refractive index transparent resin layer that becomes a layer closer to the inside than the transparent resin layer after the transfer may not have photolithographic properties. In this invention, it is preferable that a transparent resin layer has sclerosis | hardenability in the state of a transfer film, and it is preferable that the transparent resin layer used as a layer close | similar to the exterior rather than a high refractive index transparent resin layer after transfer has photolithography property.

The refractive index of the high refractive index transparent resin layer of the transfer film of the present invention needs to be adjusted by the refractive index of the transparent electrode pattern.
When the refractive index of the transparent electrode pattern is in the range of 1.8 to 2.0, for example, when formed using an oxide of In and Sn (ITO), the ITO second transparent resin layer 20 The refractive index is preferably 1.60 or more. The upper limit of the refractive index is not particularly limited, but is preferably 2.1 or less, more preferably 1.78 or less, and even more preferably 1.74 or less.
When the refractive index of the transparent electrode pattern exceeds 2.0, for example, when formed using an oxide of In and Zn (IZO), the refractive index of the second transparent resin layer 20 is 1.7. It is preferably at least 1.85.

(Thickness)
In the transfer film of the present invention, the thickness of the high refractive index transparent resin layer is preferably 0.20 μm or less (200 nm or less) from the viewpoint of improving the transparency of the transparent electrode pattern, and more preferably 110 nm or less. The film thickness of the high refractive index transparent resin layer is preferably 20 nm or more. The film thickness of the high refractive index transparent 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.
The thickness of the high refractive index transparent resin layer is determined by the method described in Examples below using a reflection spectral film thickness meter.

(composition)
In the transfer film, the high refractive index transparent resin layer preferably contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator.
The high refractive index transparent resin layer of the transfer film of the present invention may be a negative type material or a positive type material.
When the high refractive index transparent resin layer of the transfer film of the present invention is a negative material, the high refractive index transparent resin layer includes metal oxide particles, a binder polymer (preferably an alkali-soluble resin), a photopolymerizable compound, light It preferably contains a polymerization initiator. Furthermore, an additive etc. are used and it is not restricted to this.

  The method for controlling the refractive index of the high refractive index transparent resin layer is not particularly limited, but a high refractive index transparent resin layer having a desired refractive index is used alone, or particles such as metal particles and metal oxide particles are added. It is possible to use a transparent resin layer having a high refractive index, or a composite of a metal salt and a polymer.

  Furthermore, you may use an additive for the above-mentioned high refractive index transparent resin layer. 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.

  As described above, the case where the transfer film of the present invention is a negative type material has been mainly described. However, the transfer film of the present invention may be a positive type material. When the transfer film of the present invention is a positive material, for example, the material described in JP-A-2005-221726 is used for the high refractive index transparent resin layer, and the present invention is not limited thereto.

-Ammonium salt of monomer having acid group or ammonium salt of resin having acid group-
The high refractive index transparent resin layer preferably 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 of the high refractive index transparent resin layer is preferably an acrylic monomer having an acid group or an ammonium salt of an acrylic resin.

It is preferable to include a step of dissolving a monomer having an acid group or a resin having an acid group in an aqueous ammonia solution to prepare an aqueous resin composition containing a monomer or resin in which at least a part of the acid group is ammonium chloride.
The monomer having an acid group or the resin having an acid group is preferably a resin having an acid group.

--Resin having acid groups--
The resin having an acid group is more preferably a resin having a monovalent acid group (such as a carboxyl group). The binder polymer of the high refractive index transparent resin layer is particularly preferably a binder polymer having a carboxyl group.
A resin that is used for the high refractive index transparent resin layer and has solubility in an aqueous solvent (preferably water or a mixed solvent of a lower alcohol having 1 to 3 carbon atoms and water) is not contrary to the gist of the present invention. There is no restriction | limiting in particular, It can select suitably from well-known things.
The resin having an acid group used for the high refractive index transparent 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.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. As the acid group, a carboxyl group is 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, crotonic acid copolymer described in Japanese Patent Publication Nos. 46-2121 and 56-40824 A polymer, a maleic acid copolymer such as styrene / maleic acid, a partially esterified maleic acid copolymer, etc., an acidic cellulose derivative having a carboxylic acid in the side chain such as carboxyalkyl cellulose and carboxyalkyl starch, and a polymer having a hydroxyl group. Polymerization with addition of acid anhydride, etc. and having a reactive functional group such as (meth) acryloyl group in the side chain It is mentioned as also preferable.
The resin having an acid group used for the high refractive index transparent resin layer is preferably an acrylic resin, and more preferably a carboxyl group-containing acrylic resin.

Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. This polymer can be used by mixing in an arbitrary amount.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 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, etc. Is mentioned.

  As a specific structural unit of the alkali-soluble resin, 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 singly or in combination of two or more. Preferred other 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.

  Among these, the resin having an acid group is preferably an acrylic resin having an acid group. In this specification, acrylic resin includes both methacrylic resin and acrylic resin, and (meth) acrylic similarly includes methacrylic and acrylic.

--Monomer having 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 skeletons with carboxylic acid groups introduced (acid value = 80 to 120 mgKOH / g)), 5 to 6 functional radical polymerizable monomers (di Examples include pentaerythritol penta and hexaacrylate skeleton introduced with a carboxylic acid group (acid value = 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.
Among these, acrylic monomers such as (meth) acrylic acid and derivatives thereof can be used more preferably. In the present specification, the acrylic monomer includes both a methacrylic monomer and an acrylic monomer.

-Other binder polymers-
There is no restriction | limiting in particular as another binder polymer which does not have an acid group used for a high refractive index transparent resin layer, The binder polymer used for a transparent resin layer can be used.

その他の高屈折率透明樹脂層に用いられる光重合性化合物としては、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、及びリン酸基を有するモノマーが使用できる。-Polymerizable compound-
The above-mentioned high refractive index transparent resin layer preferably contains a polymerizable compound such as the above-mentioned photopolymerizable compound or thermopolymerizable compound from the viewpoint of curing and increasing the strength of the film. It is more preferable to include other photopolymerizable compounds other than the aforementioned monomer having an acid group.
As the photopolymerizable compound used for the high refractive index transparent resin layer, the photopolymerizable 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 photopolymerizable 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 total mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate is preferably 0 to 80% by mass. More preferably, it is -60 mass%.
As a photopolymerizable compound used for the high refractive index transparent resin layer, specifically, a mixture of a water-soluble polymerizable compound represented by the following structural formula 1 and pentaerythritol tetraacrylate (NK ester A-TMMT Shin-Nakamura Chemical) Manufactured by Kogyo Co., Ltd., containing about 10% of triacrylate as an impurity), a mixture of pentaerythritol tetraacrylate and triacrylate (NK ester A-TMM3LM-N, Shin-Nakamura Chemical Co., Ltd., 37% triacrylate), pentaerythritol Mixture of tetraacrylate and triacrylate (NK ester A-TMM-3L, Shin-Nakamura Chemical Co., Ltd., triacrylate 55%), mixture of pentaerythritol tetraacrylate and triacrylate (NK ester A-TMM3 Shin-Nakamura Chemical Co., Ltd.) Triac Co., Ltd. (Relate 57%), tetraacrylate of pentaerythritol ethylene oxide adduct (Kayarad RP-1040 manufactured by Nippon Kayaku Co., Ltd.), and the like.
Among these, as a photopolymerizable compound used for the high refractive index transparent resin layer, from the viewpoint of improving reticulation of a transfer film, a water-soluble polymerizable compound represented by the following structural formula 1, pentaerythritol Tetraacrylate mixture (NK ester A-TMMT, Shin-Nakamura Chemical Co., Ltd.), pentaerythritol tetraacrylate and triacrylate mixture (NK ester A-TMM3LM-N, Shin-Nakamura Chemical Co., Ltd., triacrylate 37%) A mixture of pentaerythritol tetraacrylate and triacrylate (NK ester A-TMM-3L, Shin-Nakamura Chemical Co., Ltd., triacrylate 55%) can be preferably used.

As other photopolymerizable compounds used for the high refractive index transparent resin layer, as a polymerizable compound having solubility in water or a mixed solvent of lower alcohol having 1 to 3 carbon atoms and water, a hydroxyl group is used. The monomer which has, the monomer which has ethylene oxide, a polypropylene oxide, and a phosphoric acid group in a molecule | numerator can be used.

-Photopolymerization initiator-
IRGACURE 2959 or the following structural formula 2 is used as a photopolymerization initiator used in the above-described high refractive index transparent resin layer and having solubility in water or a mixed solvent of lower alcohol having 1 to 3 carbon atoms and water. Can be used.

-Metal oxidation inhibitor-
In the transfer film of the present invention, the high refractive index transparent resin layer preferably contains a metal oxidation inhibitor. When the high refractive index transparent resin layer contains a metal oxidation inhibitor, when the high refractive index transparent resin layer is laminated on a substrate (the substrate preferably includes a transparent electrode pattern and a metal wiring portion), It becomes possible to surface-treat the metal wiring portion that is in direct contact with the high refractive index transparent resin layer, and the central portion durability can be improved. It is considered that the protection of the metal wiring portion provided by the surface treatment is effective even after the high refractive index transparent resin layer is removed.
The metal oxidation inhibitor 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 preferred. In the transfer film of the present invention, it is more preferable that the metal oxidation inhibitor has an imidazole ring, a triazole ring, or a condensed ring of these with another aromatic ring in the molecule, and an imidazole ring, or an imidazole ring and another aromatic ring. It is particularly preferable to have a condensed ring of
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.
Moreover, it is preferable that it is 0.1-20 mass% with respect to the total mass of solid content of a high refractive index transparent resin layer, and, as for content of a metal oxidation inhibitor, it is 0.5-10 mass%. More preferably, it is still more preferably 1 to 5% by mass.

-Surfactant containing fluorine atoms-
The high refractive index transparent resin layer described above may contain a surfactant containing fluorine atoms. Examples of the surfactant containing a fluorine atom that can be used in the high refractive index transparent resin layer include surfactants containing a fluorine atom that can be used in the transparent resin layer.

-Metal oxide particles-
The above-mentioned high refractive index transparent resin layer may or may not contain particles (preferably metal oxide particles) for the purpose of adjusting the refractive index and light transmittance. The inclusion of particles is preferable from the viewpoint of controlling the refractive index of the high refractive index transparent resin layer within the above range. The above-described high refractive index transparent resin layer can contain metal oxide particles at an arbitrary ratio depending on the type of polymer or polymerizable compound (preferably photopolymerizable compound) to be used.
The refractive index of the aforementioned metal oxide particles is preferably higher than the refractive index refractive index of the high refractive index transparent resin layer not including the metal oxide particles. That is, the above-described metal oxide particles preferably have a refractive index higher than that of a composition made of a material obtained by removing the particles from the high refractive index transparent resin layer. Specifically, in the transfer film of the present invention, the high refractive index transparent resin layer preferably contains particles having a refractive index of 1.50 or more in light having a wavelength of 400 to 750 nm. It is further preferable to contain 70 or more particles, particularly preferably 1.90 or more particles, and more preferably 2.00 or more particles.
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, such as titanium oxide, titanium composite oxide, zinc oxide, and zirconium oxide. More preferred are metal oxides containing zirconium atoms, indium / tin oxide and antimony / tin oxide, more preferred are titanium oxide, titanium composite oxide and zirconium oxide, and particularly preferred are titanium oxide and zirconium oxide. Titanium oxide is particularly preferably a rutile type having a high refractive index. The metal oxide containing a zirconium atom is preferably a composite of zirconium oxide and tin oxide. Examples of the tin oxide and the composite of zirconium oxide and tin oxide are described in JP-A-2005-15756 [0027] to [0078] and JP-A-2005-15324 [0026] to [0073]. The contents of these publications are incorporated herein. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.
Here, that the refractive index in light having a wavelength of 400 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. Moreover, an average refractive index is an average value of the refractive index with respect to the light of each wavelength of the said range.

