JP6865867B2 - Transfer films and transparent laminates, their manufacturing methods, capacitive input devices and image display devices - Google Patents

Description

The present invention relates to a transfer film and a transparent laminate, a method for producing them, a capacitance type input device, and an image display device. Specifically, a capacitance type input device that can detect the contact position of a finger as a change in capacitance, a transparent laminate that can be used for the input device, and a transfer film and a transfer film manufacturing method used for manufacturing the transparent laminate. The present invention relates to a method for producing a transparent laminate using the transfer film, and an image display device including the capacitance type input device as a component.

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

Such an input device (touch panel) includes a resistive film type and a capacitance type. However, since the resistance film type input device has a structure in which the film is pressed and short-circuited with a two-sheet structure of a film and glass, it has drawbacks that the operating temperature range is narrow and it is vulnerable to changes with time.

On the other hand, the capacitance type input device has an advantage that a translucent conductive film may simply be formed on a single substrate. In such a capacitance type input device, for example, the electrode patterns are extended in the directions intersecting each other, and when a finger or the like comes into contact, the change in capacitance between the electrodes is detected to detect the input position. (For example, see Patent Documents 1 to 3 below).

When using these capacitance type input devices, there is a problem of visibility such that the transparent electrode pattern is conspicuous and the appearance is not good at a position slightly away from the vicinity of specular reflection when the light source is reflected. It was. On the other hand, in Patent Document 1, an ITO pattern is formed on the substrate, and a layer made of a low refractive index dielectric material such as _{SiO 2} and a high refractive index dielectric such as _{Nb 2} O _{5 are formed only on the upper side of the ITO pattern.} It is described that by alternately stacking layers made of a material, the transparent electrode pattern becomes stealth due to the light interference effect of each of these layers, resulting in a neutral color tone.
In Patent Document 2, before forming an ITO pattern on a substrate, a low refractive index layer such as _{SiO 2} and a high refractive index layer such as _{Nb 2} O ₅ are laminated only on the lower side of the ITO pattern, and then the ITO pattern is formed. It is described that the appearance of the transparent electrode pattern shape can be prevented by forming the above.
In Patent Document 3, before forming an ITO pattern on a substrate, a low refractive index layer such as _{SiO 2} and a high refractive index layer such as _{Nb 2} O _{5 are laminated only on the lower side of the ITO pattern, and then ITO.} It is described that by forming the pattern, the transparent electrode pattern pattern and the intersections between the patterns can be made inconspicuous.

Various methods are known as methods for forming a transparent film such as a transparent insulating layer and a transparent protective film described in these documents. Here, in smartphones and tablet PCs equipped with a capacitive touch panel on a liquid crystal or organic EL display, tempered glass represented by Corning's gorilla glass is used for the front plate (the surface that comes into direct contact with a finger). It has been developed and announced. In addition, a part of the front plate having an opening for installing a pressure-sensitive (mechanical mechanism by pressing rather than changing capacitance) switch is on the market. Since these tempered glasses have high strength and are difficult to process, it is common to form the openings before the tempering treatment and then perform the tempering treatment in order to form the openings.

Patent Documents 4 and 5 describe only a method of coating when an organic material is used as a method of forming a transparent insulating layer or a transparent protective film. However, a transparent insulating layer or a transparent protective film is formed on the reinforced substrate having the above openings by using the coating method described in Patent Documents 4 and 5 using the materials described in Patent Documents 3 and 4. Attempt to do so causes leakage or protrusion of the resist component from the opening, which requires a step of removing the protruding portion, which causes a problem that the production efficiency is significantly lowered.

On the other hand, Patent Documents 6 and 7 describe transfer materials for color filters, and it is proposed to laminate the transfer material on a substrate. However, although these documents refer to the use in liquid crystal display devices, improvement of the ITO pattern visibility has not been studied, and the application of transfer materials to capacitive input devices has not been studied. Was not listed either.

Japanese Unexamined Patent Publication No. 2010-86684 JP-A-2010-152809 Japanese Unexamined Patent Publication No. 2010-257492 WO2010-061744 Japanese Unexamined Patent Publication No. 2010-061425 Japanese Unexamined Patent Publication No. 2007-334045 Japanese Unexamined Patent Publication No. 2008-107779

On the other hand, when the present inventors examined the layer configurations described in Patent Documents 1 to 3, the problem that the transparent electrode pattern was visually recognized and the transparent electrode pattern was still visually recognized was completely problematic. It turned out that it could not be solved.
An object to be solved by the present invention is to provide a transfer film capable of forming a transparent laminate in which the transparent electrode pattern is not visually recognized.

The present inventors have adjacent a temporary support and a first curable transparent resin layer having a low refractive index and a second curable transparent resin layer having a high refractive index adjusted to a specific refractive index range. A second curable transparent resin layer having a high refractive index and a first curable resin layer having a low refractive index are transferred onto the transparent electrode pattern. We have found that it is possible to solve the problem that the transparent electrode pattern in the transparent laminate is visually recognized.
The present invention, which is a specific means for solving the above problems, is as follows.

[1] A temporary support, a first curable transparent resin layer, and a second curable transparent resin layer arranged adjacent to the first curable transparent resin layer are provided in this order. The refractive index of the second curable transparent resin layer is higher than the refractive index of the first curable transparent resin layer, and the refractive index of the second curable transparent resin layer is 1.6 or more. Characteristic transfer film.
[2] In the transfer film according to [1], the refractive index of the first curable transparent resin layer is preferably 1.5 to 1.53.
[3] The transfer film according to [1] or [2] preferably has a refractive index of 1.65 or more in the second curable transparent resin layer.
[4] In the transfer film according to any one of [1] to [3], the film thickness of the second curable transparent resin layer is preferably 500 nm or less.
[5] In the transfer film according to any one of [1] to [4], the film thickness of the second curable transparent resin layer is preferably 100 nm or less.
[6] In the transfer film according to any one of [1] to [5], the film thickness of the first curable transparent resin layer is preferably 1 μm or more.
[7] In the transfer film according to any one of [1] to [6], it is preferable that the first curable transparent resin layer contains a polymerizable compound and a photopolymerization initiator.
[8] The transfer film according to any one of [1] to [7] preferably has a double bond consumption rate of 10% or less of the first curable transparent resin layer.
[9] In the transfer film according to any one of [1] to [8], it is preferable that the second curable transparent resin layer contains fine particles having a refractive index of 1.55 or more.
[10] In the transfer film according to any one of [1] to [9], it is preferable that the second curable transparent resin layer contains a polymerizable compound.
[11] In the transfer film according to any one of [1] to [10], the first curable resin layer and the second curable resin layer are both thermosetting resin layers. Is preferable.
[12] The transfer film according to any one of [1] to [11] preferably has a thermoplastic resin layer between the temporary support and the first curable transparent resin layer. ..
[13] The transfer film according to [12] preferably further contains an intermediate layer between the first curable transparent resin layer and the thermoplastic resin layer.
[14] The first curable transparent resin is formed by (b) forming a first curable transparent resin layer containing a polymerizable compound and a photopolymerization initiator on the temporary support, and (c) by exposure. It has a step of curing the layer and a step of (d) forming a second thermosetting transparent resin layer directly on the first curable transparent resin layer after curing, and the second curing A transfer characterized in that the refractive index of the transparent resin layer is higher than the refractive index of the first curable transparent resin layer and the refractive index of the second curable transparent resin layer is 1.55 or more. How to make a film.
[15] In the method for producing a transfer film according to [14], (a) a step of forming a thermoplastic resin layer is further performed before the first curable transparent resin layer is formed on the temporary support. It is preferable to include it.
[16] On the transparent electrode pattern, the second curable transparent resin layer and the first curable transparent resin layer of the transfer film according to any one of [1] to [13] are placed in this order. A method for producing a transparent laminate, which comprises a step of laminating.
[17] The method for producing a transparent laminate according to [16] preferably further includes a step of removing the temporary support.
[18] A transparent laminate produced by the method for producing a transparent laminate according to [16] or [17].
[19] A transparent electrode pattern, a second curable transparent resin layer arranged adjacent to the transparent electrode pattern, and a first curable resin layer arranged adjacent to the second curable transparent resin layer. It has a transparent resin layer, the refractive index of the second curable transparent resin layer is higher than the refractive index of the first curable transparent resin layer, and the refractive index of the second curable transparent resin layer is higher. A transparent laminate characterized by being 1.6 or more.
[20] The transparent laminate according to [19] has a refractive index of 1.6 to 1.78 and is a film on the side of the transparent electrode pattern opposite to the side on which the second curable transparent resin layer is formed. It is preferable to further have a transparent film having a thickness of 55 to 110 nm.
[21] In the transparent laminate according to [19] or [20], the double bond consumption rate of the first curable transparent resin layer is preferably 10% or less.
[22] The transparent laminate according to any one of [1] to [13], or the transparent laminate according to any one of [18] to [21]. Capacitive input device characterized by including.
[23] An image display device including the capacitance type input device according to [22] as a component.

According to the present invention, it is possible to provide a transfer film capable of forming a transparent laminate in which the transparent electrode pattern is not visually recognized.

It is sectional drawing which shows an example of the structure of the capacitance type input device of this invention. It is sectional drawing which shows another example of the structure of the capacitance type input device of this invention. It is explanatory drawing which shows an example of the front surface plate in this invention. It is explanatory drawing which shows an example of the relationship between a transparent electrode pattern and a non-pattern area in this invention. It is a top view which shows an example of the tempered glass which formed an opening. It is a top view which shows an example of the front plate on which a mask layer was formed. It is a top view which shows an example of the front plate which formed the 1st transparent electrode pattern. It is a top view which shows an example of the front plate which formed the 1st and 2nd transparent electrode patterns. It is a top view which shows an example of the front plate which formed the conductive element different from the 1st and 2nd transparent electrode patterns. It is explanatory drawing which shows the cross section of a metal nanowire. It is explanatory drawing which shows an example of the taper shape of the end part of a transparent electrode pattern. It is sectional drawing which shows an example of the structure of the transparent laminated body of this invention. It is sectional drawing which shows an example of the structure of the transfer film of this invention.

Hereinafter, the transparent laminate, the capacitance type input device, and the image display device of the present invention will be described. The description of the constituent elements described below may be based on typical embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples. The numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
In the present specification, the refractive index of each layer means the refractive index at a wavelength of 550 nm, unless otherwise specified.

[Transfer film]
In the transfer film of the present invention, the temporary support, the first curable transparent resin layer, and the second curable transparent resin layer arranged adjacent to the first curable transparent resin layer are arranged in this order. The refractive index of the second curable transparent resin layer is higher than the refractive index of the first curable transparent resin layer, and the refractive index of the second curable transparent resin layer is 1.6 or more. It is characterized by being.
With such a configuration, it is possible to form a transparent laminated body in which the transparent electrode pattern is not visually recognized. Without being bound by any theory, the difference in refractive index between the transparent electrode pattern (preferably ITO) and the second curable transparent resin layer, and the second curable transparent resin layer and the first curing. By reducing the difference in the refractive index of the transparent resin layer, light reflection is reduced, the transparent electrode pattern becomes difficult to see, and visibility can be improved.
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 capacitance type input device.

<Temporary support>
The transfer film of the present invention has a temporary support.
As the temporary support, a material that is flexible and does not significantly deform, shrink or stretch under pressure or pressure and heating can be used. Examples of such a support include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, polycarbonate film and the like, and among them, biaxially stretched polyethylene terephthalate film is particularly preferable.

The thickness of the temporary support is not particularly limited, and is generally in the range of 5 to 200 μm, and is particularly preferably in the range of 10 to 150 μm in terms of ease of handling and versatility.
Further, the temporary support may be transparent, or may contain silicon dyed, alumina sol, chromium salt, zirconium salt and the like.
Further, the temporary support can be imparted with conductivity by the method described in Japanese Patent Application Laid-Open No. 2005-221726.

<First curable transparent resin layer and second curable transparent resin layer>
The transfer film of the present invention has a first curable transparent resin layer and a second curable transparent resin layer arranged adjacent to the first curable transparent resin layer, and the second curing The refractive index of the transparent resin layer is higher than that of the first curable transparent resin layer, and the refractive index of the second curable transparent resin layer is 1.6 or more.
The first curable transparent resin layer and the second curable transparent resin layer may be thermosetting, photocurable, thermosetting and photocurable. Among them, the fact that the first curable transparent resin layer and the second curable transparent resin layer are at least thermosetting transparent resin layers can be thermally cured after transfer to impart the reliability of the film. Preferably, the thermosetting transparent resin layer and the photocurable transparent resin layer are more likely to be photocured after transfer to form a film, and to be heat-cured after film formation to impart the reliability of the film. preferable.
In the present specification, for convenience of explanation, the first curable transparent resin layer and the second curable transparent resin layer of the transfer film of the present invention are transferred onto the transparent electrode pattern, and these layers are transferred. When these layers lose their photocurability after photocuring, the first curable transparent resin layer and the second curable, respectively, continue regardless of whether these layers have thermosetting property or not. It is called a transparent resin layer. Further, these layers may be photo-cured and then heat-cured. In that case, the first curable transparent resin layer and the above-mentioned first curable transparent resin layer and the above-mentioned layers are continued regardless of whether or not these layers have curability. It is called a second curable transparent resin layer.

