JPWO2017081948A1 - Conductive laminate for touch sensor and manufacturing method thereof - Google Patents

Abstract

Provided is a conductive laminate for a touch sensor and a method for manufacturing the conductive laminate for a touch sensor that have a decorative layer made of an ultraviolet curable resin and can prevent deterioration in reliability and quality while being molded into a three-dimensional shape. To do. A plurality of first electrodes 11 and a plurality of first peripheral wirings 12 are formed on the surface 1 </ b> A of the transparent substrate 1, and a decoration layer 2 made of an ultraviolet curable resin is formed on the plurality of first peripheral wirings 12. Layer 2 is represented by R (%) = [(length at break−length before stretching) / length before stretching] × 100 when a tensile test is performed in an atmosphere at a temperature of 180 ° C. The draw ratio R is 10 to 400%.

Description

The present invention relates to a conductive laminate for a touch sensor, and more particularly to a conductive laminate for a touch sensor having a decorative layer and molded into a three-dimensional shape.
The present invention also relates to a method for manufacturing such a conductive laminate for a touch sensor.

In recent years, in various electronic devices such as portable information devices, touch sensors that are used in combination with a display device such as a liquid crystal display device and perform an input operation to the electronic device by touching a screen have been widely used. .
In addition, as the operability of electronic devices is being pursued, touch sensors that are compatible with a three-dimensional shape are required, and a touch having a detection electrode portion formed on a flexible transparent insulating substrate. Sensor development is underway.
For example, Patent Document 1 discloses a touch sensor that uses a metal mesh electrode and is bent into a three-dimensional shape.

Japanese Patent Laying-Open No. 2015-153355

In such a touch sensor, if a decorative layer is formed on the surface of the sensor using an ink containing an ultraviolet curable compound or the like, for example, by an ink jet method, further processing and modification are not necessary in the subsequent process, and A small quantity of various types of touch sensors can be easily manufactured on demand. In particular, there is a peripheral wiring portion including a lead-out wiring from the detection electrode portion around the detection electrode portion. Conventionally, a peripheral edge member is attached to the touch sensor to hide the peripheral wiring portion. If the decorative layer can be formed on the surface and the peripheral wiring portion can be hidden by the decorative layer, it is not necessary to attach a peripheral edge member, and the touch sensor can be thinned and the manufacturing process can be simplified. It becomes.
However, when the touch sensor is formed into a three-dimensional shape, the detection electrode portion and the peripheral wiring portion are stretched. However, when the decoration layer is formed using ultraviolet curable ink, the detection electrode portion and the peripheral wiring portion are stretched. Failures such as disconnection of conductive members such as peripheral wiring portions, cracking and peeling of the decorative layer, etc. may occur, leading to deterioration in reliability and quality as a touch sensor.

The present invention has been made to solve such conventional problems, and has a decorative layer made of an ultraviolet curable resin and prevents deterioration in reliability and quality while being molded into a three-dimensional shape. An object is to provide a conductive laminate for a touch sensor.
Another object of the present invention is to provide a method for manufacturing such a conductive laminate for a touch sensor.

A conductive laminate for a touch sensor according to the present invention is a conductive laminate for a touch sensor molded in a three-dimensional shape, and includes a transparent substrate, a conductive layer formed on at least one surface of the substrate, and a conductive layer. And a decorative layer made of an ultraviolet curable resin formed on the layer, and the decorative layer was subjected to a tensile test in an atmosphere at a temperature of 180 ° C. R (%) = [(length at break -Length before stretching) / Length before stretching] The stretching ratio R represented by x100 is 10 to 400%.

The conductive layer has a detection electrode part and a peripheral wiring part connected to the detection electrode part, and the decorative layer is formed on the peripheral wiring part, or at least a part of the detection electrode part and the peripheral wiring part It can be configured to be formed on top.
When the conductive layer is formed on both sides of the substrate, the decorative layer can be formed on the conductive layer on one side of the substrate.