  From the viewpoint of the transparency of the high refractive index transparent 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.
In the transfer film of the present invention, the high refractive index transparent resin layer has at least one of ZrO ₂ particles, Nb ₂ O ₅ particles, and TiO ₂ particles, and the refractive index range of the high refractive index transparent resin layer described above. From the viewpoint of controlling the refractive index, ZrO ₂ particles and Nb ₂ O ₅ particles are more preferable.
Examples of the metal oxide containing a zirconium atom that can be used in the present invention include nano-use OZ-S30M (zirconium oxide and tin oxide-containing inorganic particles, that is, a composite of zirconium oxide and tin oxide) manufactured by Nissan Chemical Industries, Nissan Examples thereof include Nanouse ZR-30BS (yttria-containing zirconium oxide particles) manufactured by Chemical Industry Co., Ltd.

The transfer film of the present invention has a viewpoint of improving the concealability of the transparent electrode pattern when the high refractive index transparent resin layer contains 40% by mass or more of metal oxide particles in a solid content ratio when laminated on the transparent electrode pattern. From 40 to 95% by mass, more preferably from 55 to 95% by mass, particularly preferably from 62 to 90% by mass from the viewpoint of improving cracking of the transfer film, from 62 to 90% by mass. The content of 75% by mass is particularly preferable from the viewpoints of further improving cracking of the transfer film and improving the substrate adhesion of the laminate of the present invention.
The high refractive index transparent resin layer preferably has at least one of ZrO ₂ particles and TiO ₂ particles. When the metal oxide particles are zirconium oxide, the high refractive index transparent resin layer preferably contains 40 to 95% by mass of metal oxide particles, more preferably 55 to 95% by mass, and 62 to 90% by mass. % Is particularly preferable, and 62 to 75% by mass is more preferable. When the metal oxide particles are titanium oxide, the high refractive index transparent resin layer preferably contains 30 to 70% by mass of the metal oxide particles.
In the transparent laminate of the present invention, the method for measuring the content of metal oxide particles in the transparent resin layer and the high refractive index transparent resin layer is as follows.
After cutting the cross section of the transparent 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 high refractive index transparent resin layer (or transparent resin layer) is measured at any three locations in the layer, and the average value is the volume fraction (VR). Consider.
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 high refractive index transparent resin layer (or transparent resin layer). calculate.
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.

<Thermoplastic resin layer>
In the transfer film of the present invention, a thermoplastic resin layer can be provided between the temporary support and the transparent resin layer. When a laminate is formed by transferring a transparent resin layer and a high refractive index transparent resin layer using the transfer film having the thermoplastic resin layer described above, bubbles are less likely to be generated in each layer formed by transfer, and image display Image unevenness or the like hardly occurs in the apparatus, and excellent display characteristics can be obtained.
The thermoplastic resin layer described above is preferably alkali-soluble. The thermoplastic resin layer plays a role as a cushioning material so as to be able to absorb unevenness of the underlying surface (for example, unevenness of an electrode pattern, including unevenness caused by an already formed image, etc.). It is preferable that it has a property that can be deformed according to the unevenness of the underlying surface.

  The thermoplastic resin layer preferably includes an organic polymer substance described in JP-A-5-72724 as a component, and is based on the Vicat method [specifically, based on the American Material Testing Method ASTM D1235. An embodiment containing at least one selected from organic polymer substances having a softening point of about 80 ° C. or lower, which is determined by the [Polymer softening point measurement method], is particularly preferable.

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

  The thickness of the thermoplastic resin layer is preferably 3 to 30 μm. When the thickness of the thermoplastic resin layer is 3 μm or more, the followability at the time of lamination is sufficient, and unevenness on the base surface is easily absorbed. In addition, when the thickness is 30 μm or less, the load on drying (solvent removal) during formation of the thermoplastic resin layer on the temporary support is reduced, the time required for development of the thermoplastic resin layer can be reduced, and process suitability is improved. Make it. As thickness of the above-mentioned thermoplastic resin layer, 4-25 micrometers is still more preferable, and 5-20 micrometers is especially preferable.

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

(Viscosity of thermoplastic resin layer)
The above-mentioned thermoplastic resin layer preferably has a viscosity measured at 100 ° C. in the region of 1000 to 10,000 Pa · s.

<Intermediate layer>
In the transfer film of the present invention, an intermediate layer can be provided between the thermoplastic resin layer and the transparent resin layer. As the intermediate layer, a layer described as “separation layer” in JP-A-5-72724 is preferable.

<Protective film>
The transfer film of the present invention preferably further includes a protective film (hereinafter also referred to as “protective release layer”) or the like on the surface of the above-described high refractive index transparent resin layer.

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

  In FIG. 12, an example of the preferable structure of the transfer film of this invention is shown. FIG. 12 shows an outline of the transfer film 30 of the present invention in which the temporary support 26, the transparent resin layer 7, the high refractive index transparent resin layer 12, and the protective release layer (protective film) 29 are laminated adjacent to each other in this order. FIG.

<Production method of transfer film>
There is no restriction | limiting in particular in the manufacturing method of a transfer film, A well-known method can be used.
When manufacturing a transfer film having a high refractive index transparent resin layer in addition to the transparent resin layer on the temporary support, the transfer film manufacturing method includes the step of forming the transparent resin layer on the temporary support, and And forming a high refractive index transparent resin layer directly on the transparent resin layer.
The step of forming the transparent resin layer is preferably a step of applying the organic solvent-based resin composition onto the temporary support.
Since the second resin layer obtained using the water-based resin composition is easily dissolved in water, it is preferable that the second resin layer has a composition that hardly causes the problem of wet heat durability of the transfer film. Specifically, the step of forming the high refractive index transparent resin layer is preferably a step of applying the aqueous resin composition. More preferably, the step of forming the high refractive index transparent resin layer is a step of applying 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. By adopting this constitution, the layer fraction is good, and the problem caused by moisture absorption of the transparent resin layer formed using the aqueous resin composition can be suppressed when aged at high temperature and high humidity. . By applying 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 on the transparent resin layer obtained by the organic solvent-based resin composition, Even if the high refractive index transparent resin layer is formed without being cured, layer mixing does not occur and the layer fraction is improved. Further, when drying a coating film obtained using 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, the ammonium salt or acid group of the monomer having an acid group is dried. Ammonia, which has a lower boiling point than water, easily volatilizes in the drying process from an ammonium salt of a resin having a high refractive index as a monomer having an acid group or a resin having an acid group by generating (regenerating) an acid group Can be present in the layer. For this reason, when the moisture is absorbed over time under high temperature and high humidity, the monomer having an acid group or the resin having an acid group constituting the high refractive index transparent resin layer is no longer dissolved in water. It is also possible to suppress problems when doing so.

(Step of forming a transparent resin layer on the temporary support)
The method for producing a transfer film has a step of forming a transparent resin layer on a temporary support, and the step of forming the transparent resin layer applies an organic solvent-based resin composition on the temporary support. It is preferable that it is a process.

-Organic solvent resin composition-
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, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.

  In the method for producing a transfer film, the organic solvent-based resin composition used for forming the transparent resin layer preferably contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator.

(Process of forming a high refractive index transparent resin layer)
In the method for producing a transfer film, the method includes a step of forming a high refractive index transparent resin layer directly on the transparent resin layer, and the step of forming the high refractive index transparent resin layer includes an ammonium salt of a monomer having an acid group. Or it is preferable that it is the process of apply | coating the aqueous resin composition containing the ammonium salt of resin which has an acid group.

-Aqueous resin composition-
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 lower alcohol having 1 to 3 carbon atoms and water is preferable. In a preferred embodiment of the method for producing a transfer film, the solvent of the aqueous resin composition used for forming the high refractive index transparent resin layer preferably contains water and an alcohol having 1 to 3 carbon atoms. It is more preferable that the alcohol content of ˜3 includes water or a mixed solvent having a mass ratio of 58/42 to 100/0. From the viewpoint of the water content / alcohol content of 1 to 3 carbon atoms, a mass ratio of 59/41 to 100/0 is particularly preferable, and 60/40 to 97/3 improves the coloration of the laminate of the present invention. More particularly preferred is 62/38 to 95/5, still more preferred from the viewpoint of improving the substrate adhesion of the laminate of the present invention, and most preferred is 62/38 to 85/15.
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 high refractive index transparent resin layer, the water / methanol mass ratio (mass% ratio) is preferably 58/42 to 100/0, The range of 41 to 100/0 is more preferable, 60/40 to 97/3 is particularly preferable, 62/38 to 95/5 is more particularly preferable, and 62/38 to 85/15 is even more particularly preferable. When the amount of water / alcohol content of 1 to 3 carbon atoms is less than the mass ratio of 58/42, the transparent resin layer is preferable because it is difficult to dissolve and cloudy.
By controlling to the said range, application | coating and quick drying are realizable without a high refractive index transparent resin layer and layer mixing.

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 high refractive index transparent resin layer is at least one among thermosetting and photocurability. When the transparent resin layer and the high refractive index transparent resin layer are curable transparent resin layers, according to the method for producing a transfer film, even if the high refractive index transparent resin layer is laminated without being cured after the transparent resin layer is laminated, The layer fraction is improved and the transparent electrode pattern concealing property can be improved. In this case, the transparent laminate described later is further transferred by photolithography after the refractive index adjusting layer (that is, the transparent resin layer and the high refractive index transparent resin layer) is simultaneously transferred from the obtained transfer film onto the transparent electrode pattern. At least the transparent resin layer that is closer to the outside than the high refractive index transparent resin layer after transfer can be developed into a desired pattern. An embodiment in which the second transparent resin layer has curability is more preferable. In this embodiment, after the transparent resin layer and the high refractive index transparent resin layer are transferred onto the transparent electrode pattern, it can be developed into a desired pattern by photolithography. .
In the transfer film manufacturing method, the aqueous resin composition used for forming the high refractive index transparent resin layer has an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group, a binder polymer, Or it is preferable that a thermopolymerizable compound and light or a thermal-polymerization initiator are included. 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.

<Ammonia volatilization>
Further, 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.

<Other processes>
Before forming the above-mentioned transparent resin layer on the above-mentioned temporary support, you may include the process of forming a thermoplastic resin layer further.

  After the step of forming the thermoplastic resin layer, a step of forming an intermediate layer between the thermoplastic resin layer and the transparent resin layer may be included. Specifically, when forming a transfer film having an intermediate layer, a solution (addition liquid for thermoplastic resin layer) in which an additive is dissolved together with a thermoplastic organic polymer is applied on a temporary support and dried. After providing a thermoplastic resin layer, a prepared solution (intermediate layer coating solution) prepared by adding a resin or an additive to a solvent that does not dissolve the thermoplastic resin layer is applied onto this thermoplastic resin layer and dried. It is preferable to laminate the intermediate layer. It is preferable that a transparent resin layer coating solution prepared using a solvent that does not dissolve the intermediate layer is further applied on the intermediate layer and dried to laminate the transparent resin layer.

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

<Uses of transfer film>
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. In the transfer film of the present invention, the transparent resin layer and the high refractive index transparent resin layer preferably have curability from the viewpoint of photolithography.
The transfer film of the present invention is preferably for a transparent insulating layer or a transparent protective layer of a capacitive input device. More specifically, the transfer film of the present invention is preferably used as a transfer film for forming a laminated pattern of a refractive index adjusting layer and an overcoat layer (transparent protective layer) on a transparent electrode pattern by a photolithography method. Can do.
The transfer film of the present invention is preferably used for a protective film for an electrode of a capacitive input device. The protective film for electrodes of the capacitive input device is obtained by removing the temporary support from the transfer film of the present invention.