(Material of the first curable transparent resin layer and the second curable transparent resin layer)
The materials of the first curable transparent resin layer and the second curable transparent resin layer are not particularly limited as long as the above-mentioned refractive index range is satisfied.
The transfer film of the present invention may be a negative type material or a positive type material.
When the transfer film of the present invention is a negative type material, metal oxide particles, a resin (preferably an alkali-soluble resin), and polymerization are formed on the first curable transparent resin layer and the second curable transparent resin layer. It preferably contains a sex compound, a polymerization initiator or a polymerization initiator system. Further, additives and the like are used, but the present invention is not limited to this.

Transfer film of the present invention, the first curable transparent resin layer and the second curable transparent resin layer is Ru transparent resin film der.

In the present invention, it is preferable that the first curable transparent resin layer and the second curable transparent resin layer are transparent resin films.
The method for controlling the refractive index of the transparent resin film is not particularly limited, but a transparent resin film having a desired refractive index can be used alone, or a transparent resin film to which fine particles such as metal fine particles and metal oxide fine particles are added can be used. It can be used.

The resin composition used for the transparent resin film preferably contains metal oxide particles for the purpose of adjusting the refractive index and light transmittance. Since the metal oxide particles have high transparency and light transmittance, a positive photosensitive resin composition having a high refractive index and excellent transparency can be obtained.
The metal oxide particles preferably have a higher refractive index than the refractive index of the resin composition made of the material excluding the particles, and specifically, the refractive index in light having a wavelength of 400 to 750 nm is high. Particles of 1.50 or more are more preferable, particles having a refractive index of 1.70 or more are further preferable, and particles of 1.90 or more are particularly preferable.
Here, the refractive index of light having a wavelength of 400 to 750 nm is 1.50 or more, which means that the average refractive index of light having a wavelength in the above range is 1.50 or more. It is not necessary that the refractive index of all light having a wavelength is 1.50 or more. The average refractive index is a value obtained by dividing the sum of the measured values of the refractive index for each light having a wavelength in the above range by the number of measurement points.

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

From the viewpoint of the transparency of the resin composition, the average primary particle size of the metal oxide particles is preferably 1 to 200 nm, particularly preferably 3 to 80 nm. Here, the average primary particle size of the particles refers to the arithmetic average of 200 arbitrary particles measured by an electron microscope. If the shape of the particle is not spherical, the longest side is the diameter.

Further, the metal oxide particles may be used alone or in combination of two or more.
The content of the metal oxide particles in the resin composition may be appropriately determined in consideration of the refractive index required for the optical member obtained by the resin composition, the light transmittance, and the like. It is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, based on the total solid content of the above.
In the transfer film of the present invention, the transparent resin film _{having at least one of ZrO 2} particles and TiO ₂ particles is a refraction of the first curable transparent resin layer and the second curable transparent resin layer. It is preferable from the viewpoint of controlling the refractive index within the range of the rate, and ZrO ₂ particles are more preferable.

The resin (referred to as a binder or polymer) or other additive used for the transparent resin film is not particularly limited as long as it does not contradict the gist of the present invention, and the second curable transparent resin in the transfer film of the present invention can be used. The resin and other additives used can be preferably used.

The resin (referred to as a binder or polymer) used for the first curable transparent resin layer and the second curable transparent resin layer is preferably an alkali-soluble resin, and the alkali-soluble resin is JP2011-95716. The polymers described in paragraphs [0025] of JP-A and paragraphs [0033] to [0052] of JP-A-2010-237589 can be used.

As the polymerizable compound, the polymerizable compound described in paragraphs [0023] to [0024] of Japanese Patent No. 4098550 can be used.
As the polymerization initiator or the polymerization initiation system, the polymerizable compounds described in [0031] to [0042] described in JP-A-2011-95716 can be used.

Further, an additive may be used for the first curable transparent resin layer and the second curable transparent resin layer. Examples of the additive include the surfactants described in paragraph [0017] of Japanese Patent No. 4502784, paragraphs [0060] to [0071] of Japanese Patent Application Laid-Open No. 2009-237362, and paragraph [0017] of Japanese Patent No. 4502784. 0018], and other additives described in paragraphs [0058] to [0071] of JP-A-2000-310706 can be mentioned.
Further, as the solvent for producing the photosensitive film by coating, the solvent described in paragraphs [0043] to [0044] of JP2011-95716A can be used.

Although the case where the transfer film of the present invention is a negative type material has been mainly described above, the transfer film of the present invention may be a positive type material. When the transfer film of the present invention is a positive type material, for example, the material described in JP-A-2005-221726 is used for the first curable transparent resin layer and the second curable transparent resin layer. However, it is not limited to this.

(First curable transparent resin layer)
In the transfer film of the present invention, the refractive index of the first curable transparent resin layer is preferably 1.5 to 1.53, more preferably 1.5 to 1.52. It is particularly preferably 51 to 1.52.

In the transfer film of the present invention, the layer thickness of the first curable transparent resin layer is sufficient when the first curable transparent resin layer is used to form a transparent protective layer of a capacitance type input device. From the viewpoint of exerting the protective ability, it is preferably 1 μm or more, more preferably 1 to 10 μm, particularly preferably 1 to 5 μm, and even more preferably 1 to 3 μm.

As the material of the first curable transparent resin layer, any polymer component or any polymerizable compound component can be used without particular limitation, but from the viewpoint of being used as a transparent protective film of a capacitance type input device, the surface is used. Those having high hardness and heat resistance are preferable, and among the alkali-soluble resins and the polymerizable compounds contained in the first curable transparent resin layer and the second curable transparent resin layer, known photosensitive siloxane resin materials. , Acrylic resin material and the like are preferably used.

In the transfer film of the present invention, the first curable transparent resin layer may contain the polymerizable compound and the photopolymerization initiator to increase the strength of the film after photocuring, and the first method. The first curable transparent resin layer is photocured between the time when the curable transparent resin layer is formed and the time before the second curable transparent resin layer is formed, and the first curable transparent resin layer is formed. It is preferable from the viewpoint of increasing the double bond consumption rate of the above, clarifying the interface between the first curable transparent resin layer and the second curable resin layer, and further improving the visibility of the transparent electrode pattern.
In the first curable transparent resin layer, the photopolymerization initiator is preferably contained in an amount of 1% by mass or more, preferably 2% by mass or more, based on the solid content of the first curable transparent resin layer. It is more preferable, and it is particularly preferable that it is contained in an amount of 3% by mass or more.
Further, the content of the photopolymerization initiator in the first curable transparent resin layer may be larger than the content of the photopolymerization initiator in the second curable transparent resin layer, as described above. It is preferable from the viewpoint that the first curable transparent resin layer is appropriately photocured between the time when the first curable transparent resin layer is formed and the time before the second curable transparent resin layer is formed. The content of the photopolymerization initiator in the first curable transparent resin layer is preferably 1.5 times or more the content of the photopolymerization initiator in the second curable transparent resin layer. It is more preferably 1.5 to 5 times, and particularly preferably 2 to 4 times.

The first curable transparent resin layer may or may not contain metal oxide particles. In order to control the refractive index of the first curable transparent resin layer in the above range, metal oxide particles can be included in an arbitrary ratio depending on the type of polymer or polymerizable compound used. In the first curable transparent resin layer, the metal oxide particles are preferably contained in an amount of 0 to 35% by mass, preferably 0 to 10% by mass, based on the solid content of the first curable transparent resin layer. It is more preferable that it is contained, and it is particularly preferable that it is not contained.

(Second curable transparent resin layer)
The transfer film of the present invention is arranged adjacent to the first curable transparent resin layer, has a refractive index higher than that of the first curable transparent resin layer, and has a refractive index of 1.6 or more. It has a second curable transparent resin layer.
In the transfer film of the present invention, the refractive index of the second curable transparent resin layer is preferably 1.65 or more.
On the other hand, the upper limit of the refractive index of the second curable transparent resin layer is not particularly limited, but is preferably 1.78 or less, and may be 1.74 or less.

In the transfer film of the present invention, the film thickness of the second curable transparent resin layer is preferably 500 nm or less, more preferably 110 nm or less. The thickness of the second curable transparent resin layer is particularly preferably 55 to 100 nm, more preferably 60 to 90 nm, and even more preferably 70 to 90 nm.

In the transfer film of the present invention, it is preferable that the second curable transparent resin layer contains the polymerizable compound from the viewpoint of curing to increase the strength of the film.

The second curable transparent resin layer may or may not contain metal oxide particles, but the inclusion of metal oxide particles includes the second curable transparent resin in the above range. This is preferable from the viewpoint of controlling the refractive index of the layer. The second curable transparent resin layer may contain metal oxide particles in an arbitrary ratio depending on the type of polymer or polymerizable compound used, but is contained in the second curable transparent resin layer. The metal oxide particles are preferably contained in an amount of 40 to 95% by mass, more preferably 55 to 95% by mass, and 82 to 90% based on the solid content of the second curable transparent resin layer. It is particularly preferable that it is contained in% by mass.

<Thermoplastic resin layer>
In the transfer film of the present invention, it is preferable that a thermoplastic resin layer is provided between the temporary support and the first curable transparent resin layer. When the first curable transparent resin layer and the second curable transparent resin layer are transferred to form a transparent laminate using the transfer film having the thermoplastic resin layer, air bubbles are formed in each element formed by the transfer. Is less likely to occur, image unevenness or the like is less likely to occur in the image display device, and excellent display characteristics can be obtained.
The thermoplastic resin layer is preferably alkali-soluble. The thermoplastic resin layer plays a role as a cushioning material so as to be able to absorb the unevenness of the base surface (including the unevenness due to the image already formed), and depends on the unevenness of the target surface. It is preferable that it has a property of being deformable.

The thermoplastic resin layer preferably contains the organic polymer substance described in JP-A-5-72724 as a component, and is preferably a polymer according to the Vicat method [specifically, the American material test method ASTMD 1235. A mode containing at least one selected from organic polymer substances having a softening point of about 80 ° C. or lower according to the softening point measuring method] is particularly preferable.

Specifically, with polyolefins such as polyethylene and polypropylene, ethylene copolymers of 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 and styrene copolymer with (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) acrylic acid and vinyl acetate, etc. Examples thereof include organic polymers such as coalesced, vinyl acetate copolymer nylon, copolymer nylon, N-alkoxymethylated nylon, and polyamide resin such as N-dimethylaminoated nylon.

The layer thickness of the thermoplastic resin layer is preferably 3 to 30 μm. When the layer thickness of the thermoplastic resin layer is less than 3 μm, the followability at the time of laminating is insufficient, and the unevenness of the base surface may not be completely absorbed. Further, when the layer thickness exceeds 30 μm, a load is applied to drying (solvent removal) at the time of forming the thermoplastic resin layer on the temporary support, and it takes time to develop the thermoplastic resin layer. May worsen process suitability. The thickness of the thermoplastic resin layer is more preferably 4 to 25 μm, and particularly preferably 5 to 20 μm.

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

(Viscosity of Thermoplastic Resin Layer and Photocurable Resin Layer)
The viscosity of the thermoplastic resin layer measured at 100 ° C. is in the region of 1000 to 10000 Pa · sec, and the viscosity of the photocurable resin layer measured at 100 ° C. is in the region of 2000 to 50,000 Pa · sec. It is preferable to satisfy A).
Formula (A): Viscosity of thermoplastic resin layer <Viscosity of photocurable resin layer

Here, the viscosity of each layer can be measured as follows. The solvent is removed from the coating liquid for the thermoplastic resin layer or the photocurable resin layer by atmospheric pressure and vacuum drying to prepare a measurement sample. For example, as a measuring instrument, Vibron (DD-III type: manufactured by Toyo Baldwin Co., Ltd.) The measurement can be performed under the conditions of a measurement start temperature of 50 ° C., a measurement end temperature of 150 ° C., a temperature rise rate of 5 ° C./min, and a frequency of 1 Hz / deg, and a measured value of 100 ° C. can be used.

<Middle layer>
The transfer film of the present invention may further contain an intermediate layer between the first curable transparent resin layer and the thermoplastic resin layer, which is a component when a plurality of layers are applied and when stored after application. It is preferable from the viewpoint of preventing mixing of the above. As the intermediate layer, an oxygen blocking film having an oxygen blocking function, which is described as a "separation layer" in Japanese Patent Application Laid-Open No. 5-72724, is preferable, the sensitivity at the time of exposure is increased, and the time load of the exposure machine is reduced. Gain and productivity are improved.

In the transfer film of the present invention, it is preferable to further provide a protective film (protective release layer) or the like on the surface of the second curable transparent resin layer.

As the intermediate layer and the protective film, those described in paragraphs [0083] to [0087] and [093] of JP-A-2006-259138 can be appropriately used.

FIG. 12 shows an example of a preferable configuration of the transfer film of the present invention. In FIG. 12, the temporary support 26, the thermoplastic resin layer 27, the intermediate layer 28, the first curable transparent resin layer 7, the second curable transparent resin layer 12, and the protective release layer (protective film) 29 are in this order. It is the schematic of the transfer film 30 of this invention which was laminated adjacent to each other.

[Manufacturing method of transfer film]
The transfer film of the present invention can be produced according to the method for producing a photosensitive transfer material described in paragraphs [0094] to [0998] of JP-A-2006-259138. Among them, the transfer film of the present invention is preferably produced by the following method for producing the transfer film of the present invention.