A method for manufacturing a conductive laminate for a touch sensor according to the present invention is a method for manufacturing a conductive laminate for a touch sensor molded into a three-dimensional shape, and a conductive layer is formed on at least one surface of a transparent substrate. A process, a process of forming a decorative layer made of an ultraviolet curable resin on the conductive layer, and a process of forming a substrate on which the conductive layer and the decorative layer are formed into a three-dimensional shape. When a tensile test is performed in an atmosphere at 180 ° C., R (%) = [(length at break−length before stretching) / length before stretching] × 100, where the stretching ratio R is 10 ~ 400%.

The step of forming the decorative layer includes a step of depositing an ultraviolet curable ink containing a compound having a polymerizable group and a polymerization initiator on the conductive layer, and a step of curing the deposited ultraviolet curable ink. Can be included.
The ultraviolet curable ink preferably contains a polymer having a glass transition temperature of 25 ° C to 100 ° C.

According to this invention, when the decorative layer made of an ultraviolet curable resin formed on the conductive layer is subjected to a tensile test in an atmosphere at a temperature of 180 to 200 ° C., R (%) = [(length at break Length−length before stretching) / length before stretching] × 100, the stretch ratio R is 10 to 400%, so it has a decorative layer made of an ultraviolet curable resin and is molded into a three-dimensional shape. However, it is possible to prevent deterioration in reliability and quality.

It is a top view which shows the structure of the electrically conductive laminated body for touch sensors which concerns on embodiment of this invention. It is a top view which shows the mesh pattern of an electrode. It is sectional drawing which shows the conductive laminated body for touch sensors which concerns on embodiment. It is sectional drawing which shows the test piece by which a tension test is performed. It is a perspective view which shows the conductive laminated body for touch sensors shape | molded by the three-dimensional shape.

Embodiments of the present invention will be described below with reference to the accompanying drawings.
FIG. 1 shows a configuration of a conductive laminate for a touch sensor according to an embodiment of the present invention. This conductive laminate for a touch sensor has a transparent substrate 1, an active area S <b> 1 serving as a detection area for the touch sensor is defined in the center of the transparent substrate 1, and a peripheral region S <b> 2 is defined outside the active area S <b> 1. ing.

On the surface 1A of the transparent substrate 1, a plurality of first electrodes that extend along the first direction D1 and are arranged in parallel in a second direction D2 orthogonal to the first direction D1 in the active area S1. 11 is formed, and a plurality of first peripheral wirings 12 connected to the plurality of first electrodes 11 are arranged close to each other in the peripheral region S2.
Similarly, on the back surface 1B of the transparent substrate 1, a plurality of second electrodes 13 each extending along the second direction D2 and arranged in parallel in the first direction D1 are formed in the active area S1, In the peripheral region S2, a plurality of second peripheral wirings 14 connected to the plurality of second electrodes 13 are arranged close to each other.
The plurality of first peripheral wirings 12 and the plurality of second peripheral wirings 14 form a peripheral wiring part.

In the peripheral region S2 on the surface 1A of the transparent substrate 1, a decorative layer 2 made of an ultraviolet curable resin is formed. In the peripheral region S2 on the surface 1A of the transparent substrate 1, both end portions in the first direction D1 of the respective first electrodes 11 and a plurality of first peripheral wirings 12 are arranged. Both end portions of the first electrode 11 and the first peripheral wiring 12 are covered.
The decorative layer 2 is formed of, for example, an opaque ultraviolet curable resin, for example, and when viewed from the surface 1A side of the transparent substrate 1, the first peripheral wiring 12 and the like arranged in the peripheral region S2 are formed by the decorative layer 2. It becomes a hidden state. On the other hand, the active area S1 in which the decorative layer 2 does not exist is transparent.

  The plurality of first electrodes 11 on the front surface 1A of the transparent substrate 1 and the plurality of second electrodes 13 on the back surface 1B of the transparent substrate 1 constitute a detection electrode portion of the touch sensor, as shown in FIG. The first electrode 11 is preferably formed by a mesh pattern made of the fine metal wires 11A, and the second electrode 13 is also preferably made by a mesh pattern made of the fine metal wires 13A.