[Laminate]
The laminate of the present invention comprises an electrode pattern,
A high refractive index transparent resin layer disposed adjacent to the electrode pattern;
A transparent resin layer disposed adjacent to the high refractive index transparent resin layer,
The refractive index of the high refractive index transparent resin layer is higher than the refractive index of the transparent resin layer,
High refractive index transparent resin layer and transparent resin layer are patterned,
A laminated body having an undercut depth of 5.0 μm or less at a pattern end of two layers comprising a high refractive index transparent resin layer and a transparent resin layer;
However, the undercut depth of the pattern end of the two layers composed of the high refractive index transparent resin layer and the transparent resin layer is an upper portion (more than half of the total film thickness of the two layers composed of the high refractive index transparent resin layer and the transparent resin layer) Parallel to the interface between the high refractive index transparent resin layer and the electrode pattern at the distance between the pattern extreme end point at the half and the upper half) and the contact point between the pattern edge of the high refractive index transparent resin layer and the electrode pattern The value of the direction component.
In the example of Japanese Patent Application Laid-Open No. 2014-108541, since the second curable transparent resin layer and the first curable transparent resin layer after transfer are not patterned, the undercut depth is unknown. There was no description regarding the shape of the pattern edge after exposure and development in the specification body of the publication -108541.

<Undercut depth>
In the laminate of the present invention, the undercut depth of the pattern end of the two layers comprising the high refractive index transparent resin layer and the transparent resin layer is 5.0 μm or less.
The “undercut depth of the pattern end of the two layers comprising the high refractive index transparent resin layer and the transparent resin layer” as referred to in the present invention is half of the total film thickness of the two layers comprising the high refractive index transparent resin layer and the transparent resin layer. The distance between the pattern uppermost point (the side far from the electrode pattern) and the contact point between the pattern edge of the high refractive index transparent resin layer and the electrode pattern is “parallel to the interface between the high refractive index transparent resin layer and the electrode pattern The value of the component in the “direction” (horizontal distance) (see FIG. 16). The above-mentioned “undercut depth” used in the present invention generally corresponds to a value called an undercut depth in the field of photolithography. The electrode pattern often has a different layer structure depending on the location and has a different height (for example, the right side is higher by the thickness of the routing wiring 6 than the left side in FIG. 16). The “electrode pattern interface” is defined between each pattern edge and the layer in contact with the high refractive index transparent resin layer in the vicinity thereof (for example, the left pattern edge in FIG. 16 has a high refractive index transparent resin layer 12). The interface between the transparent film 11 and the transparent film 11 is “the interface between the high-refractive-index transparent resin layer and the electrode pattern”, and the interface between the high-refractive-index transparent resin layer 12 and the wiring 6 at the right pattern end is And electrode pattern interface ”).
An example of the laminated body of the present invention is described on the right side of the opening 34 corresponding to the terminal portion of the routing wiring in FIG. 16, and the example of the laminated body of the present invention shown in FIG. Another conductive element 6) that is a lead-out wiring, a high refractive index transparent resin layer 12 disposed adjacent to the electrode pattern, and a transparent resin layer 7 disposed adjacent to the high refractive index transparent resin layer 12 Have One example of the laminate of the present invention described in FIG. 16 has a patterned transparent resin layer and a high refractive index transparent resin layer 33, and is composed of two layers (members) consisting of a high refractive index transparent resin layer and a transparent resin layer. 35) The undercut depth U at the pattern edge is 5.0 μm or less.
In FIG. 16, the undercut depth U of the two layers composed of the high refractive index transparent resin layer and the transparent resin layer is not less than half of the total film thickness H of the two layers composed of the high refractive index transparent resin layer and the transparent resin layer. A direction parallel to the interface between the high refractive index transparent resin layer and the electrode pattern at a distance between the pattern endmost point E on the upper side (the side far from the electrode pattern) and the contact point F between the pattern end of the high refractive index transparent resin layer and the electrode pattern The value of the component (horizontal distance), that is, the value indicated by “U”. The upper part of more than half of the total film thickness H of the two layers composed of the high refractive index transparent resin layer and the transparent resin layer means “H” in FIG. 16 out of the two layers composed of the high refractive index transparent resin layer and the transparent resin layer. / 2 "refers to the portion of the range indicated.
At this time, the contact point F between the pattern edge of the high refractive index transparent resin layer and the electrode pattern is the uppermost pattern at least half of the total film thickness H of the two layers of the high refractive index transparent resin layer and the transparent resin layer. When it is inside the end point E, the undercut depth U assumes a positive value. On the other hand, the contact point F between the pattern end of the high refractive index transparent resin layer and the electrode pattern is the uppermost pattern end point of more than half of the total film thickness H of the two layers consisting of the high refractive index transparent resin layer and the transparent resin layer. When the lower part of the total film thickness H of the two layers composed of the high refractive index transparent resin layer and the transparent resin layer is regarded as the “foot” of the pattern, In the example of “out of the pattern end point E”, the undercut depth U is a negative value (see FIG. 17). FIG. 17 is a schematic view showing an example of a cross section of the laminate of the present invention. FIG. 17 (A) shows an embodiment of an undercut depth U> 0, and FIG. 17 (B) shows an undercut depth U = 0. FIG. 17C shows an embodiment where the undercut depth U <0.
In the laminate of the present invention, the undercut depth at the pattern end of the two layers comprising the high refractive index transparent resin layer and the transparent resin layer is preferably 4 μm or less, more preferably 3 μm or less, and less than 0 μm. It is particularly preferred. Moreover, from a viewpoint of pattern resolving power, -100 micrometers or more are preferable. When patterning a high refractive index transparent resin layer and a transparent resin layer, patterning with a cutting method using a blade such as a die cut instead of patterning with a photolithography method will result in a high refractive index transparent resin layer and a transparent resin layer. The undercut depth at the pattern edge of the two layers is not less than 0 μm.

<Configuration of laminate>
The laminate of the present invention has an electrode pattern, a high refractive index transparent resin layer disposed adjacent to the electrode pattern, and a transparent resin layer disposed adjacent to the high refractive index transparent resin layer.
The electrode pattern is preferably an electrode pattern of a capacitive input device, and more preferably a transparent electrode pattern of the capacitive input device or a lead wiring of the capacitive input device. Since the extraction wiring such as a copper electrode often exists on a transparent electrode pattern such as ITO at the pattern end, it is more preferable that the electrode pattern is a routing wiring of the capacitive input device. However, the laminate of the present invention has a high refractive index transparent resin layer disposed adjacent to the transparent electrode pattern of the capacitive input device in a region where the electrode pattern that is the routing wiring does not exist in the plane, and a high It is also preferable to have a transparent resin layer disposed adjacent to the refractive index transparent resin layer.

The laminate of the present invention has a refractive index of 1.6 to 1.78 and a film thickness of 55 to 110 nm on the side of the electrode pattern opposite to the side on which the high refractive index transparent resin layer is formed. It is preferable to further have a film from the viewpoint of further improving the concealability of the transparent electrode pattern. In the present specification, when “transparent film” is described without particular notice, it refers to the “transparent film having a refractive index of 1.6 to 1.78 and a film thickness of 55 to 110 nm”.
The laminate of the present invention further includes a substrate on the side opposite to the side where the transparent electrode pattern is formed of the transparent film having the refractive index of 1.6 to 1.78 and a film thickness of 55 to 110 nm. It is preferable.

FIG. 11 shows an example of the configuration of the laminate of the present invention.
In FIG. 11, the laminate 13 of the present invention has a substrate 1, a transparent film 11 having a refractive index of 1.6 to 1.78 and a film thickness of 55 to 110 nm, a transparent electrode pattern 4, and a high refractive index. The surface 21 has a region 21 in which the transparent resin layer 12 and the transparent resin layer 7 are laminated in this order. In addition, in FIG. 11, in addition to the above-described region, the above-described laminated body is a region in which the substrate 1 and the transparent film 11 are laminated in this order (in the configuration of FIG. 11, the high refractive index transparent resin layer 12 and the transparent resin layer). 7 includes a region 22 (that is, a non-pattern region 22 in which a transparent electrode pattern is not formed) stacked in this order.
In other words, the transparent laminated body described above includes the region 21 in which the substrate 1, the transparent film 11, the transparent electrode pattern 4, the high refractive index transparent resin layer 12 and the transparent 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 substrate of the laminate. Therefore, the transparent electrode pattern 4, the high refractive index transparent resin layer 12, and the transparent resin layer 7 include in the plane a region where the transparent electrode pattern 4, the high refractive index transparent resin layer 12 and the transparent resin layer 7 are laminated in this order. This means that the orthogonal projection of the regions 7 in this order on the plane parallel to the substrate of the laminate exists in the plane parallel to the 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 substrate, the transparent film, and the high refractive index transparent resin layer 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 laminate of the present invention, the transparent film and the high refractive index transparent resin layer are adjacent to each other in a region where the substrate, the transparent film, and the high refractive index transparent resin layer are stacked in this order. It is preferable.
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, it is preferable that the substrate and the transparent film are adjacent to each other.
FIG. 11 shows a mode in which the above-described transparent film 11 is laminated adjacently on the above-described substrate 1.
However, a third transparent film may be laminated between the aforementioned substrate and the aforementioned 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 aforementioned substrate and the aforementioned transparent film.

In the laminate of the present invention, the transparent film preferably has a thickness of 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 of the present invention, 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 end of the transparent electrode pattern 4 is not particularly limited in shape, and may have a tapered shape as shown in FIG. 11, for example, the surface on the substrate side described above is the substrate described above. It may have a taper shape wider than the surface on the opposite side.
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 high refractive index transparent resin layer are adjacent to each other.
In FIG. 11, in the region 21 in which the above-described transparent electrode pattern, the above-described high refractive index transparent resin layer, and the transparent resin layer are laminated in this order, the above-described transparent electrode pattern, the above-described high refractive index transparent resin layer, and transparent resin 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 formed by the transparent film and the high refractive index transparent resin layer. It is preferably coated directly or via other layers.
Here, “continuously” means that the transparent film and the high refractive index transparent resin layer described above are not a pattern film but a continuous film. That is, it is preferable that the above-described transparent film and the above-described high refractive index transparent 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 high refractive index transparent 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 above-described high refractive index transparent resin layer 12 is laminated. The above-described high refractive index transparent 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 high refractive index transparent resin layer 12 is adjacent to the transparent film 11, and the high refractive index transparent 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 high refractive index transparent 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 transparent resin layer 7 is laminated on the surface of the high refractive index transparent resin layer 12 on the side opposite to the surface on which the transparent electrode pattern is formed. Yes.

<Material of laminate>
(substrate)
In the laminate of the present invention, the substrate is preferably a glass substrate or a film substrate. The substrate is preferably a transparent substrate. In the laminate of the present invention, the electrode pattern is preferably an electrode pattern formed on a transparent film substrate. That is, the above-mentioned substrate is preferably a transparent film substrate.
The refractive index of the aforementioned substrate is particularly preferably 1.5 to 1.52.
The aforementioned substrate may be composed of a light-transmitting substrate such as a glass substrate, and tempered glass represented by Corning's gorilla glass can be used. 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 film substrate is used as the aforementioned substrate, it is more preferable to use a substrate that is not optically distorted or that has high transparency. Specific examples of the film substrate include a film substrate containing polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and a cycloolefin polymer.
It is preferable that the laminated body of this invention has an electrode pattern, a high refractive index transparent resin layer, and a transparent resin layer on both surfaces of a transparent film board | substrate, respectively. In this case, the laminate of the present invention is preferably used as a film sensor. FIG. 9 is a schematic cross-sectional view showing a preferred configuration of a capacitive input device that is a front plate integrated sensor using a film sensor. In FIG. 9, the capacitance type input device which is a front plate integrated sensor includes a substrate 1 used as a front plate, a mask layer (second decorating layer) 2, a film sensor 43, and an adhesive material 51. The embodiment being shown is shown. In FIG. 9, two layers 35 each including a transparent electrode pattern 3 or 4, a high refractive index transparent resin layer, and a transparent resin layer are provided on both surfaces of a base sheet 1 A corresponding to a transparent film substrate. In the film sensor 43 of FIG. 9, the transparent films 11 are disposed on both surfaces of the base sheet 1A. The film sensor 43 shown in FIG. 9 includes an electrode pattern 4, a light-shielding conductive film 9, a transparent resin layer, and a high-refractive-index transparent resin layer on the surface of the base sheet 1A on the side laminated with the substrate. The two layers 35, the routing wiring 6, and the decoration layer 45 are arranged. The film sensor of FIG. 9 has an electrode pattern 3, a light-shielding conductive film 9, a transparent resin layer, and a high refractive index transparent resin layer on the surface of the base sheet 1A opposite to the side laminated with the substrate. The two layers 35 and the routing wiring 6 are arranged.