The method for producing a transfer film of the present invention comprises the steps of (b) forming a first curable transparent resin layer containing a polymerizable compound and a photopolymerization initiator on a temporary support, and (c) exposure. It includes a step of curing the first curable transparent resin layer and a step of (d) forming a second thermosetting transparent resin layer directly on the first curable transparent resin layer after curing. When the refractive index of the second curable transparent resin layer is higher than that of the first curable transparent resin layer and the refractive index of the second curable transparent resin layer is 1.55 or more. It is characterized by being.
With such a configuration, the double bond consumption rate of the first curable transparent resin layer is increased to 10% or more, and the interface between the first curable transparent resin layer and the second curable resin layer is clarified. The visibility of the transparent electrode pattern can be further improved. In particular, even when the polymer and the polymerizable compound used for the first curable transparent resin layer and the second curable resin layer are the same, the interface between the two can be clarified by such a configuration.

The method for producing a transfer film of the present invention preferably further includes (a) a step of forming a thermoplastic resin layer before forming the first curable transparent resin layer on the temporary support.

In the method for producing a transfer film of the present invention, after the step of forming the thermoplastic resin layer (a), a step of forming an intermediate layer between the thermoplastic resin layer and the first curable transparent resin layer is performed. It is preferable to include it. Specifically, when the photosensitive film having an intermediate layer is formed, a solution (a coating solution for a thermoplastic resin layer) in which an additive is dissolved together with a thermoplastic organic polymer is applied onto the temporary support. After drying to provide a thermoplastic resin layer, a preparation solution (coating solution for intermediate layer) prepared by adding a resin or an additive to a solvent that does not dissolve the thermoplastic resin layer is applied onto the thermoplastic resin layer. , Dry and laminate the intermediate layer, further apply a coating liquid for colored photosensitive resin layer prepared using a solvent that does not dissolve the intermediate layer, and dry to laminate the colored photosensitive resin layer. By doing so, it can be suitably produced.

[Transparent laminate]
The transparent laminate of the present invention was arranged adjacent to the transparent electrode pattern, the second curable transparent resin layer arranged adjacent to the transparent electrode pattern, and the second curable transparent resin layer. The second curable transparent resin having a first curable transparent resin layer and having a refractive index of the second curable transparent resin layer higher than that of the first curable transparent resin layer. The layer has a refractive index of 1.6 or more.
With such a configuration, it is possible to solve the problem that the transparent electrode pattern is visually recognized.
In the transparent laminate of the present invention, the double bond consumption rate of the first curable transparent resin layer is 10% or less, that is, the first curable transparent resin layer and the second curable transparent resin. It is preferable from the viewpoint that the interface between the layers can be easily formed and the visibility of the transparent electrode pattern is further improved.

<Structure of transparent laminate>
The transparent 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 transparent electrode pattern opposite to the side on which the second curable transparent resin layer is formed. It is preferable to have a transparent film further from the viewpoint of further improving the visibility of the transparent electrode pattern. In the present specification, when the term "transparent film" is used without particular notice, it refers to the above-mentioned "transparent film having a refractive index of 1.6 to 1.78 and a film thickness of 55 to 110 nm".
The transparent laminate of the present invention further has a transparent substrate on the side opposite to the side on which the transparent electrode pattern of the transparent film having a refractive index of 1.6 to 1.78 and a film thickness of 55 to 110 nm is formed. Is preferable.

FIG. 11 shows an example of the configuration of the transparent laminate of the present invention.
In FIG. 11, the transparent substrate 1, the transparent film 11 having a refractive index of 1.6 to 1.78 and a film thickness of 55 to 110 nm, the transparent electrode pattern 4, the second curable transparent resin layer 12, and the second. The region 21 in which one curable transparent resin layer 7 is laminated in this order is provided in the plane.
In-plane means a direction substantially parallel to a plane parallel to the transparent substrate of the transparent laminate. The fact that the transparent electrode pattern 4, the second curable transparent resin layer 12 and the first curable transparent resin layer 7 are laminated in this order is included in the plane of the transparent electrode pattern 4, the second curable transparent resin layer. For the region where the resin layer 12 and the first curable transparent resin layer 7 are laminated in this order, the normal projection onto the surface parallel to the transparent substrate of the transparent laminate is in the plane parallel to the transparent substrate of the transparent laminate. It means that it exists.
Here, when the transparent laminate of the present invention is used in a capacitance type input device described later, the transparent electrode patterns are the first transparent electrode pattern and the second transparent electrode pattern in two directions substantially orthogonal to each other in the row direction and the column direction, respectively. It may be provided as a transparent electrode pattern (see, for example, FIG. 3). For example, in the configuration of FIG. 3, the transparent electrode pattern in the transparent laminate of the present invention may be the second transparent electrode pattern 4 or the pad portion 3a of the first transparent electrode pattern 3. In other words, in the following description of the transparent laminate of the present invention, the reference numeral of the transparent electrode pattern may be represented by "4", but the transparent electrode pattern in the transparent laminate of the present invention is the static of the present invention. The use is not limited to the use for the second transparent electrode pattern 4 in the capacitance type input device, and may be used, for example, as the pad portion 3a of the first transparent electrode pattern 3.

The transparent laminate of the present invention preferably contains a non-patterned region in which the transparent electrode pattern is not formed. In the present specification, the non-patterned region means a region in which the transparent electrode pattern 4 is not formed.
FIG. 11 shows an embodiment in which the transparent laminate of the present invention includes a non-patterned region 22.
In the transparent laminate of the present invention, the transparent substrate, the transparent film, and the second curable transparent resin layer are laminated in this order on at least a part of the non-pattern region 22 on which the transparent electrode pattern is not formed. It is preferable to include the region in the plane.
In the transparent laminate of the present invention, the transparent film and the second curable transparent resin layer are adjacent to each other in a region where the transparent substrate, the transparent film and the second curable transparent resin layer are laminated in this order. It is preferable to do so.
However, other members may be arranged at arbitrary positions in the other regions of the non-patterned region 22 as long as it does not contradict the gist of the present invention. For example, the transparent laminate of the present invention has a capacitance described later. When used in a mold input device, the mask layer 2 in FIG. 1A, the insulating layer 5, the conductive element 6, and the like can be laminated.

In the transparent laminate of the present invention, it is preferable that the transparent substrate and the transparent film are adjacent to each other.
FIG. 11 shows a mode in which the transparent film 11 is laminated adjacent to the transparent substrate 1.
However, a third transparent film may be laminated between the transparent substrate and the 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 having a refractive index of 1.5 to 1.52 (not shown in FIG. 11) between the transparent substrate and the transparent film.

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

In the transparent 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 a mode in which the transparent electrode pattern 4 is laminated adjacent to a part of the region of the transparent film 11.
As shown in FIG. 11, the end portion of the transparent electrode pattern 4 may have a tapered shape, although the shape is not particularly limited. For example, the surface on the transparent substrate side is the transparent substrate. It may have a tapered shape that is wider than the surface on the opposite side.
Here, when the end of the transparent electrode pattern has a tapered shape, the angle of the end of the transparent electrode pattern (hereinafter, also referred to as a taper angle) is preferably 30 ° or less, preferably 0.1 to 15 °. Is more preferable, and 0.5 to 5 ° is particularly preferable.
The method for measuring the taper angle in the present specification can be obtained by taking a micrograph of the end portion of the transparent electrode pattern, approximating the tapered portion of the micrograph to a triangle, and directly measuring the taper angle.
FIG. 10 shows an example of a case where the end portion of the transparent electrode pattern has a tapered shape. The triangle that approximates the tapered portion in FIG. 10 has a bottom surface of 800 nm and a height (thickness of the upper bottom portion substantially parallel to the bottom surface) of 40 nm, and the taper angle α at this time is about 3 °. The bottom surface of the triangle that approximates the tapered portion is preferably 10 to 3000 nm, more preferably 100 to 1500 nm, and particularly preferably 300 to 1000 nm. The preferable range of the height of the triangle that approximates the tapered portion is the same as the preferable range of the film thickness of the transparent electrode pattern.

The transparent laminate of the present invention preferably includes a region in which the transparent electrode pattern and the second curable transparent resin layer are adjacent to each other in the plane.
FIG. 11 shows the transparent electrode pattern, the second curable transparent resin layer, and the second curable transparent resin layer in the region 21 in which the transparent electrode pattern, the second curable transparent resin layer, and the first curable transparent resin layer are laminated in this order. A mode in which the resin layer and the first curable transparent resin layer are adjacent to each other is shown.

Further, in the transparent laminate of the present invention, both the transparent electrode pattern and the non-patterned region 22 in which the transparent electrode pattern is not formed are continuously directly formed by the transparent film and the second curable transparent resin layer. Alternatively, it is preferably coated via another layer.
Here, "continuously" means that the transparent film and the second curable transparent resin layer are not a pattern film but a continuous film. That is, it is preferable that the transparent film and the second curable transparent resin layer do not have an opening from the viewpoint of making the transparent electrode pattern less visible.
Further, it is preferable that the transparent electrode pattern and the non-patterned region 22 are directly coated by the transparent film and the second curable transparent resin layer rather than being coated through other layers. Examples of the "other layer" when coated via another layer include the insulating layer 5 included in the capacitance type input device of the present invention described later, and the capacitance type input device of the present invention described later. When two or more transparent electrode patterns are included as in the above, a second layer transparent electrode pattern and the like can be mentioned.
In FIG. 11, the second curable transparent resin layer straddles the region where the transparent electrode pattern 4 on the transparent film 11 is not laminated and the transparent electrode pattern 4 and is adjacent to each other. A mode in which 12 are laminated is shown.
When the end portion of the transparent electrode pattern 4 has a tapered shape, it is preferable that the second curable transparent resin layer 12 is laminated along the tapered shape (with the same inclination as the taper angle).

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

<Material of transparent laminate>
(Transparent board)
In the transparent laminate of the present invention, it is preferable that the transparent substrate is a glass substrate having a refractive index of 1.5 to 1.55. The refractive index of the transparent substrate is particularly preferably 1.5 to 1.52.
The transparent substrate is made of a translucent substrate such as a glass substrate, and tempered glass typified by Corning's gorilla glass can be used. Further, as the transparent substrate, the materials used in JP-A-2010-86684, JP-A-2010-152809 and JP-A-2010-257492 can be preferably used, and the contents of these documents are described. Incorporated herein.

(Transparent electrode pattern)
The refractive index of the transparent electrode pattern is preferably 1.75 to 2.1.
The material of the transparent electrode pattern is not particularly limited, and a known material can be used. For example, it can be produced of a translucent conductive metal oxide film such as ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide). Examples of such a 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 film 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. Further, the first transparent electrode pattern 3, the second transparent electrode pattern 4, and the conductive element 6 described later are made of a photosensitive film having a photocurable resin layer using the conductive fibers. It can also be manufactured. In addition, when the first conductive pattern or the like is formed by ITO or the like, paragraphs [0014] to [0016] of Japanese Patent No. 4506785 can be referred to. Among them, the transparent electrode pattern is preferably an ITO film.
In the transparent laminate of the present invention, it is preferable that the transparent electrode pattern is an ITO film having a refractive index of 1.75 to 2.1.

(First curable transparent resin layer and second curable transparent resin layer)
The preferable range of the first curable transparent resin layer and the second curable transparent resin layer is the preferable range of the first curable transparent resin layer and the second curable transparent resin layer in the transfer film of the present invention. Is similar to.

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

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

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

(Third transparent film)
The refractive index of the third transparent film is preferably 1.5 to 1.55 from the viewpoint of improving the visibility of the transparent electrode pattern by approaching the refractive index of the transparent substrate, and 1.5 to 1 It is more preferably .52.

[Manufacturing method of transparent laminate]
The method for producing a transparent laminate of the present invention involves laminating the second curable transparent resin layer and the first curable transparent resin layer of the transfer film of the present invention on a transparent electrode pattern in this order. It is characterized by including.
With such a configuration, the second curable transparent resin layer and the first curable transparent resin layer of the transparent laminate can be collectively transferred, and there is no problem that the transparent electrode pattern is visually recognized. The body can be easily and productively manufactured.
The second curable transparent resin layer in the method for producing a transparent laminate of the present invention is directly on the transparent electrode pattern and on the transparent film in the non-patterned region, or via another layer. , The film is formed.

(Surface treatment of transparent substrate)
Further, in order to improve the adhesion of each layer by laminating in the subsequent transfer step, the non-contact surface of the transparent substrate (front plate) can be surface-treated in advance. As the 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 (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3% by mass aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) is sprayed with a shower for 20 seconds to wash with pure water shower. To do. After that, it is reacted 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 transparent electrode pattern is formed by using the method for forming the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 in the description of the capacitance type input device of the present invention described later. It is possible to form a film on a transparent substrate or a transparent film having a refractive index of 1.6 to 1.78 and a film thickness of 55 to 110 nm, and a method using a photosensitive film is preferable.

(Formation of the first curable transparent resin layer and the second curable transparent resin layer)
The method for forming the first curable transparent resin layer and the second curable transparent resin layer includes a protective film removing step of removing the protective film from the transfer film of the present invention and the protective film being removed. The transfer step of transferring the first curable transparent resin layer and the second curable transparent resin layer of the transfer film of the present invention onto the transparent electrode pattern, and the first curability transferred onto the transparent electrode pattern. It has an exposure step of exposing the transparent resin layer and the second curable transparent resin layer, and a development step of developing the exposed first curable transparent resin layer and the second curable transparent resin layer. The method can be mentioned.

-Transfer process-
The transfer step is a step of transferring the first curable transparent resin layer and the second curable transparent resin layer of the transfer film of the present invention from which the protective film has been removed onto a transparent electrode pattern.
At this time, a method including a step of laminating the first curable transparent resin layer and the second curable transparent resin layer of the transfer film of the present invention on the transparent electrode pattern and then removing the temporary support is preferable.
The transfer (bonding) of the first curable transparent resin layer and the second curable transparent resin layer to the substrate surface is performed by the first curable transparent resin layer and the second curable transparent resin. The layer is superposed on the surface of the transparent electrode pattern, and is pressurized and heated. For bonding, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used.