As shown in FIG. 3, the decorative layer 2 is not disposed on the back surface 1 </ b> B of the transparent substrate 1 but is disposed only in the peripheral region S <b> 2 on the front surface 1 </ b> A of the transparent substrate 1. The decorative layer 2 covers the surface 1A of the transparent substrate 1 exposed from between the first peripheral wiring 12 and the like on the first peripheral wiring 12 and the like disposed on the surface 1A of the transparent substrate 1 in the peripheral region S2. It is formed as follows.
This conductive laminate for a touch sensor is used so that the surface 1A of the transparent substrate 1 faces the viewing side of the touch sensor when the touch sensor is configured.

The decorative layer 2 is subjected to a tensile test in an atmosphere at a temperature of 180 ° C. R (%) = [(length at break-length before stretching) / length before stretching] × 100・ (1)
The stretching ratio R represented by is 10 to 400%.
Here, as shown in FIG. 4, the tensile test is performed on a test piece prepared by cutting out a decorative layer 2 formed on the entire surface 1 </ b> A of the transparent substrate 1 to a size of 5 cm × 2 cm, for example. The length of the test piece when the decorative layer 2 is broken by pulling using a tensile tester (Tensilon (trade name), manufactured by Shimadzu Corporation) at a temperature of 180 ° C. and a pulling speed of 50 mm / min. It can be implemented by measuring. The stretching ratio R is obtained by substituting the measured length of the test piece at the time of fracture and the length before the test, that is, the length of 5 cm before the stretching, into the above formula (1).

  When the decorative layer 2 has a stretching ratio R of 10 to 400% when a tensile test is performed in an atmosphere at a temperature of 180 ° C., the conductive laminate for a touch sensor shown in FIG. Even if it is formed into a three-dimensional shape such as the box shape shown, disconnection of the plurality of first electrodes 11 and the plurality of first peripheral wirings 12 on the surface 1A of the transparent substrate 1, cracking and peeling of the decorative layer 2, etc. It is possible to configure a touch sensor with high reliability and high quality that does not occur.

  Such a conductive laminate for a touch sensor having a three-dimensional shape forms a patterned conductive layer composed of a plurality of first electrodes 11 and a plurality of first peripheral wirings 12 on the surface 1A of the transparent substrate 1, and After forming a patterned conductive layer composed of a plurality of second electrodes 13 and a plurality of second peripheral wirings 14 on the back surface 1B of the transparent substrate 1, a decorative layer is formed in the peripheral region S2 of the surface 1A of the transparent substrate 1 2 and further, the transparent substrate 1 on which the conductive layer and the decorative layer 2 are formed is bent and formed into a three-dimensional shape.

  In addition, a conductive material composed of a plurality of first electrodes 11 and a plurality of first peripheral wirings 12 on the front surface 1A of the transparent substrate 1 and a plurality of second electrodes 13 and a plurality of second peripheral wirings 14 on the back surface 1B of the transparent substrate 1. The method for forming the layer is not particularly limited. For example, as described in JP-A-2012-185813, paragraphs 0067 to 0083, a photosensitive material having an emulsion layer containing a photosensitive silver halide salt is exposed and developed to form a conductive layer. Can be formed.

  Alternatively, a metal foil is formed on each of the front and back surfaces of the transparent substrate 1, and a resist is printed in a pattern on each metal foil, or the resist applied on the entire surface is exposed and developed to form a pattern, thereby opening the openings. These conductive layers can also be formed by etching part of the metal. In addition to this, a paste containing fine particles of the material constituting the conductive layer is printed on the front and back surfaces of the transparent substrate 1 and the paste is subjected to metal plating, and an ink containing fine particles of the material constituting the conductive layer is used. A method using an inkjet method used, a method of forming ink containing fine particles of the material constituting the conductive layer by screen printing, a method of forming a groove in the transparent substrate 1 and applying a conductive ink to the groove, microcontact A printing patterning method or the like can be used.

  Further, these conductive layers include conductive fibers such as metal nanowires, metal nanotubes, and carbon nanotubes (CNT) and a binder as described in paragraphs 0046 to 0124 of JP2013-77234A, for example. It can also be formed using a transparent conductive film. In this specification, a fiber having a solid structure is referred to as a “wire”, and a fiber having a hollow structure is referred to as a “tube”.