The film sensor preferably has a decorative layer 45 (a decorative layer of the film sensor).
Even when laminating a colored composition layer across the lead wiring 6 and the overcoat layer that require a certain thickness, it is possible to use a transfer film in a simple process without using expensive equipment such as a vacuum laminator. Lamination with no generation of bubbles at the boundary of the mask portion is possible.
The decorative layer is preferably a frame-shaped decorative layer. That is, when a film sensor is used in an image display device having a front plate integrated sensor, which will be described later, as a constituent element, the decorative layer surrounds the central image display portion (electronic device display window) in a frame shape. preferable. As a preferable aspect of the decoration layer of a film sensor, the same aspect as the frame-shaped light shielding layer described in Japanese Patent No. 5020580 can be exemplified.

(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 the metal oxide film and the metal film include an ITO film; a metal film such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; and a metal oxide film 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.

(Transparent resin layer and high refractive index transparent resin layer)
The preferable ranges of the transparent resin layer and the high refractive index transparent resin layer contained in the laminate of the present invention are the same as the preferable ranges of the above transparent resin layer and the above high refractive index transparent resin layer in the transfer film of the present invention. .
Among them, the laminate of the present invention preferably has a C / H ratio of 0.68 or more, which is a ratio of carbon and hydrogen in the mass of the transparent resin layer. In the laminate of the present invention, the high refractive index transparent resin layer preferably contains a metal oxidation inhibitor, and the metal oxidation inhibitor has an imidazole ring, a triazole ring or a condensed ring of these and other aromatic rings in the molecule. It is more preferable to have. In the laminate of the present invention, the high refractive index transparent resin layer preferably contains 40% by mass or more of metal oxide particles in a solid content ratio, and the amount of metal oxide particles contained in the high refractive index transparent resin layer is preferred. The range is the same as the preferable range of the amount of metal oxide particles contained in the high refractive index transparent resin layer of the transfer film of the present invention.

(Transparent film)
In the laminate of the present invention, the refractive index of the transparent film is preferably 1.6 to 1.78, more 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.
It is preferable to satisfy the refractive index range, but the material of 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 high refractive index transparent resin layer.
In the laminate of the present invention, the above-described transparent film and the above-described high refractive index transparent resin layer are preferably composed of the same material from the viewpoint of optical homogeneity.

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 above-described high refractive index transparent resin layer in the transfer film of the present invention. Resins and other additives used in the above can be preferably used.
In the laminate of the present invention, the transparent film may be an inorganic film.

(Third transparent film)
From the viewpoint of improving the concealability of the transparent electrode pattern, the refractive index of the third transparent film is preferably 1.5 to 1.55 from the viewpoint of improving the concealability of the transparent electrode pattern. More preferably, it is 1.52.

<Method for producing laminate>
There is no restriction | limiting in particular in the manufacturing method of a laminated body.
The laminate of the present invention is preferably produced by laminating the high refractive index transparent resin layer and the transparent resin layer of the transfer film of the present invention in this order on the electrode pattern. It is more preferable to include a step of transferring the high refractive index transparent resin layer and the transparent resin layer of the transfer film of the present invention onto the substrate including the electrode pattern of the capacitive input device using the transfer film of the present invention.

It is preferable that the manufacturing method of a laminated body includes the process of laminating | stacking the above-mentioned high refractive index transparent resin layer of the transfer film of this invention, and the above-mentioned transparent resin layer in this order on a transparent electrode pattern.
With this configuration, the high refractive index transparent resin layer of the laminate and the above-described transparent resin layer can be collectively transferred, and a laminate having no problem of visually recognizing the transparent electrode pattern is easily produced with high productivity. be able to.
In addition, the above-mentioned high refractive index transparent resin layer is formed on the above-mentioned transparent electrode pattern and on the above-mentioned transparent film in the above-mentioned non-pattern area | region directly or via another layer.

(Surface treatment of substrate)
In addition, in order to improve the adhesion of each layer after the lamination in the subsequent transfer step, an input means such as a finger is used in advance for the non-contact surface of the substrate (the surface of the substrate constituting the capacitive input device). Surface treatment can be performed on the surface opposite to the surface to be contacted. 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 silane coupling solution (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, and a pure water shower Wash. 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 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.

(Transparent resin layer and high refractive index transparent resin layer film formation)
The method for forming the above-mentioned transparent resin layer and the above-described high refractive index transparent resin layer includes a protective film removing step for removing the above-mentioned protective film from the transfer film of the present invention, and a method for removing the above-mentioned protective film from the present invention. A transfer step of transferring the transparent resin layer and the high refractive index transparent resin layer of the transfer film onto the transparent electrode pattern; and the transparent resin layer transferred onto the transparent electrode pattern and the high refractive index transparent resin layer of the transfer film. Examples thereof include an exposure step of exposing, and a developing step of developing the exposed transparent resin layer and the above-described high refractive index transparent resin layer.

-Transfer process-
The above-mentioned transfer step is preferably a step of transferring the above-mentioned transparent resin layer and the above-mentioned high refractive index transparent resin layer of the transfer film of the present invention from which the above-mentioned protective film has been removed onto a transparent electrode pattern.
Under the present circumstances, the method of including the process of removing the base material (temporary support body) after laminating the above-mentioned transparent resin layer and the above-mentioned high refractive index transparent resin layer of the transfer film of this invention on a transparent electrode pattern is preferable.
Transfer (bonding) of the transparent resin layer and the high refractive index transparent resin layer to the transparent electrode pattern surface is performed by superimposing the transparent resin layer and the high refractive index transparent resin layer on the transparent electrode pattern surface, This is done 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 preferably used in the present invention.

The exposure process is a process of exposing the transparent resin layer and the high refractive index transparent resin layer transferred onto the transparent electrode pattern.
Specifically, a predetermined mask is disposed above the transparent resin layer and the high refractive index transparent resin layer formed on the transparent electrode pattern and the temporary support, and then a light source above the mask ( And a method of exposing the aforementioned transparent resin layer and the aforementioned high refractive index transparent resin layer (via a mask and a temporary support).
Here, the light source for the exposure is appropriately selected as long as it can irradiate light (for example, 365 nm, 405 nm, etc.) in a wavelength region capable of curing the transparent resin layer and the high refractive index transparent resin layer. Can be 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 aforementioned developing step is a step of developing the exposed transparent resin layer and high refractive index transparent resin layer.
In the present invention, the above-described development step is a development step in a narrow sense that pattern-develops the pattern-exposed transparent resin layer and the high refractive index transparent 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 dissolution type developing behavior. For example, a compound having pKa (power of Ka; Ka is an acid dissociation constant) = 7 to 13 is 0.05 to 5 mol / mol. A developer containing a concentration of L is preferred. On the other hand, the developer in the case where the transparent resin layer and the high refractive index transparent resin layer itself do not form a pattern is preferably a developer having a development behavior that does not dissolve the non-alkaline development type colored composition layer. For example, a developer containing a compound having pKa = 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable. A small amount of an organic solvent miscible with water may be added 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. By spraying a developer onto the transparent resin layer and the high refractive index transparent resin layer after exposure, the uncured portion can be removed. 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 manufacturing method of the above-mentioned laminated body may have other processes, such as a post exposure process.

  The patterning exposure and the entire surface exposure may be performed after the substrate (temporary support) is peeled off, or may be exposed before the temporary support is peeled, 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 of the present invention includes a step of heat-treating the transparent resin layer after transfer to make at least a part of the carboxyl group-containing acrylic resin a carboxylic acid anhydride. From the viewpoint of improving The heat treatment for the transparent resin layer after transfer is preferably after exposure and development, that is, a post-baking step after exposure and development. When the above-mentioned transparent resin layer and the above-described high refractive index transparent 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.
When the film substrate is used as the substrate, the heating temperature in the step of heat-treating the transparent resin layer after the transfer so that at least a part of the carboxyl group-containing acrylic resin is a carboxylic acid anhydride is 100 to 160 ° C. It is preferable that it is 140-150 degreeC.

(Transparent film formation)
The laminate of the present invention has 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 above-described high refractive index transparent resin layer is formed. When it has a film | membrane further, the above-mentioned transparent film is formed into a film directly on the above-mentioned transparent electrode pattern, or through other layers, such as the above-mentioned 3rd 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 of the present invention is preferably formed by transferring the transparent curable resin film formed on the temporary support onto the above-mentioned substrate, and curing after transfer. More preferably, the film is formed. As a transfer and curing method, the above-mentioned transparent resin layer and the above-described high-refractive-index transparent resin layer in the laminate manufacturing method are transferred using a photosensitive film in the description of the capacitance-type input device of the present invention described later. 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. That is, in the laminated body of the present invention, it is also preferable that the transparent film is 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 the substrate.

The method for producing a laminate preferably includes a step of simultaneously curing the transparent resin layer and the high refractive index transparent resin layer, and more preferably includes a step of pattern curing at the same time. The transfer film of the present invention is preferably laminated with a high refractive index transparent resin layer without curing the transparent resin layer after laminating the transparent resin layer. The transparent resin layer and the high refractive index transparent resin layer transferred from the transfer film of the present invention thus obtained can be simultaneously cured. Thereby, after transferring the transparent resin layer and the high refractive index transparent 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 the step of simultaneously curing the transparent resin layer and the high refractive index transparent resin layer, and then the uncured portion of the transparent resin layer and the high refractive index transparent 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 1st aspect of the capacitance-type input device of this invention is produced using the transfer film of this invention.
The 2nd aspect of the capacitive input device of this invention contains the laminated body of this invention.
The capacitance-type input device of the present invention includes a high-refractive-index transparent resin layer and a transparent resin layer disposed adjacent to the above-described high-refractive-index transparent resin layer from the transfer film of the present invention. It is preferable to transfer and produce on the electrode pattern of an apparatus.
In the capacitance type input device of the present invention, it is preferable that the transparent resin layer and the high refractive index transparent resin layer transferred from the transfer film of the present invention are cured at the same time. More preferably, pattern curing is performed simultaneously. In addition, when hardening simultaneously the transparent resin layer and high refractive index transparent resin layer which were transferred from the transfer film of this invention, it is preferable not to peel a temporary support body from the transfer film of this invention.
More preferably, the capacitive input device of the present invention develops and removes the uncured portions of the transparent resin layer and the high refractive index transparent resin layer that are transferred from the transfer film of the present invention and simultaneously pattern-cured. In addition, it is preferable to peel the temporary support from the transfer film of the present invention after simultaneously curing the transparent resin layer and the high refractive index transparent 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 an arbitrary flexible wiring (for example, a flexible wiring manufactured on a polyimide film) at the terminal portion of the routing wiring, the transparent resin layer (and high refraction) It is preferable that the transparent resin layer is not covered.
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 transparent 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 transparent resin layer and a high refractive index transparent resin layer is laminated on a transparent electrode pattern of a capacitive input device and cured by exposure or the like. Indicates. When using photolithography, that is, when cured by exposure, the unexposed transparent resin layer and the high refractive index transparent resin layer are patterned by pattern exposure and development of the unexposed area using a mask. A transparent resin layer and a high refractive index transparent resin layer 33 can be obtained. Specifically, in FIG. 15, openings 34 (at the pattern ends of the transparent resin layer and the high refractive index transparent resin layer) corresponding to the terminal portions of the routing wiring as uncured portions of the transparent resin layer and the high refractive index transparent resin layer. The enclosed region) and the end of the transfer film of the present invention having the transparent resin layer and the high refractive index transparent resin layer that protruded outside the outline of the frame portion of the capacitive input device were removed, A patterned transparent resin layer and a high-refractive-index transparent resin layer 33 (desired pattern) for not covering the terminal portion (lead-out wiring portion) of the routing wiring are obtained.
As a result, an arbitrary flexible wiring can be directly connected to the terminal portion 31 of the routing wiring, and the signal of the sensor can be sent to the electric circuit.
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 has the laminate of the present invention, and includes at least the following (3) on the substrate (corresponding to the aforementioned substrate in the laminate of the present invention) and the non-contact surface side of the aforementioned substrate It is preferable to have the element of (8).
(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;
(6) Separately from the first transparent electrode pattern and the second electrode pattern, which are electrically connected to at least one of the first transparent electrode pattern and the second electrode pattern. Conductive elements;
(7) A high-refractive-index transparent resin layer formed so as to cover all or part of the above-described elements (3) to (6);
(8) A transparent resin layer formed so as to cover the element of (7) described above.
Here, the above (7) high refractive index transparent resin layer corresponds to the above high refractive index transparent resin layer in the laminate of the present invention. Moreover, the above-mentioned (8) transparent resin layer corresponds to the above-mentioned transparent resin layer in the laminate of the present invention. The above-mentioned transparent resin layer is preferably a so-called transparent protective layer in a generally known electrostatic 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 (2) a transparent film, (3) the first transparent electrode pattern and the substrate, and (4) the second electrode pattern and the above-described substrate. It is preferable to have between the substrates or between the aforementioned (6) another conductive element and the aforementioned substrate. 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 is formed between the above-mentioned (2) transparent film and the above-mentioned substrate, (3) between the above-mentioned first transparent electrode pattern and the above-mentioned substrate, 4) It is preferable to have between the 2nd transparent electrode pattern and the above-mentioned board | substrate, or between the above-mentioned (6) another electroconductive element and the above-mentioned board | substrate. The aforementioned (1) mask layer and / or decorative layer is more preferably provided adjacent to the aforementioned substrate.