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

The exposure step is a step of exposing the first curable transparent resin layer and the second curable transparent resin layer transferred onto the transparent electrode pattern.
Specifically, a predetermined mask is placed above the first curable transparent resin layer and the second curable transparent resin layer formed on the transparent electrode pattern, and then the mask and the thermoplastic resin. A method of exposing the first curable transparent resin layer and the second curable transparent resin layer from above the mask via the layer and the intermediate layer, or the thermoplastic resin layer and the intermediate layer without using the mask. Examples thereof include a method of fully exposing the first curable transparent resin layer and the second curable transparent resin layer through the surface.
Here, the light source for the exposure is one that can irradiate light in a wavelength range (for example, 365 nm, 405 nm, etc.) capable of curing the first curable transparent resin layer and the second curable transparent resin layer. If there is, it can be appropriately selected and used. Specific examples thereof include ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure amount is usually ^{about 5 to 200 mJ / cm 2} , preferably about 10 to 100 mJ / cm ^2.

The developing step is a step of developing the exposed photocurable resin layer.
In the present invention, the developing step is not a developing step in a narrow sense in which the pattern-exposed first curable transparent resin layer and the second curable transparent resin layer are pattern-developed with a developing solution, but is exposed to the entire surface. This is a developing step including the case where the first curable transparent resin layer and the second curable transparent resin layer itself do not form a pattern only by removing the thermoplastic resin layer and the intermediate layer later.
The development can be carried out using a developing solution. The developing solution is not particularly limited, and known developing solutions such as those described in JP-A-5-72724 can be used. The developing solution preferably has a photocurable resin layer having a dissolution-type developing behavior, and for example, a developing solution containing a compound having pKa = 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable. On the other hand, when the first curable transparent resin layer and the second curable transparent resin layer itself do not form a pattern, the developing solution has a development behavior of a type that does not dissolve the non-alkali development type coloring composition layer. Those containing, for example, a compound having pKa = 7 to 13 at a concentration of 0.05 to 5 mol / L are preferable. A small amount of an organic solvent miscible with water may be further added to the developing solution. Organic solvents that are 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.

The development method may be any of paddle development, shower development, shower & spin development, dip development and the like. Here, the shower development will be described. The uncured portion can be removed by spraying a developing solution on the first curable transparent resin layer and the second curable transparent resin layer after exposure by a shower. it can. When a thermoplastic resin layer or an intermediate layer is provided, an alkaline liquid having low solubility in the photocurable resin layer is sprayed by a shower or the like before development to remove the thermoplastic resin layer and the intermediate layer. It is preferable to keep it. Further, after development, it is preferable to spray a cleaning agent or the like with a shower and rub with a brush or the like to remove the development residue. The liquid temperature of the developing solution is preferably 20 ° C. to 40 ° C., and the pH of the developing solution is preferably 8 to 13.

The method for manufacturing the capacitance type input device may include other steps such as a post-exposure step and a post-baking step. When the first curable transparent resin layer and the second curable transparent resin layer are thermosetting transparent resin layers, it is preferable to carry out a post-baking step.

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

(Transparent film formation)
The transparent 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 transparent electrode pattern opposite to the side on which the second curable transparent resin layer is formed. When further having a transparent film, the transparent film is formed directly on the transparent electrode pattern or via another layer such as the third transparent film.
The method for forming the transparent film is not particularly limited, but it is preferable to form the transparent film by transfer or sputtering.
Among them, the transparent laminate of the present invention is preferably formed by transferring the transparent curable resin film formed on the temporary support onto the transparent substrate, and after the transfer. It is more preferable that the film is cured to form a film. As the transfer and curing methods, the photosensitive film described later in the description of the capacitive input device of the present invention is used, and the first curable transparent resin layer and the first curable transparent resin layer in the method for producing a transparent laminate of the present invention. Similar to the method of transferring the second curable transparent resin layer, a method of performing transfer, exposure, development and other steps can be mentioned. In that case, it is preferable to adjust the refractive index of the transparent film within the above range by dispersing the metal oxide fine 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 transparent laminate of the present invention, it is also preferable that the transparent film is formed by sputtering.
As the method of sputtering, the methods used in JP-A-2010-86684, JP-A-2010-152809 and JP-A-2010-257492 can be preferably used, and the contents of these documents are described in the present specification. Incorporated in the book.

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

[Capacitive input device]
The capacitance type input device of the present invention is made by using the transfer film of the present invention, or has the transparent laminate of the present invention.
The capacitance type input device of the present invention has a transparent electrode pattern, a second curable transparent resin layer arranged adjacent to the transparent electrode pattern, and adjacent to the second curable transparent resin layer. It has a first curable transparent resin layer arranged, and the refractive index of the second curable transparent resin layer is higher than the refractive index of the first curable transparent resin layer, and the second curing It is preferable to have a transparent laminate having a refractive index of 1.6 or more in the transparent resin layer.
Hereinafter, the details of the preferred embodiment of the capacitance type input device of the present invention will be described.

The capacitance type input device of the present invention has at least the following (3) to (5), (7) on the non-contact side of the front plate (corresponding to the transparent substrate in the transparent laminate of the present invention) and the front plate. ) And (8), and preferably has the transparent laminate of the present invention.
(3) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via a connecting portion (4) Electrically insulated from the first transparent electrode pattern. A plurality of second electrode patterns composed of a plurality of pad portions extending in a direction intersecting the first direction (5) The first transparent electrode pattern and the second electrode pattern are electrically connected. Insulating layer (7) Second curable transparent resin layer formed so as to cover all or part of the elements (3) to (5) (8) Covering the element of (7). First curable transparent resin layer formed so as to be adjacent here, the second curable transparent resin layer (7) is the second curable transparent resin layer in the transparent laminate of the present invention. Equivalent to. Further, the (8) first curable transparent resin layer corresponds to the first curable transparent resin layer in the transparent laminate of the present invention. The first curable transparent resin layer is preferably a so-called transparent protective layer in a generally known capacitance type input device.

In the capacitance type input device of the present invention, the second electrode pattern (4) may or may not be a transparent electrode pattern, but a transparent electrode pattern is preferable.
The capacitance type input device of the present invention may further have the following element (6).
(6) A conductive element that is electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern and is different from the first transparent electrode pattern and the second transparent electrode pattern. Here, when the (7) second electrode pattern is not a transparent electrode pattern and (8) does not have another conductive element, the (7) first transparent electrode pattern of the present invention is used. It corresponds to the transparent electrode pattern in the transparent laminate.
When the (7) second electrode pattern is a transparent electrode pattern and does not have the (6) another conductive element, the (3) first transparent electrode pattern and the (7) second At least one of the electrode patterns corresponds to the transparent electrode pattern in the transparent laminate of the present invention.
When the (7) second electrode pattern is not a transparent electrode pattern and has (6) another conductive element, the (3) first transparent electrode pattern and the (6) another conductive element At least one of them corresponds to the transparent electrode pattern in the transparent laminate of the present invention.
When the (7) second electrode pattern is a transparent electrode pattern and has (6) another conductive element, the (3) first transparent electrode pattern and the (7) second electrode pattern And at least one of the other conductive elements (6) corresponds to the transparent electrode pattern in the transparent laminate of the present invention.

In the capacitance type input device of the present invention, (2) a transparent film is further provided between (3) the first transparent electrode pattern and the front plate, (4) between the second transparent electrode pattern and the front plate, or. , (6) It is preferable to have it between the other conductive element and the front plate. Here, the fact that the transparent film (2) corresponds to the transparent film having a refractive index of 1.6 to 1.78 and a film thickness of 55 to 110 nm in the transparent laminate of the present invention is visually recognized of the transparent electrode pattern. It is preferable from the viewpoint of further improving the sex.

The capacitive input device of the present invention preferably further has (1) a mask layer and / or a decorative layer, if necessary. The mask layer is provided as a black frame around the area touched by a finger or a touch pen so that the wiring of the transparent electrode pattern cannot be seen from the contact side or is decorated. The decorative layer is provided for decoration, and it is preferable to provide, for example, a white decorative layer.
The (1) mask layer and / or the decorative layer is formed between the (2) transparent film and the front plate, (3) between the first transparent electrode pattern and the front plate, and (4) the second transparent electrode pattern. It is preferable to have it between the front plate and the front plate, or between the other conductive element (6) and the front plate. It is more preferable that the (1) mask layer and / or the decorative layer is provided adjacent to the front plate.

The capacitance type input device of the present invention has the second curable transparent resin layer arranged adjacent to the transparent electrode pattern and the second curable transparent resin layer even when the capacitance type input device includes such various members. By including the first curable transparent resin layer arranged adjacent to the curable transparent resin layer, the transparent electrode pattern can be made inconspicuous, and the problem of visibility of the transparent electrode pattern can be improved. it can. Further, as described above, the transparent electrode pattern is sandwiched between the transparent film having a refractive index of 1.6 to 1.78 and a film thickness of 55 to 110 nm and the second curable transparent resin layer. Thereby, the problem of visibility of the transparent electrode pattern can be further improved.

<Configuration of capacitive input device>
First, a preferable configuration of the capacitance type input device of the present invention will be described together with a method of manufacturing each member constituting the device. FIG. 1A is a cross-sectional view showing a preferable configuration of the capacitance type input device of the present invention. In FIG. 1A, the capacitance type input device 10 includes a transparent substrate (front plate) 1, a mask layer 2, a transparent film 11 having a refractive index of 1.6 to 1.78 and a film thickness of 55 to 110 nm, and a third layer. One transparent electrode pattern 3, a second transparent electrode pattern 4, an insulating layer 5, a conductive element 6, a second curable transparent resin layer 12, a first curable transparent resin layer 7, and the like. An aspect composed of is shown.
Further, FIG. 1B showing a cross section of XX'in FIG. 3 described later is also a cross-sectional view showing a preferable configuration of the capacitance type input device of the present invention. In FIG. 1B, the capacitance type input device 10 includes a transparent substrate (front plate) 1, a transparent film 11 having a refractive index of 1.6 to 1.78 and a film thickness of 55 to 110 nm, and a first transparent electrode pattern. An aspect composed of 3, a second transparent electrode pattern 4, a second curable transparent resin layer 12, and a first curable transparent resin layer 7 is shown.

As the transparent substrate (front plate) 1, the material listed as the material for the transparent electrode pattern in the transparent laminate of the present invention can be used. Further, in FIG. 1A, the side on which each element of the front plate 1 is provided is referred to as a non-contact surface. In the capacitance type input device 10 of the present invention, input is performed by bringing a finger or the like into contact with the contact surface (the surface opposite to the non-contact surface) of the front plate 1.

Further, a mask layer 2 is provided on the non-contact surface of the front plate 1. The mask layer 2 is a frame-shaped pattern around the display area formed on the non-contact side of the touch panel front plate, and is formed so that the routing wiring and the like cannot be seen.
As shown in FIG. 2, the capacitance type input device 10 of the present invention is provided with the mask layer 2 so as to cover a part of the front plate 1 (the region other than the input surface in FIG. 2). There is. Further, the front plate 1 may be partially provided with an opening 8 as shown in FIG. A mechanical switch by pressing can be installed in the opening 8.

On the contact surface of the front plate 1, a plurality of first transparent electrode patterns 3 formed by extending a plurality of pad portions in a first direction via a connecting portion, and a first transparent electrode pattern 3 A plurality of second transparent electrode patterns 4 composed of a plurality of pad portions that are electrically insulated and are formed so as to extend in a direction intersecting the first direction, and a first transparent electrode pattern 3 and a 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 the conductive element 6 described later, those listed as the material of the transparent electrode pattern in the transparent laminate of the present invention can be used. It is preferably an ITO film.

Further, at least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4 straddles both the non-contact surface of the front plate 1 and the surface of the mask layer 2 opposite to the front plate 1. Can be installed. FIG. 1A shows a diagram in which the second transparent electrode pattern is installed across the regions of both the non-contact surface of the front plate 1 and the surface of the mask layer 2 opposite to the front plate 1. There is. In this way, even when the photosensitive film is laminated over the mask layer that requires a certain thickness and the back surface of the front plate, it is expensive to use a photosensitive film having a specific layer structure described later, such as a vacuum laminator. Lamination without the generation of bubbles at the boundary of the mask portion becomes possible in a simple process without using equipment.

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 a first transparent electrode pattern and a second transparent electrode pattern in the present invention. As shown in FIG. 3, the first transparent electrode pattern 3 is formed by the pad portion 3a extending in the first direction via the connecting portion 3b. Further, the second transparent electrode pattern 4 is electrically insulated by the first transparent electrode pattern 3 and the insulating layer 5, and extends in the direction intersecting the first direction (the second direction in FIG. 3). It is composed of a plurality of pad portions that are present and formed. Here, when the first transparent electrode pattern 3 is formed, the pad portion 3a and the connecting portion 3b may be integrally manufactured, or only the connecting portion 3b may be manufactured to form the pad portion 3a and the second. The transparent electrode pattern 4 may be integrally manufactured (patterned). When the pad portion 3a and the second transparent electrode pattern 4 are integrally manufactured (patterned), as shown in FIG. 3, a part of the connecting portion 3b and a part of the pad portion 3a are connected and an insulating layer. Each layer is formed by 5 so that the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are electrically insulated from each other.
Further, the region in which the first transparent electrode pattern 3, the second transparent electrode pattern 4, or the conductive element 6 described later is not formed corresponds to the non-pattern region 22 in the transparent laminate of the present invention.

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

Further, in FIG. 1A, the first curable transparent resin layer 7 is installed so as to cover all of the constituent elements. The first curable transparent resin layer 7 may be configured to cover only a part of each component. The insulating layer 5 and the first curable transparent resin layer 7 may be made of the same material or different materials. As the material constituting the insulating layer 5, those listed as the material of the first or second curable transparent resin layer in the transparent laminate of the present invention can be preferably used.

<Manufacturing method of capacitance type input device>
Examples of aspects formed in the process of manufacturing the capacitance type input device of the present invention include aspects shown in FIGS. 4 to 8. FIG. 4 is a top view showing an example of the tempered glass 11 in which the opening 8 is formed. FIG. 5 is a top view showing an example of the front plate on which the mask layer 2 is formed. FIG. 6 is a top view showing an example of a front plate on which the first transparent electrode pattern 3 is formed. FIG. 7 is a top view showing an example of a front plate on which the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are formed. FIG. 8 is a top view showing an example of a front plate on which a conductive element 6 different from the first and second transparent electrode patterns is formed. These are examples that embody the following description, and the scope of the present invention is not construed as limiting by these drawings.

In the method of manufacturing the capacitance type input device, when the first curable transparent resin layer 12 and the first curable transparent resin layer 7 are formed, each element is arbitrary by using the transfer film of the present invention. It can be formed by transferring the first curable transparent resin layer and the first curable transparent resin layer to the surface of the front plate 1 formed in.

In the method for manufacturing a 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 the conductive element 6 is used. It is preferably formed by using the photosensitive film having a temporary support and a photocurable resin layer in this order.
When each of the above elements is formed using the transfer film of the present invention or the photosensitive film, there is no leakage of the resist component from the opening even in the substrate (front plate) having an opening, and a light-shielding pattern is particularly formed up to the boundary of the front plate. Since the resist component does not protrude from the edge of the glass in the mask layer that needs to be formed, it is possible to manufacture a touch panel with the merit of thinning / weight reduction in a simple process without contaminating the back side of the substrate. ..

Permanent materials such as the first transparent electrode pattern, the second transparent electrode pattern, and the conductive element when the mask layer, the insulating layer, and the conductive photocurable resin layer are used are formed by using the photosensitive film. In this case, the photosensitive film is laminated on the substrate and then exposed in a pattern as needed, and the unexposed portion in the case of a negative type material and the exposed portion in the case of a positive type material are developed and removed. The pattern can be obtained by doing. For development, the thermoplastic resin layer and the photocurable layer may be developed and removed with separate liquids, or may be removed with the same liquid. If necessary, known developing equipment such as a brush or a high-pressure jet may be combined. After development, post-exposure and post-baking may be performed as needed.

(Photosensitive film)
The photosensitive film other than the transfer film of the present invention, which is preferably used when manufacturing the capacitance type input device of the present invention, will be described. The photosensitive film preferably has a temporary support and a photocurable resin layer, and preferably has a thermoplastic resin layer between the temporary support and the photocurable resin layer. When a mask layer or the like is formed by using the photosensitive film having the thermoplastic resin layer, bubbles are less likely to be generated in the element formed by transferring the photocurable resin layer, and image unevenness or the like occurs in the image display device. It becomes difficult to do so, and excellent display characteristics can be obtained.
The photosensitive film may be a negative type material or a positive type material.

-Layer other than photocurable resin layer, manufacturing method-
As the temporary support and the thermoplastic resin layer in the photosensitive film, the same ones used for the transfer film of the present invention can be used. Further, as the method for producing the photosensitive film, the same method as the method for producing the transfer film of the present invention can be used.

-Photocurable resin layer-
Additives are added to the photocurable resin layer of the photosensitive film depending on its use. That is, when the photosensitive film is used for forming the mask layer, the photocurable resin layer contains a colorant. When the photosensitive film has a conductive photocurable resin layer, the photocurable resin layer contains conductive fibers and the like.

When the photosensitive film is a negative material, the photocurable resin layer preferably contains an alkali-soluble resin, a polymerizable compound, a polymerization initiator or a polymerization initiator. Further, conductive fibers, colorants, other additives, etc. are used, but the present invention is not limited thereto.

--Alkali-soluble resin, polymerizable compound, the above-mentioned polymerization initiator or polymerization initiator ---
As the alkali-soluble resin, the polymerizable compound, the polymerization initiator or the polymerization initiator system contained in the photosensitive film, the same ones used for the transfer film of the present invention can be used.

--Conductive fiber (when used as a conductive photocurable resin layer) ---
When the photosensitive film on which the conductive photocurable resin layer is laminated is used for forming a transparent electrode pattern or another conductive element, the following conductive fibers or the like may be used for the photocurable resin layer. it can.

The structure of the conductive fiber is not particularly limited and may be appropriately selected depending on the intended purpose, but either a solid structure or a hollow structure is preferable.
Here, the fiber having a solid structure may be referred to as a "wire", and the fiber having a hollow structure may be referred to as a "tube". Further, conductive fibers having an average minor axis length of 5 nm to 1,000 nm and an average major axis length of 1 μm to 100 μm may be referred to as “nanowire”.
Further, a conductive fiber having an average minor axis length of 1 nm to 1,000 nm and an average major axis length of 0.1 μm to 1,000 μm and having a hollow structure may be referred to as “nanotube”.
The material of the conductive fiber is not particularly limited as long as it has conductivity, and can be appropriately selected depending on the intended purpose. However, at least one of metal and carbon is preferable, and among these, the above-mentioned The conductive fibers are particularly preferably at least one of metal nanowires, metal nanotubes, and carbon nanotubes.

The material of the metal nanowire is not particularly limited, and for example, at least one metal selected from the group consisting of the 4th period, the 5th period, and the 6th period of the Long Periodic Table (IUPAC1991) is preferable. At least one metal selected from the 2nd to 14th groups is more preferable, and the 2nd, 8th, 9th, 10th, 11th, 12th, 13th, and 14th groups are preferable. At least one metal selected from the group is more preferable, and it is particularly preferable to include it as a main component.

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

The shape of the metal nanowire is not particularly limited and may be appropriately selected depending on the intended purpose. For example, any shape such as a columnar shape, a rectangular parallelepiped shape, or a columnar shape having a polygonal cross section can be taken. For applications that require high transparency, a columnar shape or a polygonal cross-sectional shape with rounded corners is preferable.
The cross-sectional shape of the metal nanowire can be examined by applying the metal nanowire aqueous dispersion on the base material and observing the cross section with a transmission electron microscope (TEM).
The angle of the cross section of the metal nanowire means a peripheral portion of a point where each side of the cross section is extended and intersects with a perpendicular line drawn from an adjacent side. Further, "each side of the cross section" is a straight line connecting these adjacent corners. In this case, the ratio of the "outer peripheral length of the cross section" to the total length of the "each side of the cross section" was defined as the sharpness. For example, in the cross section of a metal nanowire as shown in FIG. 9, the sharpness can be expressed by the ratio of the outer peripheral length of the cross section shown by the solid line to the outer peripheral length of the pentagon shown by the dotted line. A cross-sectional shape having a sharpness of 75% or less is defined as a cross-sectional shape with rounded corners. The sharpness is preferably 60% or less, more preferably 50% or less. If the sharpness exceeds 75%, electrons are localized at the corners and plasmon absorption is increased, or yellowness may remain and the transparency may be deteriorated. In addition, the linearity of the edge portion of the pattern may decrease, resulting in rattling. The lower limit of the sharpness is preferably 30%, more preferably 40%.

The average minor axis length (sometimes referred to as "average minor axis diameter" or "average diameter") of the metal nanowire is preferably 150 nm or less, more preferably 1 nm to 40 nm, further preferably 10 nm to 40 nm. 15 nm to 35 nm is particularly preferable.
If the average minor axis length is less than 1 nm, oxidation resistance may be deteriorated and durability may be deteriorated, and if it exceeds 150 nm, scattering due to metal nanowires may occur to obtain sufficient transparency. Sometimes you can't.
The average minor axis length of the metal nanowires is determined by observing 300 metal nanowires using a transmission electron microscope (TEM; JEM-2000FX, manufactured by JEOL Ltd.) and using the average value of the metal nanowires. The average minor axis length of was calculated. When the minor axis of the metal nanowire was not circular, the longest minor axis length was taken as the minor axis length.

The average major axis length (sometimes referred to as "average length") of the metal nanowires is preferably 1 μm to 40 μm, more preferably 3 μm to 35 μm, still more preferably 5 μm to 30 μm.
If the average major axis length is less than 1 μm, it is difficult to form a dense network and sufficient conductivity may not be obtained. If it exceeds 40 μm, the metal nanowires are too long to be manufactured. Occasionally they become entangled and agglomerates form during the manufacturing process.
The average major axis length of the metal nanowires is determined by observing 300 metal nanowires using, for example, a transmission electron microscope (TEM; JEM-2000FX manufactured by JEOL Ltd.), and using the average value, the metal nanowires The average major axis length of the wire was calculated. When the metal nanowire was bent, a circle having an arc as the arc was taken into consideration, and the value calculated from the radius and the curvature was taken as the major axis length.

The thickness of the conductive photocurable resin layer is preferably 0.1 to 20 μm, preferably 0.5 to 18 μm, from the viewpoint of process suitability such as stability of the coating liquid, drying during coating, and development time during patterning. More preferably, 1 to 15 μm is particularly preferable. The content of the conductive fibers with respect to the total solid content of the conductive photocurable resin layer is preferably 0.01 to 50% by mass, preferably 0.05 to 30% by mass, from the viewpoint of conductivity and stability of the coating liquid. % Is more preferable, and 0.1 to 20% by mass is particularly preferable.

--Colorant (when used as a mask layer) ---
When the photosensitive film is used as a mask layer, a colorant can be used for the photocurable resin layer. As the colorant used in the present invention, known colorants (organic pigments, inorganic pigments, dyes, etc.) can be preferably 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 the photocurable resin layer is used as a black mask layer, it is preferable to contain a black colorant from the viewpoint of optical density. Examples of the black colorant include carbon black, titanium carbon, iron oxide, titanium oxide, graphite and the like, and among them, carbon black is preferable.

When the photocurable resin layer is used as a white mask layer, the 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, the pigments or dyes described in paragraphs [0183] to [0185] of Japanese Patent No. 4546276 may be mixed and used. Specifically, the pigments and dyes described in paragraph numbers [0038] to [0054] of JP-A-2005-17716, and the pigments described in paragraph numbers [0068] to [0072] of JP-A-2004-361447. , The colorants and the like described in paragraph numbers [0080] to [0088] of JP-A-2005-17521 can be preferably used.

It is desirable that the colorant (preferably a pigment, more preferably carbon black) be used as a dispersion. This dispersion can be prepared by adding a composition obtained by premixing the colorant and the pigment dispersant to an organic solvent (or vehicle) described later and dispersing the composition. The vehicle refers to a portion of a medium in which a pigment is dispersed when the paint is in a liquid state, and a component (binder) that is liquid and combines with the pigment to form a coating film and dissolves and dilutes the component (binder). Contains components (organic solvent).
The disperser used when dispersing the pigment is not particularly limited, and for example, Kunizo Asakura, "Encyclopedia of Pigments", First Edition, Asakura Shoten, 2000, 438, Kneader. Known dispersers such as roll mills, Atriders, super mills, dissolvers, homomixers, and sand mills can be mentioned. Further, it may be finely pulverized by utilizing the frictional force by the mechanical grinding described on page 310 of the document.

From the viewpoint of dispersion stability, the colorant preferably has a number average particle size of 0.001 μm to 0.1 μm, and more preferably 0.01 μm to 0.08 μm. The "particle size" referred to here refers to the diameter when the electron micrograph image of the particles is made into a circle having the same area, and the "number average particle diameter" refers to the above-mentioned particle size for a large number of particles. This is the average value of 100 particles.

The layer 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 the thickness difference from other layers. The content of the colorant in the solid content of the colored photosensitive resin composition is not particularly limited, but is preferably 15 to 70% by mass, preferably 20 to 60% by mass, from the viewpoint of sufficiently shortening the developing time. It is more preferably by mass%, and even more preferably 25 to 50% by mass.
The total solid content as used herein means the total mass of the non-volatile components excluding the solvent and the like from the colored photosensitive resin composition.

When the insulating layer is formed by using the photosensitive film, the thickness of the photocurable resin layer is preferably 0.1 to 5 μm, more preferably 0.3 to 3 μm from the viewpoint of maintaining the insulating property. , 0.5 to 2 μm is particularly preferable.

--Other additives ---
Further, other additives may be used for the photocurable resin layer. As the additive, the same additive as that used for the transfer film of the present invention can be used.
Further, as the solvent for producing the photosensitive film by coating, the same solvent as that used for the transfer film of the present invention can be used.

Although the case where the photosensitive film is a negative type material has been mainly described above, the photosensitive film may be a positive type material. When the photosensitive film is a positive type material, for example, the material described in JP-A-2005-221726 is used for the photocurable resin layer, but the present invention is not limited thereto.