  The capacitance-type input device of the present invention includes the above-described high-refractive index transparent resin layer and the above-described high-refractive index transparent resin layer that are disposed adjacent to the transparent electrode pattern, even when various members are included. By including the above-described transparent resin layer disposed adjacent to the transparent electrode pattern, 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 high refractive index transparent resin layer. As a result, the problem of concealment of the transparent electrode pattern can be improved.

<Configuration of capacitance type input device>
First, a preferable configuration of the capacitive input device will be described together with a method for manufacturing each member constituting the device.
FIG. 16 is a schematic cross-sectional view showing another example of a preferable configuration of the capacitance-type input device of the present invention. 16 is a schematic cross-sectional view showing another example of the configuration of the capacitance-type input device of the present invention. The terminal portion 31 of the routing wiring (another conductive element) in FIG. 14 and the routing wiring in FIG. It is an enlarged view of the vicinity of the opening part 34 corresponding to this terminal part. In the center of FIG. 16, there is an opening 34 corresponding to the terminal portion of the routing wiring. A mode in which the transparent resin layer 7 and the high refractive index transparent resin layer 12 are laminated on the base sheet 1A and the transparent film 11 is described on the left side of the opening 34 corresponding to the terminal portion of the routing wiring in FIG. ing. On the other hand, an example of the laminate of the present invention is described on the right side of the opening 34 corresponding to the terminal portion of the routing wiring in FIG. 16, and the details have been described in the configuration of the laminate of the present invention.
FIG. 1A is a schematic cross-sectional view showing an example of a preferred configuration of the capacitive input device of the present invention. 1A, a capacitive input device 10 includes a substrate 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, and a first transparent electrode pattern. (The connection portion 3b of the first transparent electrode pattern is shown), the second transparent electrode pattern 4, the insulating layer 5, another conductive element 6, and the high refractive index transparent resin layer 12 The aspect comprised from the transparent 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 substrate 1, a transparent film 11 having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm, a first transparent electrode pattern 3, and a second electrode. The aspect comprised from this transparent electrode pattern 4, the high refractive index transparent resin layer 12, and the transparent resin layer 7 is shown.

  For the substrate 1, the materials listed as materials for the laminate of the present invention can be used. Moreover, in FIG. 1A, the side in which each element of the board | substrate 1 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 of the substrate 1 (the surface opposite to the non-contact surface).

A mask layer 2 is provided on the non-contact surface of the substrate 1. The mask layer 2 is a frame-shaped pattern around the display area formed on the non-contact surface side of the touch panel substrate, and is formed so as to prevent the lead-out wiring and the like from being seen.
In the capacitive input device 10 of the present invention, as shown in FIG. 2, a mask layer 2 is provided so as to cover a part of the substrate 1 (a region other than the input surface in FIG. 2). . Further, the substrate 1 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 substrate 1, a plurality of first transparent electrode patterns 3 formed by extending a plurality of pad portions in the first direction via connection portions, a first transparent electrode pattern 3, A plurality of second transparent electrode patterns 4 made of a plurality of pad portions that are electrically insulated and extend in a direction intersecting the first direction, the first transparent electrode pattern 3 and the second An insulating layer 5 that electrically insulates the transparent electrode pattern 4 is 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.

In addition, at least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4 is installed across both regions of the non-contact surface of the substrate 1 and the surface of the mask layer 2 opposite to the substrate 1. be able to. In FIG. 1A, a diagram is shown in which the second transparent electrode pattern 4 is installed across both regions of the non-contact surface of the substrate 1 and the surface of the mask layer 2 opposite to the substrate 1. .
Thus, even when laminating a photosensitive film across a mask layer that requires a certain thickness and the non-contact surface of the substrate, a vacuum laminator or the like can be obtained by using a photosensitive film having a specific layer configuration to be 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 provided on the side of the mask layer 2 opposite to the substrate 1. 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 transparent resin layer 7 is installed so that all of each component may be covered. The transparent resin layer 7 may be configured to cover only a part of each component. The insulating layer 5 and the transparent resin layer 7 may be the same material or different materials. As the material constituting the insulating layer 5, those listed as the materials for the transparent resin layer or the high refractive index transparent resin layer in the laminate of the present invention can be preferably used.

<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 a transparent substrate 1 made of tempered glass with openings 8 formed therein. FIG. 5 is a top view showing an example of the substrate on which the mask layer 2 is formed. FIG. 6 is a top view showing an example of the substrate on which the first transparent electrode pattern 3 is formed. FIG. 7 is a top view showing an example of a substrate 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 substrate on which a conductive element 6 different from the first and second transparent electrode patterns is 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 high refractive index transparent resin layer 12 and the transparent resin layer 7 described above are formed, each element is arbitrarily formed using the transfer film of the present invention. It can be formed by transferring the above-described high refractive index transparent resin layer and the above transparent resin layer to the surface of the substrate 1.

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.
Each element (mask layer 2, first transparent electrode pattern 3, second transparent electrode pattern 4, insulating layer 5 and other conductive elements) using the transfer film of the present invention and the photosensitive film described above. Forming at least one element of the conductive element 6), even in a substrate having an opening, there is no leakage and / or protrusion of the resist component from the opening, and it is particularly necessary to form a light-shielding pattern directly above the boundary line of the edge of the substrate In the mask layer, there is no leakage and / or protrusion of the resist component from the substrate edge. Therefore, the touch panel reduced in thickness and weight can be manufactured by a simple process without contaminating the non-contact surface of the substrate.

  Using the above-mentioned photosensitive film as a permanent material such as a first transparent electrode pattern, a second transparent electrode pattern and another conductive element when a mask layer, an insulating layer, and a conductive photocurable resin layer are used In the case of forming the photosensitive film, the photosensitive film may be subjected to pattern exposure as necessary after being laminated on the substrate. The aforementioned photosensitive film may be a negative type material or a positive type material. When the above-mentioned photosensitive film is a negative type material, a pattern can be obtained by developing and removing the non-exposed portion and when the positive film is a positive type 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 above-described photosensitive film other than the transfer film of the present invention, which is preferably used when manufacturing the capacitive input device of the present invention, will be described. The aforementioned photosensitive film preferably has a temporary substrate and a photocurable resin layer, and preferably has a thermoplastic resin layer between the temporary substrate and the photocurable resin layer. When a mask layer or the like is formed using the photosensitive film having the thermoplastic resin layer described above, bubbles are less likely to be generated in an element formed by transferring the photocurable resin layer, and image unevenness or the like may occur in the image display device. It is less likely to occur and excellent display characteristics can be obtained.

-Layers other than the photocurable resin layer, production method-
As the above-mentioned temporary base material and the above-mentioned thermoplastic resin layer in the above-mentioned photosensitive film, those similar to those respectively used as the temporary support and the thermoplastic resin layer in the transfer film of the present invention can be used. Moreover, the same method as the manufacturing method of a transfer film can be used also as the preparation methods of the above-mentioned photosensitive film.

-Photocurable resin layer-
The above-mentioned photosensitive film adds an additive to a photocurable resin layer according to the use. That is, when the above-mentioned photosensitive film is used for forming the mask layer, a colorant is contained in the photocurable resin layer. Moreover, when the above-mentioned photosensitive film has an electroconductive photocurable resin layer, electroconductive fiber etc. contain in the above-mentioned photocurable resin layer.

  When the above-mentioned photosensitive film is a negative material, the photocurable resin layer preferably contains an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. Furthermore, conductive fibers, colorants, other additives, and the like are used, but are not limited thereto.

--Alkali-soluble resin, polymerizable compound, or the aforementioned polymerization initiator--
As the alkali-soluble resin, the polymerizable compound, and the polymerization initiator contained in the photosensitive film, the same alkali-soluble resin, polymerizable compound, or polymerization initiator as those used in the transfer film of the present invention is used. be able to.

--Conductive fiber (when used as conductive photocurable resin layer)-
When the above-mentioned photosensitive film laminated with the above-mentioned conductive photocurable resin layer is used for forming a transparent electrode pattern or another conductive element, the following conductive fibers are used for the photocurable resin layer. be able to.

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

  There is no restriction | limiting in particular as a material of the above-mentioned metal nanowire, For example, it consists of the 4th period, the 5th period, and the 6th period of the Long Periodic Table (The International Union of Pure and Applied Chemistry (IUPAC) 1991). At least one metal selected from the group is preferred, at least one metal selected from Group 2 to Group 14 is more preferred, Group 2, Group 8, Group 9, Group 10, Group 11 , At least one metal selected from Group 12, Group 13, and Group 14 is more preferable, and it is particularly preferable to include as a main component.

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

There is no restriction | limiting in particular as a shape of the above-mentioned metal nanowire, According to the objective, it can select suitably, For example, it can take arbitrary shapes, such as a column shape, a rectangular parallelepiped shape, and a column shape whose section becomes a polygon. However, in applications where high transparency is required, a cylindrical shape and a cross-sectional shape with rounded polygonal corners are preferred.
The cross-sectional shape of the above-mentioned metal nanowire can be examined by applying a metal nanowire aqueous dispersion on a temporary base material and observing the cross-section with a transmission electron microscope (TEM).

The average minor axis length of the metal nanowire is preferably 150 nm or less, more preferably 1 nm to 40 nm, still more preferably 10 nm to 40 nm, and particularly preferably 15 nm to 35 nm.
When the average minor axis length is less than 1 nm, the oxidation resistance may be deteriorated and the durability may be deteriorated. When the average minor axis length is more than 150 nm, scattering due to metal nanowires occurs and sufficient transparency is obtained. There are things you can't get.
The average minor axis length of the above-mentioned metal nanowires was determined by observing 300 metal nanowires using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). The average minor axis length of the wire was determined.
The short axis length when the short axis of the metal nanowire is not circular was the shortest axis.