-Viscosity of thermoplastic resin layer and photocurable resin layer-
The viscosity of the thermoplastic resin layer measured at 100 ° C. is in the region of 1000 to 10000 Pa · sec, and the viscosity of the photocurable resin layer measured at 100 ° C. is in the region of 2000 to 50,000 Pa · sec. It is preferable to satisfy A).
Formula (A): Viscosity of thermoplastic resin layer <Viscosity of photocurable resin layer

Here, the viscosity of each layer can be measured as follows. The solvent is removed from the coating liquid for the thermoplastic resin layer or the photocurable resin layer by atmospheric pressure and vacuum drying to prepare a measurement sample. For example, as a measuring instrument, Vibron (DD-III type: manufactured by Toyo Baldwin Co., Ltd.) The measurement can be performed under the conditions of a measurement start temperature of 50 ° C., a measurement end temperature of 150 ° C., a temperature rise rate of 5 ° C./min, and a frequency of 1 Hz / deg, and a measured value of 100 ° C. can be used.

(Formation of mask layer and insulating layer with photosensitive film)
The mask layer 2 and the insulating layer 5 can be formed by transferring the photocurable resin layer to the front plate 1 or the like using the photosensitive film. For example, when the black mask layer 2 is formed, the photosensitive film having a black photocurable resin layer is used as the photocurable resin layer, and the black photocurable resin is used on the surface of the front plate 1. It can be formed by transferring the layers. When the insulating layer 5 is formed, the front plate 1 on which the first transparent electrode pattern is formed is formed by using the photosensitive film having an insulating photocurable resin layer as the photocurable resin layer. It can be formed by transferring the photocurable resin layer to the surface.
Further, for forming the mask layer 2 that requires light-shielding property, the photosensitive film having a specific layer structure having a thermoplastic resin layer between the photocurable resin layer and the temporary support is used to form the photosensitive film. It is possible to prevent the generation of air bubbles during lamination and to form a high-quality mask layer 2 or the like without light leakage.

(First and second transparent electrode patterns with photosensitive film, formation of another conductive element)
The first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 are made of the photosensitive film having an etching treatment or a conductive photocurable resin layer, or a photosensitive film. It can be formed by using it as a lift-off material.

-Etching process-
When the first transparent electrode pattern 3, the second transparent electrode pattern 4 and another conductive element 6 are formed by the etching process, first, on the non-contact surface of the front plate 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 photosensitive film having a photocurable resin layer for etching as the photocurable resin layer on the transparent electrode layer. After that, the transparent electrode layer is etched to pattern the transparent electrode, and the etching pattern is removed to form the first transparent electrode pattern 3 and the like.

When the photosensitive film is used as an etching resist (etching pattern), a resist pattern can be obtained in the same manner as in the above method. For the etching, etching and resist peeling can be applied by a known method described in paragraphs [0048] to [0054] of JP-A-2010-152155.

For example, as an etching method, a commonly used wet etching method of immersing in an etching solution can be mentioned. As the etching solution used for wet etching, an acidic type or an alkaline type may be appropriately selected according to the etching target. Examples of the acidic type etching solution include an aqueous solution of an acidic component alone such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and a mixed aqueous solution of an acidic component and a salt such as ferric chloride, ammonium fluoride, and potassium permanganate. Will be done. As the acidic component, a combination of a plurality of acidic components may be used. As the alkaline type etching solution, an aqueous solution of an alkaline component alone such as sodium hydroxide, potassium hydroxide, ammonia, an organic amine, a salt of an organic amine such as tetramethylammonium hydroxide, an alkaline component and potassium permanganate. A mixed aqueous solution of salts such as, etc. is exemplified. As the alkaline component, a combination of a plurality of alkaline components may be used.

The temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower. The resin pattern used as the etching mask (etching pattern) in the present invention is formed by using the above-mentioned photocurable resin layer, so that it is particularly resistant to acidic and alkaline etching solutions in such a temperature range. Demonstrates excellent 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 etching, a cleaning step and a drying step may be performed as necessary to prevent line contamination. The cleaning step is performed by cleaning the substrate with pure water for 10 to 300 seconds at room temperature, for example, and the drying step is performed by appropriately adjusting the ^{air blow pressure (about 0.1 to 5 kg / cm 2) using an air blow.} Just do it.

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

As the stripping solution, for example, an inorganic alkaline component such as sodium hydroxide or potassium hydroxide or an organic alkaline component such as a tertiary amine or a quaternary ammonium salt can be used in water, dimethyl sulfoxide, N-methylpyrrolidone, or these. Examples thereof include those dissolved in a mixed solution of. The peeling liquid may be used and peeled by a spray method, a shower method, a paddle method or the like.

-Photosensitive film with a conductive photocurable resin layer-
When the first transparent electrode pattern 3, the second transparent electrode pattern 4 and another conductive element 6 are formed by using the photosensitive film having the conductive photocurable resin layer, the front plate 1 It can be formed by transferring the conductive photocurable resin layer to the surface.
When the first transparent electrode pattern 3 or the like is formed by using the photosensitive film having the conductive photocurable resin layer, there is no leakage of the resist component from the opening even in the substrate (front plate) having the opening. It is possible to manufacture a touch panel that has the merit of thinning and weight reduction in a simple process without contaminating the back side of the substrate.
Further, the photosensitive film having a specific layer structure having a thermoplastic resin layer between the conductive photocurable resin layer and the temporary support is used for forming the first transparent electrode pattern 3 and the like. It is possible to prevent the generation of air bubbles during laminating the resin 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 a lift-off material-
Further, the photosensitive film can be used as a lift-off material to form a first transparent electrode layer, a second transparent electrode layer, and other conductive members. In this case, after patterning with the photosensitive film, a transparent conductive layer is formed on the entire surface of the base material, and then the photocurable resin layer is dissolved and removed together with the deposited transparent conductive layer to obtain a desired transparent conductive layer. A pattern can be obtained (lift-off method).

[Image display device]
The image display device of the present invention is characterized by including the capacitance type input device of the present invention.
The capacitance type input device of the present invention and the image display device including the capacitance type input device as a component are "Latest Touch Panel Technology" (Techno Times Co., Ltd., published on July 6, 2009), Mitani. Supervision of Yuji, "Touch Panel Technology and Development", CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Display Corporation Application Note AN2292, etc. can be applied. ..

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[Examples 1 to 13, Comparative Examples 1 and 2]
[Preparation of transfer film]
<Formation of thermoplastic resin layer and intermediate layer>
A coating liquid for a thermoplastic resin layer having the following formulation H1 was applied and dried on a 75 μm-thick polyethylene terephthalate film temporary support using a slit-shaped nozzle. Next, a coating liquid for an intermediate layer consisting of the following formulation P1 was applied and dried.

(Coating liquid for thermoplastic resin layer: Formulation H1)
-Methanol: 11.1 parts by mass-Propropylene 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) (Moral ratio) =
55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg ≈ 70 ° C)
: 5.83 parts by mass ・ Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37,
Weight average molecular weight = 10,000, Tg ≒ 100 ° C): 13.6 parts by mass Monomer 1 (Product name: BPE-500, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
: 9.1 parts by mass, fluoropolymer: 0.54 parts by mass The above fluoropolymers are C ₆ F ₁₃ CH ₂ CH ₂ OCOCH = CH ₂ 40 parts and H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH. = a copolymer of _CH 2 55 parts of _{H (OCHCH 2) 7 OCOCH =} CH 2 5 parts, weight average molecular weight 30,000, methyl ethyl ketone 30 wt% solution (trade name: Megafac F780F, Dainippon ink and chemicals Made by Kogyo Co., Ltd.)

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

<First curable transparent resin layer>
The materials-1, material-2 and material-11 for the first curable transparent resin layer prepared according to the compositions shown in Table 1 below were adjusted to the desired film thicknesses shown in Table 2 below while changing the coating amount. The first curable transparent resin layer was formed on the intermediate layer by adjusting so as to be, applied and dried.
In Table 1 below and the general formula (1) below, "%" and "wt%" both represent mass%.

When the first curable transparent resin layer was applied and dried, a section of the first curable transparent resin layer was cut from the surface using a microtome. To 0.1 mg of this section, 2 mg of KBr powder was added and mixed well under a yellow light to prepare a measurement sample of a UV uncured product in the measurement of the double bond consumption rate described later.

In Examples 1 to 12 and Comparative Examples 1 and 2, after the film of the first curable transparent resin layer was irradiated with UV lamp irradiation (exposure dose 300 mJ / cm ^2, Metall halide lamp). However, in Example 13, UV lamp irradiation was not performed.
When the first layer was applied, dried, and cured, a section of the first curable transparent resin layer was cut from the surface using a microtome. To 0.1 mg of this section, 2 mg of KBr powder was added and mixed well under a yellow light to prepare a measurement sample after coating, drying and curing in the measurement of the double bond consumption rate described later.

(Measurement of double bond consumption rate)
FT-IR apparatus (Thermo Nicolet Japan Ltd., Nicolet 710) ^was used to measure the wavelength region of 400cm ^-1 ~4000cm -1, was determined peak intensity of 810 cm ^-1 derived from C = C bond. The peak intensity (= residual amount of double bonds) A of the UV uncured product that was only coated / dried / dried and the peak intensity B of each film section after coating / drying / curing were determined. For the first curable transparent resin layer formed in each Example and Comparative Example, the double bond consumption rate was calculated according to the following formula.
formula:
Double bond consumption rate = {1- (B / A)} x 100%
"Evaluation criteria"
〇: Double bond consumption rate is 10% or more Δ: Double bond consumption rate is less than 10% The double bond consumption rate is an index of the degree of interfacial mixing between the first layer and the second layer.

<Formation of a second curable transparent resin layer>
Then, the materials for the second curable transparent resin layer-3 to 10 prepared according to the compositions shown in Table 1 below are adjusted to have the desired film thickness shown in Table 2 below while changing the coating amount. Then, it was applied and dried to form a second curable transparent resin layer on the first curable transparent resin layer.

<Crimping of protective film>
In this way, a thermoplastic resin layer having a dry film thickness of 15.1 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a first layer having a dry film thickness in Table 2 below are obtained on the temporary support. A curable transparent resin layer and a second curable transparent resin layer were provided, and finally a protective film (thickness 12 μm polypropylene film) was pressure-bonded.

In this way, a transfer film in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen blocking film), the first curable transparent resin layer, the second curable transparent resin layer, and the protective film are integrated was produced. The obtained transfer film was used as a transfer film of each Example and Comparative Example.

[Preparation of transparent laminate]
Using the transfer films of each Example and Comparative Example obtained above, a transparent laminate was prepared by the following method.

<1. Formation of transparent film>
On a transparent glass substrate having a refractive index of 1.51, a transparent film having a refractive index of 1.60 and a film thickness of 80 nm using the material-3 shown in Table 1 above was formed by the following method.

(Preparation of transfer material)
A coating liquid for a thermoplastic resin layer made of the above-mentioned formulation H1 was applied and dried on a 75 μm-thick polyethylene terephthalate film temporary support using a slit-shaped nozzle. Next, the coating liquid for the intermediate layer made of the above-mentioned formulation P1 was applied and dried. Further, Material-3 for a transparent curable composition prepared according to the composition shown in Table 1 above was applied and dried. In this way, a thermoplastic resin layer having a dry film thickness of 15.1 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a transparent curable resin layer having a dry film thickness of 80 nm are formed on the temporary support. Finally, a protective film (thickness 12 μm polypropylene film) was pressure-bonded. In this way, a transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen blocking film), the transparent curable resin layer, and the protective film are integrated was produced.

(Formation of transparent film)
Using the transfer material from which the protective film was peeled off, the transparent curable resin layer was transferred together with the thermoplastic resin, the intermediate layer and the PET temporary support onto the transparent glass substrate, and then the PET temporary support was peeled off.
Next, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp, the entire surface was exposed with ^{i-line, 40 mJ / cm 2 from the thermoplastic resin layer side.} Next, a triethanolamine-based developer (containing 30% triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) is 10 times as much as pure water (1 part of T-PD2 and 9 parts of pure water). The solution (diluted in proportion) was shower-developed at 30 C for 60 seconds at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin and the intermediate layer. Subsequently, air is blown onto the upper surface (transparent curable resin layer side) of the transparent glass substrate to drain the liquid, then pure shower is sprayed for 10 seconds, the pure shower is washed, and air is blown onto the transparent glass substrate. Reduced the amount of liquid in the shower. Next, the substrate was heat-treated (post-baked) at 230 ° C. for 60 minutes to obtain a substrate in which a transparent film was laminated on a transparent glass substrate.

<2. Formation of transparent electrode pattern>
A substrate in which a transparent film is laminated on the transparent glass substrate obtained above is introduced into a vacuum chamber, and _{an ITO target having a SnO 2} content of 10% by mass (indium: tin = 95: 5 (molar ratio)). )) By DC magnetron sputtering (conditions: substrate temperature 250 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa) to form an ITO thin film with a thickness of 40 nm and a refractive index of 1.82, which is transparent. A front plate on which an electrode layer was formed was obtained. The surface resistance of the ITO thin film was 80Ω / □.

(Preparation of photosensitive film E1 for etching)
A coating liquid for a thermoplastic resin layer made of the above-mentioned formulation H1 was applied and dried on a 75 μm-thick polyethylene terephthalate film temporary support using a slit-shaped nozzle. Next, the coating liquid for the intermediate layer made of the above-mentioned formulation P1 was applied and dried. Further, a coating liquid for a photocurable resin layer for etching: Formulation E1 was applied and dried. In this way, the temporary support is composed of a thermoplastic resin layer having a dry film thickness of 15.1 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a photocurable resin layer for etching having a film thickness of 2.0 μm. A laminate was obtained, and finally a protective film (thickness 12 μm polypropylene film) was pressure-bonded. In this way, a transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen blocking film), and the transparent curable resin layer are integrated was produced.

(Coating liquid for photocurable resin layer for etching: Formulation E1)
-Methyl methacrylate / styrene / methacrylic acid copolymer (copolymer composition (mass%): 31/40/29, mass average molecular weight 60,000,
Acid value 163 mgKOH / g): 16 parts by mass, monomer 1 (trade name: BPE-500, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
: 5.6 parts by mass-0.5 mol of tetraethylene oxide monomethacrylate of hexamethylene diisocyanate: 7 parts by mass-cyclohexanedimethanol monoacrylate as a compound having one polymerizable group in the molecule: 2.8 parts by mass -2-Chloro-N-butylacridone: 0.42 parts by mass-2,2-bis (o-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole: 2.17 parts by mass-Malachite Green oxalate: 0.02 parts by mass, leuco crystal violet: 0.26 parts by mass, phenothiazine: 0.013 parts by mass, surfactant (trade name: 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 The viscosity of the coating liquid E1 for the photocurable resin layer for etching at 100 ° C. after removing the solvent is 2500 Pa · sec. Met.

(Formation of transparent electrode pattern)
The front plate on which the transparent electrode layer was formed was washed, and the photosensitive film E1 for etching from which the protective film was removed was laminated (base material temperature: 130 ° C., rubber roller temperature 120 ° C., linear pressure 100 N / cm, transport speed 2. 2m / min). After peeling off the temporary support, the distance between the surface of the exposure mask (quartz exposure mask having a transparent electrode pattern) and the photocurable resin layer for etching is set to 200 μm, and the exposure amount is 50 mJ / cm ² (i-line). ) Was used for pattern exposure.
Next, a triethanolamine-based developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) diluted 10-fold with pure water) was added at 25 ° C. for 100 seconds. Treat with a surfactant-containing developer (trade name: T-SD3 (manufactured by FUJIFILM Corporation) 10-fold diluted with pure water) at 33 ° C. for 20 seconds, and use a rotating brush and an ultra-high pressure cleaning nozzle. The residue was removed, and post-baking treatment was further performed at 130 ° C. for 30 minutes to obtain a front plate on which a transparent electrode layer and a photocurable resin layer pattern for etching were formed.
The front plate on which the transparent electrode layer and the photocurable resin layer pattern for etching are formed is immersed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), treated for 100 seconds, and used for etching. The transparent electrode layer in the exposed region not covered with the photocurable resin layer was dissolved and removed to obtain a front plate having a transparent electrode layer pattern with a photocurable resin layer pattern for etching.
Next, a resist stripping solution (N-methyl-2-pyrrolidone, monoethanolamine, surfactant (trade name: Surfinol 465) is applied to the front plate with the transparent electrode layer pattern with the photocurable resin layer pattern for etching. , Air Products) Immerse in a resist stripping tank containing liquid temperature 45 ° C) and treat for 200 seconds to remove the photocurable resin layer for etching and form a transparent film and transparent electrode pattern on a transparent glass substrate. Obtained the substrate.

After the end of the transparent electrode pattern is coated with Pt (about 20 nm thick) to impart conductivity and surface protection, the shape of the end of the transparent electrode pattern is observed using a Nova200 type FIB / SEM multifunction device manufactured by FEI (2). Next electron image, acceleration voltage 20 kV) was performed.
The formed ITO pattern had a tapered shape as shown in FIG. 10, and the taper angle α = about 3 °.

<3. Formation of a first curable transparent resin layer and a second curable transparent resin layer>
On the substrate on which the transparent film and the transparent electrode pattern are formed on the transparent glass substrate obtained above, the transfer films of the respective Examples and Comparative Examples are used to form the transparent film on the transparent glass substrate. By the same method, a transparent laminate in which the transparent electrode pattern, the second curable transparent resin layer, and the first curable transparent resin layer were continuous in this order was formed.
In this way, a transparent laminate was obtained in which a transparent film, a transparent electrode pattern, a second curable transparent resin layer, and a first curable transparent resin layer were laminated in this order on a transparent glass substrate. The obtained transparent laminate was used as a transparent laminate of each Example and Comparative Example.

[Evaluation of transparent laminate]
<Evaluation of visibility of transparent electrode pattern>
The transparent laminates of Examples and Comparative Examples in which a transparent film, a transparent electrode pattern, a second curable transparent resin layer, and a first curable transparent resin layer are laminated in this order on a transparent glass substrate are transparent. The transparent laminate and the black PET material were adhered to each other via an adhesive tape (manufactured by 3M, trade name, OCA tape 8171CL) to shield the entire substrate from light.
The visibility of the transparent electrode pattern was performed by injecting light from the glass surface side of the fluorescent lamp (light source) and the prepared substrate in a dark room and visually observing the reflected light from the glass surface from an oblique angle.
"Evaluation criteria"
⊚: The transparent electrode pattern cannot be seen at all.
〇: The transparent electrode pattern is slightly visible, but almost invisible.
Δ: The transparent electrode pattern is visible (difficult to understand).
△△: A transparent electrode pattern can be seen, but it is practically acceptable.
X: The transparent electrode pattern is clearly visible (easy to understand).
The results obtained are shown in Table 2 below.

<Evaluation of pencil hardness>
The pencil hardness evaluation described in JIS K 5400 was performed as an index of scratch resistance. The transfer film of each Example and Comparative Example was transferred to a transparent glass substrate, a transparent film, and a substrate having a transparent electrode pattern, and the transparent laminate of each Example and Comparative Example was obtained at a temperature of 25 ° C. After adjusting the humidity at a relative humidity of 60% for 1 hour, evaluation of n = 7 was performed with a load of 500 g using a 2H test pencil specified in JIS S 6006.
"Evaluation criteria"
⊚: There are less than 3 scratches.
◯: There are 3 or more and less than 5 scratches.
Δ: There are 5 or more scratches and less than 6 scratches.
X: There are 6 or more scratches.
The results obtained are shown in Table 2 below.

From Table 2 above, it was found that the transparent laminate of the present invention produced by using the transfer film of the present invention has no problem of visually recognizing the transparent electrode pattern.
On the other hand, in Comparative Example 1 using a transfer film having a refractive index of 1.59 for the second curable transparent resin layer, which is below the range of the present invention, the transparent electrode pattern of the obtained transparent laminate is clearly visible. Met. In Comparative Example 2 using the transfer film not containing the second curable transparent resin layer, the transparent electrode pattern of the obtained transparent laminate was clearly visible.

[Examples 101 to 113, Comparative Examples 101 and 102: Manufacture of a capacitance type input device]
<< Formation of mask layer >>
[Preparation of photosensitive film K1 for mask layer formation]
A coating liquid for a thermoplastic resin layer made of the above-mentioned formulation H1 was applied and dried on a 75 μm-thick polyethylene terephthalate film temporary support using a slit-shaped nozzle. Next, the coating liquid for the intermediate layer made of the above-mentioned formulation P1 was applied and dried. Further, a coating liquid for a black photocurable resin layer composed of the following formulation K1 was applied and dried. In this way, the thermoplastic resin layer having a dry film thickness of 15.1 μm, the intermediate layer having a dry film thickness of 1.6 μm, and the dry film thickness having an optical density of 4.0 are formed on the temporary support. A 2.2 μm black photocurable resin layer was provided, and finally a protective film (12 μm thick polypropylene film) was pressure-bonded. In this way, a transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen blocking film), and the black photocurable resin layer were integrated was produced, and the sample name was designated as the mask layer forming photosensitive film K1.

(Coating liquid for black photocurable resin layer: Formulation K1)
・ K pigment dispersion 1: 31.2 parts by mass ・ R pigment dispersion 1 (composition below): 3.3 parts by mass ・ MMPGAc (manufactured by Daicel Chemical Co., Ltd.): 6.2 parts by mass ・ Methyl ethyl ketone (Tonen Chemical Corporation) (Manufactured by Co., Ltd.): 34.0 parts by mass, cyclohexanone (manufactured by Kanto Denka Kogyo Co., Ltd.): 8.5 parts by mass, binder 2 (benzyl methacrylate / methacrylate = 78/22 molar ratio)
Random copolymer, weight average molecular weight 38,000): 10.8 parts by mass ・ Phenothiazine (manufactured by Tokyo Kasei Co., Ltd.): 0.01 parts by mass ・ DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku Co., Ltd.) Made)
Propylene glycol monomethyl ether acetate solution (76% by mass)
: 5.5 parts by mass · 2,4-bis (trichloromethyl) -6- [4'-(N, N-bis (ethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine
: 0.4 parts by mass, surfactant (trade name: Megafuck F-780F, manufactured by Dainippon Ink Co., Ltd.)
: 0.1 part by mass The viscosity of the coating liquid K1 for the black photocurable resin layer at 100 ° C. after removing the solvent was 10000 Pa · sec.

(Composition of K Pigment Dispersion 1)
-Carbon black (trade name: Nipex35, manufactured by Degussa): 13.1% by mass
-The following dispersant 1: 0.65% by mass
Binder 1 (random copolymer with benzyl methacrylate / methacrylic acid = 72/28 molar ratio, weight average molecular weight 37,000): 6.72% by mass
-Propylene glycol monomethyl ether acetate: 79.53% by mass

-Composition of R Pigment Dispersion 1-
-Pigment (CI Pigment Red 177): 18% by mass
Binder 1 (random copolymer with benzyl methacrylate / methacrylic acid = 72/28 molar ratio, weight average molecular weight 37,000): 12% by mass
-Propylene glycol monomethyl ether acetate: 70% by mass

[Formation of mask layer]
Next, the tempered glass (300 mm × 400 mm × 0.7 mm) having an opening (15 mmΦ) formed was washed with a rotating brush having nylon hair while spraying a glass cleaning agent solution adjusted to 25 ° C. with a shower for 20 seconds. After washing with pure water shower, shower the silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3% by mass aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) by shower 20. It was sprayed for seconds and washed with pure water shower. This base material was heated at 140 ° C. for 2 minutes with a base material preheating device. On the obtained silane coupling-treated glass substrate, the cover film was removed from the mask layer-forming photosensitive film K1 obtained above, and the surface of the black photocurable resin layer exposed after the removal was subjected to the silane coupling treatment. Laminated so that they are in contact with the surface of the glass base material, and using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), the base material heated at 140 ° C. was subjected to a rubber roller temperature of 130 ° C. and a linear pressure. Laminating was performed at 100 N / cm and a transport speed of 2.2 m / min. Subsequently, the temporary support of polyethylene terephthalate was peeled off at the interface with the thermoplastic resin layer to remove the temporary support. After peeling off the temporary support, the base material and the exposure mask (quartz exposure mask with a frame pattern) were erected vertically with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp. In this state, the distance between the exposure mask surface and the black photocurable resin layer was set to 200 μm, ^{and pattern exposure was performed with an exposure amount of 70 mJ / cm 2} (i-line).

Next, a triethanolamine-based developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) diluted 10-fold with pure water) was added at 33 ° C. for 60 seconds. Shower development was performed at a flat nozzle pressure of 0.1 MPa to remove the thermoplastic resin layer and the intermediate layer. Subsequently, after air was blown onto the upper surface of the glass base material to drain the liquid, pure water was sprayed by a shower for 10 seconds, the pure water shower was washed, and air was blown to reduce the liquid pool on the base material.

Then, using a sodium carbonate / sodium hydrogen carbonate developer (trade name: T-CD1 (manufactured by FUJIFILM Corporation) diluted 5 times with pure water), the shower pressure was adjusted to 0.1 MPa at 32 ° C. It was set, developed for 45 seconds, and washed with pure water.

Subsequently, using a surfactant-containing cleaning liquid (trade name: T-SD3 (manufactured by FUJIFILM Corporation) diluted 10-fold with pure water) at 33 ° C. for 20 seconds, the cone-type nozzle pressure was set to 0.1 MPa. Then, the residue was removed by rubbing the formed pattern image with a rotating brush having soft nylon bristles. Furthermore, ultrapure water is sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove the residue.

Next, post-exposure was performed in the atmosphere at an exposure rate of 1300 mJ / cm ² , and post-baking was further performed at 240 ° C. for 80 minutes before the mask layer having an optical density of 4.0 and a film thickness of 2.0 μm was formed. I got a face plate.

《Transparent film》
On the front plate on which the mask layer was formed, a transparent film was formed in the same manner as the film formation on the transparent film on the glass transparent substrate in the formation of the laminates of Examples 1 to 13 and Comparative Examples 1 and 2. A film was formed.

<< Formation of the first transparent electrode pattern >>
[Formation of transparent electrode layer]
A front plate on which a mask layer and a transparent film are formed is introduced into a vacuum chamber, and a DC magnetron is used with an ITO target (indium: tin = 95: 5 (molar ratio)) having _{a SnO 2 content of 10% by mass.} By sputtering (conditions: substrate temperature 250 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), an ITO thin film having a thickness of 40 nm was formed to obtain a front plate on which a transparent electrode layer was formed. The surface resistance of the ITO thin film was 80Ω / □.

[Preparation of photosensitive film E1 for etching]
In the preparation of the photosensitive film K1 for forming a mask layer, the photosensitive film for forming a mask layer is photosensitive except that the coating liquid for a black photocurable resin layer is replaced with a coating liquid for an etching photocurable resin layer having the following formulation E1. A photosensitive film E1 for etching was obtained in the same manner as in the preparation of the film K1 (the thickness of the photocurable resin layer for etching was 2.0 μm).