The average major axis length of the metal nanowire is preferably 1 μm to 40 μm, more preferably 3 μm to 35 μm, and still more preferably 5 μm to 30 μm.
The average major axis length of the metal nanowires described above was observed from 300 metal nanowires using, for example, a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). The average major axis length of the nanowire was determined. In addition, when the above-mentioned metal nanowire was bent, the circle | round | yen which makes it an arc was considered and the value calculated from the radius and curvature was made into the major axis length.

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

--Colorant (when used as a mask layer)-
Moreover, when using the above-mentioned photosensitive film as a mask layer, a coloring agent can be used for a photocurable resin layer. As the colorant used in the present invention, known colorants (organic pigments, inorganic pigments, dyes, etc.) can be suitably used. In the present invention, in addition to the black colorant, a mixture of pigments such as red, blue, and green can be used.

  When using the above-mentioned photocurable resin layer as a black mask layer, it is preferable that a black colorant is included from the viewpoint of optical density. Examples of the black colorant include carbon black, titanium carbon, iron oxide, titanium oxide, and graphite. Among these, carbon black is preferable.

  When the above-mentioned photocurable resin layer is used as a white mask layer, white pigments described in paragraphs 0015 and 0114 of JP-A-2005-7765 can be used. In order to use it as a mask layer of other colors, pigments or dyes described in paragraphs 0183 to 0185 of Japanese Patent No. 4546276 may be mixed and used. Specifically, pigments and dyes described in paragraphs 0038 to 0054 of JP-A-2005-17716, pigments described in paragraphs 0068 to 0072 of JP-A-2004-361447, paragraphs of JP-A-2005-17521 The colorants described in 0080 to 0088 can be suitably used.

The aforementioned colorant (preferably a pigment, more preferably carbon black) is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the aforementioned colorant and pigment dispersant in an organic solvent (or vehicle). The aforementioned vehicle refers to a portion of the medium in which the pigment is dispersed when the paint is in a liquid state, and is a liquid component that binds with the aforementioned pigment to form a coating film (binder) and dissolves this. Component to dilute (organic solvent).
The disperser used for dispersing the pigment is not particularly limited. For example, the kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, First Edition, Asakura Shoten, 2000, Item 438. , Known dispersers such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, a sand mill, and a bead mill.
Further, fine grinding may be performed using frictional force by mechanical grinding described in page 310 of this document.

  From the viewpoint of dispersion stability, the above-mentioned colorant is preferably a colorant having a number average particle diameter of 0.001 μm to 0.1 μm, and more preferably 0.01 μm to 0.08 μm. The “particle size” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle size” is the above-mentioned particle size for a large number of particles, Among these, the average value of 100 particle diameters arbitrarily selected is said.

The thickness of the photocurable resin layer containing the colorant is preferably 0.5 to 10 μm, more preferably 0.8 to 5 μm, and particularly preferably 1 to 3 μm from the viewpoint of a difference in thickness from the other layers. Although there is no restriction | limiting in particular as content rate of the coloring agent in solid content of the coloring photosensitive resin composition for forming the photocurable resin layer containing a coloring agent, From a viewpoint of fully shortening development time, 15 It is preferably ˜70% by mass, more preferably 20 to 60% by mass, still more preferably 25 to 50% by mass.
The total solid content of the colored photosensitive resin composition means the total mass of nonvolatile components excluding the solvent and the like from the colored photosensitive resin composition.

  In addition, when forming an insulating layer using the above-mentioned photosensitive film, 0.1-5 micrometers is preferable from a viewpoint of maintenance of insulation, and, as for the thickness of a photocurable resin layer, 0.3-3 micrometers is still more preferable. 0.5-2 μm is particularly preferable.

-Other additives-
Furthermore, other additives may be used for the above-mentioned photocurable resin layer. As the aforementioned additive, the same additives as those used for the transfer film of the present invention can be used.
Moreover, as a solvent at the time of manufacturing the above-mentioned photosensitive film by application | coating, the solvent similar to what is used for the transfer film of this invention can be used.

  As mentioned above, although the case where the above-mentioned photosensitive film was a negative type material was demonstrated centering, the above-mentioned photosensitive film may be a positive type material. In the case where the above-described photosensitive film is a positive type material, for example, a material described in JP-A-2005-221726 is used for the photocurable resin layer, but is not limited thereto.

(Formation of mask layer and insulating layer using photosensitive film)
The mask layer 2 and the insulating layer 5 described above can be formed by transferring the photocurable resin layer to the substrate 1 or the like using the above-described photosensitive film. For example, when the black mask layer 2 is formed, the above-described black light is applied to the surface of the substrate 1 using the above-described photosensitive film having the black photo-curable resin layer as the above-described photo-curable resin layer. It can be formed by transferring a curable resin layer. In the case of forming the insulating layer 5, the above-mentioned substrate on which the first transparent electrode pattern is formed using the above-mentioned photosensitive film having an insulating photo-curable resin layer as the above-mentioned photo-curable resin layer. It can be formed by transferring the above-mentioned photocurable resin layer to the first transparent electrode pattern formed on the surface of 1.
Furthermore, in forming the mask layer 2 that needs light shielding properties, the above photosensitive film having a specific layer structure having a thermoplastic resin layer between the photocurable resin layer and the temporary base material is used for photosensitivity. It is possible to prevent the generation of bubbles during film lamination and to form a high quality mask layer 2 or the like having no light leakage.

(First and second transparent electrode patterns using photosensitive film, formation of another conductive element)
The first transparent electrode pattern 3, the second transparent electrode pattern 4, and the other conductive element 6 are etched using the above-described photosensitive film having an etching process or a conductive photo-curable resin layer, or photosensitive. A film can be formed using the lift-off material.

-Etching treatment-
When the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 are formed by etching, first, on the non-contact surface of the substrate 1 on which the mask layer 2 and the like are formed. A transparent electrode layer such as ITO is formed by sputtering. Next, an etching pattern is formed by exposure and development using the above-described photosensitive film having the photocurable resin layer for etching as the above-mentioned photocurable resin layer on the above-described transparent electrode layer. Thereafter, the transparent electrode layer is etched to pattern the transparent electrode, and the etching pattern is removed, whereby the first transparent electrode pattern 3 and the like can be formed.

  Also when using the above-mentioned photosensitive film as an etching resist (etching pattern), a resist pattern can be obtained in the same manner as described above. For the above-described etching, etching and resist stripping can be applied by a known method described in paragraphs 0048 to 0054 of JP 2010-152155 A.

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

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

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

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

-Photosensitive film having a conductive photocurable resin layer-
In the case where the first transparent electrode pattern 3, the second transparent electrode pattern 4, and the other conductive element 6 are formed using the photosensitive film having the conductive photocurable resin layer, the substrate described above is used. It can be formed by transferring the conductive photocurable resin layer described above to the surface of 1.
When the first transparent electrode pattern 3 or the like described above is formed using the photosensitive film having the conductive photocurable resin layer, the resist component may be leaked and / or protruded from the opening even on the substrate having the opening. Without touching the non-contact surface side of the substrate, it is possible to manufacture a touch panel having a merit of thin layer / light weight by a simple process.
Furthermore, by using the above-described photosensitive film having a specific layer structure having a thermoplastic resin layer between the conductive photocurable resin layer and the temporary base material for forming the first transparent electrode pattern 3 and the like. It is possible to prevent the generation of bubbles when laminating the photosensitive film, and to form the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 with excellent conductivity and low resistance.

-Use of photosensitive film as lift-off material-
Moreover, a 1st transparent electrode layer, a 2nd transparent electrode layer, and another electroconductive member can also be formed using the above-mentioned photosensitive film as a lift-off material.
In this case, after patterning using the above-described photosensitive film, a transparent conductive layer is formed on the entire surface of the temporary substrate, and then the above-described photoconductive resin layer is dissolved and removed together with the laminated transparent conductive layer. A transparent conductive layer pattern can be obtained (lift-off method).

[Image display device]
The image display device of the present invention is an image display device including the capacitive input device of the present invention as a constituent element. The image display device of the present invention includes “latest touch panel technology” (published July 6, 2009, Techno Times), supervised by Yuji Mitani, “Technology and Development of Touch Panel”, CM Publishing (2004, 12), The configurations disclosed in 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.

[Examples 1 to 21 and Comparative Examples 1 to 4]
<1. Production of Transfer Films of Examples and Comparative Examples>
(Preparation of coating solution for transparent resin layer)
Materials A-1 to A-16, which are coating solutions for the transparent resin layer, were prepared so as to have compositions as shown in Table 1 below.

(Preparation of coating solution for high refractive index transparent resin layer)
Next, materials B-1 to B-7, which are coating solutions for the high refractive index transparent resin layer, were prepared so as to have the composition as shown in Table 2 below.
In the specification, “Mw” is synonymous with “weight average molecular weight”.

(Production of transfer film)
On the temporary support which is a polyethylene terephthalate film, using a slit-shaped nozzle, the coating amount is adjusted so that the thickness of the transparent resin layer after drying is as shown in Table 4 below. Any one of materials A-1 to A-16 was applied according to the following Table 4 to form a transparent resin layer.
After volatilizing the solvent in the drying zone of 120 ° C. in the formed transparent resin layer, using a slit nozzle on the transparent resin layer, the thickness of the high refractive index transparent resin layer after drying is shown in Table 5 below. The coating amount is adjusted so as to be a thickness, and any one of the materials B-1 to B-7 for the high refractive index transparent resin layer is applied according to the following Table 5, dried, and the high refractive index transparent resin layer Formed.

(Crimping of protective film)
Finally, a protective film (16 μm thick PET film) was pressure-bonded on the formed high refractive index transparent resin layer.
Thus, a temporary support, a transparent resin layer, a high refractive index transparent resin layer, and a protective film were laminated in this order to produce a transfer film. The obtained transfer film was used as a transfer film of each example and comparative example.

<2. Evaluation of Transfer Films of Examples and Comparative Examples>
(Acid value of transparent resin layer)
A sample consisting of only the transparent resin layer was prepared separately, and the acid value of the transparent resin layer was determined according to the method described in JIS K 0070: 1992. The obtained results are shown in Table 4 below.

(Amount of crosslinkable group in transparent resin layer)
The amount of the crosslinkable group in the transparent resin layer was calculated from the material composition. The obtained results are shown in Table 4 below.
In addition, the amount of the crosslinkable group obtained by calculation is prepared separately by preparing a sample consisting of only the transparent resin layer, dissolving a predetermined amount of the sample in a suitable solvent, and analyzing various crosslinkable groups by analysis such as NMR or FT-IR. It was comparable to the value calculated by quantifying.

(I / O value of transparent resin layer)
The I / O value of the transparent resin layer was calculated from the material composition according to the method shown in “Organic Conceptual Diagram” (Yoshio Koda, Sankyo Publishing, 1984). The obtained results are shown in Table 4 below.

(C / H ratio of transparent resin layer)
A sample consisting of only the transparent resin layer was separately prepared, a predetermined amount of the sample was burned, and the weight of water and carbon dioxide generated was measured to obtain the C / H ratio of the transparent resin layer. The obtained results are shown in Table 4 below.

(Thickness and refractive index of transparent resin layer and high refractive index transparent resin layer)
The thickness and refractive index of the transparent resin layer and the high refractive index transparent resin layer were determined as follows using a reflection spectral film thickness meter FE-3000 (manufactured by Otsuka Electronics Co., Ltd.).
(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. The reflection spectrum (wavelength: 430 to 800 nm) of the laminate of the temporary support and black PET was evaluated using a reflection spectral film thickness meter FE-3000, and the refractive index n ₀ of the temporary support at each wavelength was determined.
(2) A transparent adhesive tape (on a temporary support surface of a sample in which only a transparent resin layer is formed on a temporary support in the same manner as in each of the Examples and Comparative Examples, which is cut to a length of 5 cm × 5 cm in length and width. OCA tape 8171CL: manufactured by 3M Co., Ltd.) was used to produce a laminate in which a black PET material was brought into contact. Using a transmission electron microscope (TEM: HT7700, Hitachi High-Tech Fielding Co., Ltd.), the transparent resin layer, the temporary support, and the black PET laminate were structurally analyzed. The thickness of the transparent 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 transparent resin layer was determined. The reflection spectrum (wavelength: 430 to 800 nm) of the laminate of the transparent resin layer, the temporary support and the black PET was evaluated using a reflection spectral film thickness meter FE-3000 manufactured by Otsuka Electronics Co., Ltd., and the transparent resin layer at each wavelength. The second expected value T ₁ (II) of the average value of the refractive index n ₁ and the thickness of the transparent resin layer was determined. At this time, in order to consider reflection at the interface between the transparent resin layer and the temporary support, the first value of the refractive index n ₀ of the temporary support obtained in (1) above and the average value of the thickness of the transparent resin layer is used. The expected value T ₁ (I) is input to the thickness calculation software attached to the FE 3000, and then the refractive index n ₁ of the transparent resin layer and the transparent resin layer are determined from the reflection spectrum of the laminate of the transparent resin layer, the temporary support, and the black PET. The second expected value T ₁ (II) of the average value of the thickness was obtained by fitting by simulation calculation.
(3) A transparent adhesive tape (OCA tape 8171CL: 3M Co., Ltd.) was 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. A sample piece in which a black PET material was brought into contact was prepared. Analyzing the structure of the sample piece using a transmission electron microscope (TEM), measuring the thickness of the high refractive index transparent resin layer at 10 points, obtaining the average value, and predicting the average value of the thickness of the high refractive index transparent resin layer The value T 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, in order to consider reflection at the interface between the transparent resin layer and the temporary support and the interface between the transparent resin layer and the high refractive index transparent resin layer, the refractive index n ₀ of the temporary support obtained in (1) above, The second expected value T ₁ (II) of the average value of the refractive index n ₁ of the transparent resin layer and the thickness of the transparent resin layer obtained in (2), and the expected value of the average value of the thickness of the high refractive index transparent resin layer With the value T ₂ (I) substituted into the calculation formula, the refractive index n _{2 of the} high refractive index transparent resin layer is determined from the reflection spectrum of the laminate of the high refractive index transparent resin layer, the transparent resin layer, the temporary support, and the black PET. The thicknesses of the transparent resin layer and the high refractive index transparent resin layer at 1000 measurement points were obtained by fitting by simulation calculation. Furthermore, the average value of the thickness of a transparent resin layer and a high refractive index transparent resin layer was computed, and it was set as the thickness of the transparent resin layer and the thickness of a high refractive index transparent resin layer.
As for the thickness of the transparent resin layer and the thickness of the high-refractive-index transparent resin layer, it is possible to improve the fitting accuracy of the simulation by inputting the expected value obtained by conducting the structural analysis with TEM to the reflection spectral film thickness meter.
The thickness of the obtained transparent resin layer, the thickness of the high refractive index transparent resin layer, and the refractive index at a wavelength of 550 nm are shown in Table 4 or Table 5 below.

(Measurement of swelling rate on PET film laminated with copper foil)
Using the transfer film of each Example and Comparative Example from which the protective film was peeled off, on the copper foil of a Cu film (Geomatec / PET thickness 250 μm, Cu 300 nm monolayer film) which is a PET film laminated with a copper foil The high refractive index transparent resin layer, the transparent resin layer and the temporary support were transferred in this order (temperature of the copper foil laminated PET film: 40 ° C., rubber roller temperature 110 ° C., linear pressure 3 N / cm, conveyance speed 2 m / min. ).
Then, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, between the exposure mask (quartz exposure mask having a pattern for overcoat formation) and the temporary support. The distance was set to 125 μm, and pattern exposure was performed with an exposure amount of 80 mJ / cm ² (i-line) through a temporary support. After peeling off the temporary support, the amount of change in film thickness was measured before and after immersing two layers consisting of a transparent resin layer and a high refractive index transparent resin layer in a 1% by weight aqueous sodium carbonate solution at 33 ° C. for 55 seconds. For the measurement, a stand type electric micrometer E-ST-100DB manufactured by Tokyo Seimitsu Co., Ltd. was used. The amount of change in film thickness of the two layers consisting of the transparent resin layer and the high refractive index transparent resin layer obtained is relative to the film thickness before dipping the two layers consisting of the transparent resin layer and the high refractive index transparent resin layer measured separately. The swelling rate was calculated as a percentage of the percentage. The results are shown in Table 5 below.

<3. Production of transparent electrode pattern film used for production of laminate of first aspect>
(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 Table 3 below was coated on a transparent film substrate using a slit 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.

In the specification, “wt%” is synonymous with “mass%”.
Formula (3)

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

-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. Thus, 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 on the temporary base material. Finally, a protective film (12 μm thick polypropylene film) was pressure-bonded. In this way, a photosensitive film E1 for etching in which the temporary base material, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the photocurable resin layer for etching were integrated was produced.

--- 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, Glass
s Transition Temperature (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 (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.)
: 9.1 parts by mass Fluorine-based polymer: 0.54 parts by mass The above fluorine-containing _{polymer, C 6 F 13 CH 2 CH} 2 OCOCH = CH 2 40 parts of _{H (OCH (CH 3) CH} 2) 7 OCOCH = Copolymer of 55 parts of CH _{2 and} 5 parts of H (OCH ₂ CH ₂ ) ₇ OCOCH = CH ₂ , which is a solution having a weight average molecular weight of 30,000 and 30% by mass of methyl ethyl ketone (trade name: MegaFuck F780F, Dainippon Ink Chemical Industry Co., Ltd.)

-Intermediate layer coating solution: Formulation P1--
Polyvinyl alcohol: 32.2 parts by mass (trade name: PVA205, manufactured by Kuraray Co., Ltd., degree of saponification = 88%,
Degree of polymerization 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

-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 60000, acid value 163 mg KOH / g): 16 parts by mass / monomer 1 (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.)
: 5.6 parts by mass-tetramethylene oxide monomethacrylate 0.5 mol adduct of hexamethylene diisocyanate: 7 parts by mass-cyclohexane dimethanol monoacrylate as a compound having one polymerizable group in the molecule: 2.8 parts by mass・ 0.42 mass parts of 2-chloro-N-butylacridone ・ 2,2-bis (orthochlorophenyl) -4,4 ′, 5,5 ′
-Tetraphenyl: 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: Megafuck F -780F, manufactured by Dainippon Ink Co., Ltd.): 0.03 parts by mass / methyl ethyl ketone: 40 parts by mass / 1-methoxy-2-propanol: 20 parts by mass In addition, the solvent for the photocurable resin layer coating liquid E1 for etching The viscosity at 100 ° C. after the removal was 2500 Pa · s.

-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 this 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) Liquid temperature 45 ° C) is immersed in a resist stripping tank, treated for 200 seconds (peeling treatment), the photocurable resin layer for etching is removed, and a transparent film and a transparent electrode pattern are formed on the transparent film substrate. The formed transparent electrode pattern film was obtained.

(Preparation of laminate of first aspect)
The transparent film and transparent electrode pattern of the transparent electrode pattern film in which the transparent film and the transparent electrode pattern are formed on the transparent film substrate by using the transfer film of each Example and Comparative Example from which the protective film was peeled off, a high refractive index transparent resin The high refractive index transparent resin layer, the transparent resin layer, and the temporary support were transferred in this order so that the layers were covered to obtain a laminate (transparent film substrate temperature: 40 ° C., rubber roller temperature 110 ° C., linear pressure) 3 N / cm, conveyance speed 2 m / min).
Thereafter, using the proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the surface of the obtained laminate is temporarily exposed to an exposure mask (quartz exposure mask having an overcoat formation pattern) surface. The distance between the support and the support was set to 125 μm, and pattern exposure was performed at an exposure amount of 80 mJ / cm ² (i-line) through the temporary support. After peeling off the temporary support, the laminate (film substrate) after pattern exposure was washed with a 1% by mass aqueous sodium carbonate solution at 33 ° C. for 55 seconds. Residues were removed by spraying ultrapure water from the ultra-high pressure cleaning nozzle onto the transparent film substrate after the cleaning treatment. Further, air was blown to remove moisture on the transparent film substrate. Thereafter, the entire surface was exposed with an exposure amount of 400 mJ / cm ² (i-line) without a mask using the above-described proximity type exposure machine. Finally, a heating (post-baking) treatment at 145 ° C. for 30 minutes was performed, and a laminate in which a transparent film, a transparent electrode pattern, a high refractive index transparent resin layer pattern, and a transparent resin layer pattern were continuously arranged in this order on a transparent film substrate. Got. The obtained laminate of the first aspect was used as a laminate of each example and comparative example.

<4. Production of laminate of second aspect and measurement of undercut depth>
(Preparation of laminate of second aspect)
Using the transfer film of each Example and Comparative Example from which the protective film was peeled off, a copper foil (in place of the electrode of the capacitive input device) was used instead of the transparent electrode pattern film in the production of the laminate of the first aspect. From the transfer of the high refractive index transparent resin layer and the transparent resin layer in the same manner as the production of the laminate of the first aspect except that the transfer is performed on the copper foil of the laminated PET film (manufactured by Geomat Co.), Processes (peeling of the temporary support, exposure, development, post-baking, etc.) were carried out to produce a laminate of the second embodiment in which a high refractive index transparent resin layer pattern and a transparent resin layer pattern were formed.

(Measurement of undercut depth)
After the process, the cross-sectional shape of the pattern edge of the formed transparent resin layer pattern and high refractive index transparent resin layer pattern is observed using a surface scanning electron microscope, and consists of a high refractive index transparent resin layer pattern and a transparent resin layer pattern. The depth of the undercut entering the pattern edge of the two layers was measured. The undercut depth is a value determined depending on the type of transfer film, and is a value determined regardless of process conditions such as exposure, development, and post-baking.
The obtained results are shown in Table 5 below.

[Evaluation]
<Evaluation of transparency of transparent electrode pattern>
On a transparent film substrate, a transparent film, a transparent electrode pattern, a laminate in which a high refractive index transparent resin layer pattern and a transparent resin layer pattern are laminated in this order, and a black PET material are made of a transparent adhesive tape (manufactured by 3M, product Through the name, OCA tape 8171CL), a black PET material and a transparent resin layer pattern were adhered adjacent to each other to produce a substrate for evaluation in which the entire substrate was shielded from light.
In the dark room, the fluorescent lamp (light source) and the produced evaluation substrate are incident on the transparent film substrate surface side of the evaluation substrate, and the reflected light from the surface of the transparent film substrate on which the light is incident is obliquely It observed visually and evaluated the transparent electrode pattern concealment property based on the following evaluation criteria. A, B or C is at a practical level, preferably A or B, and more preferably A.
"Evaluation criteria"
A: The transparent electrode pattern is not visible at all.
B: The transparent electrode pattern is slightly visible but hardly visible.
C: A transparent electrode pattern is visible (unclear).
D: The transparent electrode pattern is clearly visible (easy to understand).

<Development evaluation>
A laminate obtained by laminating a transparent film, a transparent electrode pattern, a high refractive index transparent resin layer pattern and a transparent resin layer pattern in this order on a transparent film substrate was performed by visual observation and observation with an optical microscope. A or B is preferable, and A is more preferable.
"Evaluation criteria"
A: A residue cannot be confirmed visually in an unexposed part.
B: A slight residue can be confirmed visually in the unexposed area.
C: There is a portion that is not developed in the unexposed portion, and many residues can be visually confirmed.
D: The temporary support could not be peeled from the substrate, and the developability could not be evaluated.