(Coating liquid for photocurable resin layer for etching: Formulation E1)
-Methyl methacrylate / styrene / methacrylic acid copolymer (copolymer composition (mass%): 31/40/29, mass average molecular weight 60,000,
Acid value 163 mgKOH / g): 16 parts by mass, monomer 1 (trade name: BPE-500, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
: 5.6 parts by mass-0.5 mol of tetraethylene oxide monomethacrylate of hexamethylene diisocyanate: 7 parts by mass-cyclohexanedimethanol monoacrylate as a compound having one polymerizable group in the molecule: 2.8 parts by mass -2-Chloro-N-butylacridone: 0.42 parts by mass-2,2-bis (o-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole: 2.17 parts by mass-Malachite Green oxalate: 0.02 parts by mass, leuco crystal violet: 0.26 parts by mass, phenothiazine: 0.013 parts by mass, surfactant (trade name: 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 The viscosity of the coating liquid E1 for the photocurable resin layer for etching at 100 ° C. after removing the solvent is 2500 Pa · sec. Met.

[Formation of the first transparent electrode pattern]
In the same manner as the formation of the mask layer, the front plate on which the mask layer, the transparent film, and the transparent electrode layer were formed was washed, and the photosensitive film E1 for etching from which the cover film was removed was laminated (base material temperature: 130 ° C., rubber). Roller temperature 120 ° C., linear pressure 100 N / cm, transport speed 2.2 m / min). After peeling off the temporary support, the distance between the surface of the exposure mask (quartz exposure mask having a transparent electrode pattern) and the photocurable resin layer for etching is set to 200 μm, and the exposure amount is 50 mJ / cm ² (i-line). ) Was used for pattern exposure.
Next, a triethanolamine-based developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) diluted 10-fold with pure water) was added at 25 ° C. for 100 seconds. Treat with a surfactant-containing developer (trade name: T-SD3 (manufactured by FUJIFILM Corporation) 10-fold diluted with pure water) at 33 ° C. for 20 seconds, and use a rotating brush and an ultra-high pressure cleaning nozzle. The residue was removed, and post-baking treatment was further performed at 130 ° C. for 30 minutes to obtain a front plate on which a transparent electrode layer and a photocurable resin layer pattern for etching were formed.

The front plate on which the transparent electrode layer and the photocurable resin layer pattern for etching are formed is immersed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), treated for 100 seconds, and used for etching. The transparent electrode layer in the exposed region not covered with the photocurable resin layer was dissolved and removed to obtain a front plate having a transparent electrode layer pattern with a photocurable resin layer pattern for etching.

Next, a resist stripping solution (N-methyl-2-pyrrolidone, monoethanolamine, surfactant (trade name: Surfinol 465) is applied to the front plate with the transparent electrode layer pattern with the photocurable resin layer pattern for etching. , Air Products) Immerse in a resist stripping tank containing liquid temperature 45 ° C.) and treat for 200 seconds to remove the photocurable resin layer for etching to form a mask layer, transparent film and first transparent electrode pattern. I got the front plate.

<< Formation of insulating layer >>
[Preparation of photosensitive film W1 for forming an insulating layer]
In the preparation of the photosensitive film K1 for forming a mask layer, the photosensitive film for forming a mask layer is photosensitive except that the coating liquid for a black photocurable resin layer is replaced with a coating liquid for a photocurable resin layer for an insulating layer having the following formulation W1. A photosensitive film W1 for forming an insulating layer was obtained in the same manner as in the preparation of the film K1 (the thickness of the photocurable resin layer for the insulating layer was 1.4 μm).

(Coating liquid for forming an insulating layer: Formulation W1)
Binder 3 (cyclohexylmethacrylate (a) / methylmethacrylate (b) / methacrylic acid copolymer (c) glycidyl methacrylate adduct (d) (composition (% by mass): a / b / c / d = 46/1) 1/10/43, mass average molecular weight: 36000, acid value 66 mgKOH / g) 1-methoxy-2-propanol, methyl ethyl ketone solution (solid content: 45%))
12.5 parts by mass ・ DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)
Propylene glycol monomethyl ether acetate solution (76% by mass)
: 1.4 parts by mass, urethane-based monomer (trade name: NK oligo UA-32P, manufactured by Shin-Nakamura Chemical Co., Ltd .: non-volatile content 75%, propylene glycol monomethyl ether acetate:
25%): 0.68 parts by mass, tripentaerythritol octaacrylate (trade name: V # 802,
Osaka Organic Chemical Industry Co., Ltd.): 1.8 parts by mass, diethylthioxanthone: 0.17 parts by mass, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1-
[4- (4-morpholinyl) phenyl] -1-butanone (trade name: Irgacare379, manufactured by BASF): 0.17 parts by mass / dispersant (trade name: Solsparse 20000, manufactured by Abyssia): 0.19 parts by mass / surfactant Activator (Product name: Megafuck F-780F, manufactured by Dainippon Ink)
: 0.05 parts by mass, methyl ethyl ketone: 23.3 parts by mass, MMPGAc (manufactured by Daicel Chemical Co., Ltd.): 59.8 parts by mass The viscosity of the coating liquid W1 for forming an insulating layer at 100 ° C. after removing the solvent is 4000 Pa. -It was sec.

Similar to the formation of the mask layer, the mask layer, the transparent film, and the front plate with the first transparent electrode pattern are washed, subjected to silane coupling treatment, and the photosensitive film W1 for forming the insulating layer from which the cover film is removed is laminated. (Base film temperature: 100 ° C., rubber roller temperature 120 ° C., linear pressure 100 N / cm, transport speed 2.3 m / min). After peeling off the temporary support, the distance between the surface of the exposure mask (quartz exposure mask having a pattern for the insulating layer) and the photocurable resin layer for etching is set to 100 μm, and the exposure amount is 30 mJ / cm ² (i). The pattern was exposed with lines).

Next, a triethanolamine-based developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) diluted 10-fold with pure water) was added at 33 ° C. for 60 seconds. Sodium carbonate / sodium hydrogen carbonate developer (trade name: T-CD1 (manufactured by FUJIFILM Corporation) diluted 5 times with pure water) at 25 ° C for 50 seconds, surfactant-containing cleaning solution (trade name) : Treat with T-SD3 (manufactured by FUJIFILM Corporation) 10-fold diluted with pure water at 33 ° C for 20 seconds, remove the residue with a rotating brush and ultra-high pressure washing nozzle, and further 230 ° C. After 60 minutes of post-baking treatment, a front plate on which a mask layer, a transparent film, a first transparent electrode pattern, and an insulating layer pattern were formed was obtained.

<< Formation of second transparent electrode pattern >>
[Formation of transparent electrode layer]
In the same manner as in the formation of the first transparent electrode pattern, the front plate on which the mask layer, the transparent film, the first transparent electrode pattern, and the insulating layer pattern are formed is subjected to DC magnetron sputtering treatment (condition: temperature of the base material is 50 ° C.). An ITO thin film having an argon pressure of 0.13 Pa and an oxygen pressure of 0.01 Pa) and a thickness of 80 nm was formed to obtain a front plate on which a transparent electrode layer was formed. The surface resistance of the ITO thin film was 110Ω / □.

Similar to the formation of the first transparent electrode pattern, the photosensitive film E1 for etching is used to mask the mask layer, the transparent film, the first transparent electrode pattern, the insulating layer pattern, the transparent electrode layer, and the photocuring for etching. A front plate having a sex resin layer pattern formed was obtained (post-baking treatment; 130 ° C. for 30 minutes).
Further, by etching (30 ° C. for 50 seconds) and removing the photocurable resin layer for etching (45 ° C. for 200 seconds) in the same manner as the formation of the first transparent electrode pattern, the mask layer, the transparent film, and the transparent film. A front plate on which the first transparent electrode pattern, the insulating layer pattern, and the second transparent electrode pattern were formed was obtained.

<< Formation of a conductive element different from the first and second transparent electrode patterns >>
DC magnetron sputtering of the front plate on which the mask layer, the transparent film, the first transparent electrode pattern, the insulating layer pattern, and the second transparent electrode pattern are formed in the same manner as in the formation of the first and second transparent electrode patterns. The treatment was carried out to obtain a front plate on which an aluminum (Al) thin film having a thickness of 200 nm was formed.

Similar to the formation of the first and second transparent electrode patterns, the mask layer, the transparent film, the first transparent electrode pattern, the insulating layer pattern, and the second transparent electrode are used by using the photosensitive film E1 for etching. A front plate having a pattern and a photocurable resin layer pattern for etching was obtained. (Post-baking treatment; 130 ° C. for 30 minutes).
Further, by etching (30 ° C. for 50 seconds) and removing the photocurable resin layer for etching (45 ° C. for 200 seconds) in the same manner as the formation of the first transparent electrode pattern, the mask layer, the transparent film, A front plate having a conductive element different from the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns was obtained.

<< First curable transparent resin layer and second curable transparent resin layer >>
For the mask layer, the transparent film, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the front plate on which a conductive element different from the first and second transparent electrode patterns is formed. A first curable transparent resin layer and a second curable transparent resin layer are formed in the same manner as in Examples 1 to 11 and Comparative Examples 1 to 15, and a mask layer and a transparent layer are formed on a transparent glass substrate. A film, a first transparent electrode pattern, an insulating layer pattern, a second transparent electrode pattern, a conductive element different from the first and second transparent electrode patterns, a second curable transparent resin layer and a second curing Capacitive input devices (front plates) of Examples 101 to 113 and Comparative Examples 101 and 102 in which the transparent resin layers were formed in this order were obtained.

<< Manufacturing of image display device (touch panel) >>
The front plates of Examples 101 to 113 and Comparative Examples 101 and 102 manufactured earlier are attached to the liquid crystal display device manufactured by the method described in JP-A-2009-47936, and the capacitance type input is performed by a known method. The image display devices of Examples 101 to 113 and Comparative Examples 101 and 102 including the device as a component were produced.

<< Evaluation of front plate and image display device >>
The capacitance type input device and the image display device of Examples 101 to 113 did not have a problem that the transparent electrode pattern was visually recognized.
In each of the above steps, the mask layer, the transparent film, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, the conductive element different from the first and second transparent electrode patterns, the second The front plate 1 on which the curable transparent resin layer and the second curable transparent resin layer were formed had no stains on the openings and the back surface, was easy to clean, and had no problem of contamination of other members.
In addition, the mask layer had no pinholes and had excellent light shielding properties.
Then, there is no problem in the conductivity of the first transparent electrode pattern, the second transparent electrode pattern, and the conductive elements other than these, while the first transparent electrode pattern and the second transparent electrode pattern and the second. It had insulating properties between the transparent electrode patterns.
Further, the first curable transparent resin layer also has no defects such as air bubbles, and an image display device having excellent display characteristics has been obtained.

1 Transparent substrate (front plate)
2 Mask layer 3 Transparent electrode pattern (first transparent electrode pattern)
3a Pad part 3b Connection part 4 Transparent electrode pattern (second transparent electrode pattern)
5 Insulation layer 6 Another conductive element 7 First curable transparent resin layer (preferably having the function of a transparent protective layer)
8 Opening 10 Capacitive input device 11 Transparent film 12 Second curable transparent resin layer (may have the function of a transparent insulating layer)
13 Transparent laminate 21 Region where the transparent electrode pattern, the second curable transparent resin layer, and the first curable 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 (protective film)
30 transfer film

Claims (14)

Temporary support and
With the first curable transparent resin layer,
A second curable transparent resin layer arranged adjacent to the first curable transparent resin layer ,
With a protective film, in this order,
The film thickness of the first curable transparent resin layer is 1 μm or more, and the film thickness is 1 μm or more.
The refractive index of the second curable transparent resin layer is higher than that of the first curable transparent resin layer.
A transfer film having a refractive index of 1.6 or more in the second curable transparent resin layer. The transfer film according to claim 1, wherein the temporary support is a biaxially stretched polyethylene terephthalate film. The transfer film according to claim 1 or 2 , wherein the first curable transparent resin layer has a refractive index of 1.5 to 1.53. Wherein the first curable transparent resin layer, the transfer film according to any one of claims 1 to 3, characterized in that it comprises a polymerizable compound and photopolymerization GoHiraki initiator. The transfer film according to any one of claims 1 to 4, wherein the first curable transparent resin layer contains an alkali-soluble resin. The transfer film according to any one of claims 1 to 4, wherein the first curable transparent resin layer contains an acrylic resin. The transfer film according to any one of claims 1 to 6, wherein the first curable transparent resin layer contains a urethane-based monomer. The transfer film according to any one of claims 1 to 7, wherein the first curable transparent resin layer has a film thickness of 1 to 10 μm. The transfer film according to any one of claims 1 to 8, wherein the second curable transparent resin layer has a refractive index of 1.65 or more. The transfer film according to any one of claims 1 to 9 , wherein the film thickness of the second curable transparent resin layer is 500 nm or less. The transfer film according to any one of claims 1 to 10 , wherein the second curable transparent resin layer contains fine particles having a refractive index of 1.55 or more. The transfer film according to any one of claims 1 to 11 , wherein the second curable transparent resin layer contains a polymerizable compound. The transfer film according to any one of claims 1 to 11, wherein the second curable transparent resin layer contains a polymerizable compound and a photopolymerization initiator. The transfer film according to any one of claims 1 to 13, wherein the second curable transparent resin layer contains an alkali-soluble resin.

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