<Evaluation of pattern edge durability>
The laminated body of the second embodiment used for measurement of the undercut depth was allowed to age for 300 hours under high temperature and high humidity (85 ° C., relative humidity 85%), and then the surface state of the sample was observed to obtain a high refractive index transparent resin. The discoloration of copper inside the pattern ends of the layer and the transparent resin layer was evaluated according to the following rating. AA, A or B is at a practical level, more preferably AA or A, and particularly preferably AA.
"Evaluation criteria"
AA: The copper inside the pattern is not changed. In addition, no change after 200 hours.
A: The copper inside the pattern is not changed. In addition, after 200 hours, there is a slight discoloration that can be observed with a microscope.
B: Although it cannot be discerned visually, the discoloration of copper progresses to the inside of the pattern when observed with a microscope.
C: Discoloration of copper progresses to the inside of the pattern at a level that can be visually discerned.

<Evaluation of center durability>
Evaluation of the center part durability of the laminated body of each Example and Comparative Example was performed using the following samples for evaluation having an unpatterned high refractive index transparent resin layer and a transparent resin layer.
Using the transfer film of each Example and Comparative Example from which the protective film was peeled off, a copper foil (in place of the electrode of the capacitive input device) was used instead of the transparent electrode pattern film in the production of the laminate of the first aspect. A high refractive index is obtained in the same manner as in the production of the laminate of the first embodiment, except that it is transferred onto a copper foil of a laminated PET film (manufactured by Geomat Co.) and exposed to the whole surface without using an exposure mask. The transparent resin layer and the transparent resin layer were transferred to the subsequent processes (temporary support peeling, exposure, development, post-baking, etc.).
After the process, 5 cm ³ of salt water with a concentration of 50 g / L is dropped on the surface of the sample and uniformly spread to 50 cm ² , and then the water is volatilized at room temperature, at high temperature and high humidity (85 ° C., relative humidity 85%). Aged for 24 hours. Then, the salt water was wiped off, the surface state of the sample was observed, and evaluated according to the following scores. A, B or C is preferred, A or B is more preferred, and A is particularly preferred.
"Evaluation criteria"
A: No change on copper, high refractive index transparent resin layer and transparent resin layer surface B: Some traces are visible on the high refractive index transparent resin layer and transparent resin layer surface, but copper does not change.
C: Traces are visible on the surface of the high refractive index transparent resin layer and the transparent resin layer, but copper remains unchanged.
D: Copper is discolored.

  The above evaluation results are summarized in Table 5.

From the above Tables 4 and 5, the transfer film of the present invention has a good concealability of the transparent electrode pattern when laminated on the transparent electrode pattern, and a laminate having excellent pattern end durability when the pattern is formed after transfer. It was found that can be formed. Specifically, the transfer film of the present invention having a low swelling rate is less likely to be undercut during pattern formation, and as a result, the copper surface is transformed from the pattern end to the inside of the two layers of the high refractive index transparent resin layer and the transparent resin layer. Progress could be suppressed. Further, the transfer film of the present invention is excellent in pattern concealing property because the refractive index of the high refractive index transparent resin layer is larger than the refractive index of the transparent resin layer.
On the other hand, the transfer films of Comparative Examples 1 to 3 having a large swelling rate were easily subjected to undercut during pattern formation, and as a result, the pattern end durability was poor. The reason is considered to be that the copper surface has been modified from the pattern end of the two layers comprising the high refractive index transparent resin layer and the transparent resin layer to the inside. Deterioration of the copper surface leads to an increase in local resistance, leading to functional failure of the film sensor.
In addition, the transfer film of Comparative Example 4 in which the refractive index of the high refractive index transparent resin layer was equivalent to the refractive index of the transparent resin layer resulted in significantly inferior transparency of the transparent electrode pattern.
Furthermore, when the content of the metal oxide particles in the high refractive index transparent resin layer of the laminate of each Example and Comparative Example was measured by the following method, it was the value described in Table 5 above.
After cutting the cross section of the laminate, the cross section is observed with a TEM (transmission electron microscope). The ratio of the area occupied by the metal oxide particles in the film cross-sectional area of the high refractive index transparent resin layer is measured at any three locations in the layer, and the average value is regarded as the volume fraction (VR).
The volume fraction (VR) and the weight fraction (WR) are calculated by the following formula to calculate the weight fraction (WR) of the metal oxide particles in the high refractive index transparent resin layer.
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, content of the metal oxide particle of the high refractive index transparent resin layer of the laminated body of each Example and a comparative example can also be computed from the composition of a high refractive index transparent resin layer.

[Production of image display device (touch panel)]
A liquid crystal display device manufactured by the method described in JP-A-2009-47936, [0097] to [0119], is bonded to a film containing the laminate of each of the previously manufactured examples, and a front glass plate is further attached. By laminating, an image display device including the laminated body of each example provided with a capacitive input device as a constituent element by a known method was produced.

[Evaluation of Capacitive Input Device and Image Display Device]
The capacitive input device and the image display device including the laminated body of each example had no problem that the transparent electrode pattern was visually recognized.
The transparent resin layer and the high refractive index transparent resin layer were free from defects such as bubbles, and an image display device excellent in display characteristics was obtained.

1 substrate 1A film base material 2 mask layer (second decorative layer)
3 Transparent electrode pattern (first transparent electrode pattern)
3a Pad portion 3b Connection portion 4 Transparent electrode pattern (second transparent electrode pattern)
5 Insulating layer 6 Another conductive element (lead-out wiring)
7 transparent resin layer (preferably having the function of a transparent protective layer)
8 Opening 9 Light-shielding conductive film 10 Capacitive input device 11 Transparent film 12 High refractive index transparent resin layer (may have a function of a transparent insulating layer)
13 Laminated body 21 A region in which a transparent electrode pattern, a high refractive index transparent resin layer, and a transparent resin layer are laminated in this order 22 Non-pattern region α Taper angle 26 Temporary support 27 Thermoplastic resin layer 28 Intermediate layer 29 Protective release layer the film)
30 Transfer film 31 Terminal part 33 of routing wiring (another conductive element) Patterned transparent resin layer and high refractive index transparent resin layer 34 Opening corresponding to the terminal part of the routing wiring (another conductive element) ( (A region surrounded by the pattern edges of the transparent resin layer and the high refractive index transparent resin layer)
35 Two layers 43 consisting of a transparent resin layer and a high refractive index transparent resin layer 43 Film sensor 45 decoration layer (decoration layer of a film sensor)
51 Adhesive material C 1st direction D 2nd direction E Pattern end point F in the upper part more than half of the total film thickness of two layers which consist of a high refractive index transparent resin layer and a transparent resin layer of high refractive index transparent resin layer Contact point H between pattern edge and electrode pattern Total film thickness U of two layers consisting of high refractive index transparent resin layer and transparent resin layer U Undercut depth

Claims (26)

A temporary support;
A transparent resin layer;
It has a high refractive index transparent resin layer disposed adjacently so as to be in direct contact with the transparent resin layer in this order,
The refractive index of the high refractive index transparent resin layer is higher than the refractive index of the transparent resin layer,
A transfer film having a swelling ratio of 6.0% or less of the two layers comprising the transparent resin layer and the high refractive index transparent resin layer;
However, the swelling rate of the two layers consisting of the transparent resin layer and the high refractive index transparent resin layer is the same as that of the PET film in which a copper foil is laminated from the transfer film to the high refractive index transparent resin layer and the transparent resin layer. The percentage of the change in film thickness before and after immersion in a 1% by mass sodium carbonate aqueous solution at 33 ° C. for 55 seconds after being transferred onto the foil and exposed at an exposure amount of 80 mJ / cm ² as a percentage. It is the expressed value. The transfer film according to claim 1, wherein the transparent resin layer has a crosslinkable group of 2.50 × 10 ⁻³ pieces / g or more.   The transfer film according to claim 1, wherein the transparent resin layer contains a photopolymerization initiator in a solid content ratio of 0.3% by mass or more.   The transfer film according to claim 1, wherein an I / O value, which is a measure of hydrophilicity / hydrophobicity of the transparent resin layer, is 1.10 or less.   The transfer film according to any one of claims 1 to 4, wherein a C / H ratio, which is a ratio of carbon and hydrogen in the mass of the transparent resin layer, is 0.68 or more.   The transfer film according to any one of claims 1 to 5, wherein the acid value of the transparent resin layer is 35 to 80 mgKOH / g.   The transfer film according to any one of claims 1 to 6, wherein the transparent resin layer contains a binder polymer having an acid value of 55 to 150 mgKOH / g.   The transfer film according to claim 1, wherein the transparent resin layer has a thickness of 4 to 15 μm.   The transfer film according to claim 1, wherein the high refractive index transparent resin layer contains a metal oxidation inhibitor.   The transfer film according to claim 9, wherein the metal oxidation inhibitor has an imidazole ring, a triazole ring, or a condensed ring of these with another aromatic ring in the molecule.   The transfer film according to any one of claims 1 to 10, wherein the high refractive index transparent resin layer has a refractive index of 1.60 or more.   The transfer film according to any one of claims 1 to 11, wherein the high-refractive-index transparent resin layer contains 40% by mass or more of metal oxide particles in a solid content ratio.   The transfer film according to claim 1, wherein the high refractive index transparent resin layer has a thickness of 0.20 μm or less.   The transfer film according to any one of claims 1 to 13, wherein the swelling ratio of the two layers including the transparent resin layer and the high refractive index transparent resin layer is 1.5% or more.   It is a film for dry resists, The transfer film as described in any one of Claims 1-14. An electrode pattern;
A high refractive index transparent resin layer disposed adjacent to the electrode pattern;
A transparent resin layer disposed adjacent to the high refractive index transparent resin layer,
The refractive index of the high refractive index transparent resin layer is higher than the refractive index of the transparent resin layer,
The high refractive index transparent resin layer and the transparent resin layer are patterned,
A laminate having an undercut depth of 5.0 μm or less at a pattern end of two layers comprising the high refractive index transparent resin layer and the transparent resin layer;
However, the undercut depth of the pattern end of the two layers composed of the high refractive index transparent resin layer and the transparent resin layer is half of the total film thickness of the two layers composed of the high refractive index transparent resin layer and the transparent resin layer. The component in the direction parallel to the interface between the high refractive index transparent resin layer and the electrode pattern of the distance between the pattern end point at the upper part and the contact point between the pattern end of the high refractive index transparent resin layer and the electrode pattern. Value.   The laminate according to claim 16, wherein a C / H ratio, which is a ratio of carbon and hydrogen in the mass of the transparent resin layer, is 0.68 or more.   The laminate according to claim 16 or 17, wherein the high refractive index transparent resin layer contains a metal oxidation inhibitor.   The laminate according to claim 18, wherein the metal oxidation inhibitor has an imidazole ring, a triazole ring, or a condensed ring thereof with another aromatic ring in the molecule.   The laminate according to any one of claims 16 to 19, wherein the high refractive index transparent resin layer contains 40% by mass or more of metal oxide particles in a solid content ratio.   The high refractive index transparent resin layer and the transparent resin layer of the transfer film according to any one of claims 1 to 15 on the electrode pattern according to any one of claims 16 to 20 in this order. The laminated body of description.   The laminate according to any one of claims 16 to 21, wherein the electrode pattern is an electrode pattern located on a transparent film substrate.   The laminate according to claim 22, wherein the transparent film substrate has the electrode pattern, the high-refractive-index transparent resin layer, and the transparent resin layer, respectively, on both surfaces of the transparent film substrate.   The electrostatic capacitance type input device produced using the transfer film as described in any one of Claims 1-15.   The electrostatic capacitance type input device containing the laminated body as described in any one of Claims 16-23.   An image display device comprising the capacitive input device according to claim 24 or 25 as a component.

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