(Metal nanowires)
Examples of the material of the metal nanowire include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, and antimony. , Lead, or an alloy thereof. Among these, silver and an alloy with silver are preferable in terms of excellent conductivity.
The shape of the metal nanowire can take any shape such as a columnar shape, a rectangular parallelepiped shape, or a columnar shape with a polygonal cross section. Among these, since the columnar shape or the cross-sectional shape with rounded polygonal corners provides high transparency, the first electrode 11 and the second electrode 13 disposed in the active area S1 of the touch sensor are obtained. Is preferable.

The average minor axis length of the metal nanowire is preferably 1 nm to 50 nm, more preferably 10 nm to 40 nm, and further preferably 15 nm to 35 nm.
The average major axis length of the metal nanowire is preferably 1 μm to 50 μm, more preferably 5 μm to 45 μm, and still more preferably 10 μm to 40 μm.
As a manufacturing method of metal nanowire, it describes in Unexamined-Japanese-Patent No. 2009-215594, Unexamined-Japanese-Patent No. 2009-242880, Unexamined-Japanese-Patent No. 2009-299162, Unexamined-Japanese-Patent No. 2010-84173, Unexamined-Japanese-Patent No. 2010-86714, etc. This method can be used.

(Metal nanotube)
There is no restriction | limiting in particular as a material of a metal nanotube, What kind of metal may be sufficient, For example, the material of said metal nanowire can be used.
The shape of the metal nanotube may be a single layer or may be a multilayer, but a single layer is preferable from the viewpoint of excellent conductivity and thermal conductivity.
The thickness of the metal nanotube (the difference between the outer diameter and the inner diameter) is preferably 3 nm to 80 nm, and more preferably 3 nm to 30 nm.
The average major axis length of the metal nanotube is preferably 1 μm to 40 μm, more preferably 3 μm to 35 μm, and even more preferably 5 μm to 30 μm.

(carbon nanotube)
A carbon nanotube (CNT) is a substance in which a graphite-like carbon atomic surface (graphene sheet) is a single-layer or multilayer coaxial tube. The carbon nanotube may be a single wall or a multilayer, but a single wall is preferable from the viewpoint of excellent conductivity and thermal conductivity.

  Although there is no limitation in particular as a binder contained in a transparent conductive film with these electroconductive fibers, A photosensitive compound is preferable and can also contain another component as needed.

  However, the conductive layer in the present invention is preferably formed of a fine metal wire or conductive fiber from the viewpoint of bending in a three-dimensional shape, and in particular, a conductive layer formed of a fine metal wire. preferable. The fine metal wire is preferably a fine metal wire made of copper or silver.

  The decorative layer 2 is formed by ejecting ultraviolet curable ink onto the peripheral region S2 from the surface 1A side of the transparent substrate 1 by, for example, an inkjet method, and then irradiating the ejected ink with ultraviolet rays to cure the ink. Can be formed. That is, the decorative layer 2 is a layer formed by curing an ultraviolet curable ink. In addition, the ultraviolet curable resin mentioned above intends resin (cured resin) obtained by hardening ultraviolet curable ink.

Here, the ultraviolet curable ink (ultraviolet curable ink composition) that can be used to form the decorative layer 2 in the present invention will be described.
In addition, “(meth) acrylate” and the like are synonymous with “acrylate and / or methacrylate” and the like, “(meth) acryl” and the like are synonymous with “acryl and / or methacryl” and so on. .
The component contained in the ultraviolet curable ink is not particularly limited as long as the decorative layer exhibiting the above-mentioned predetermined R (%) is obtained, but contains a compound having a polymerizable group (polymerizable compound) and a polymerization initiator. It is preferable.
The kind of the polymerizable group in the compound having a polymerizable group is not particularly limited, and examples thereof include known groups, such as a radical polymerizable group or a cationic polymerizable group. Groups are preferred. Examples of the radical polymerizable group include methacryloyloxy group, acryloyloxy group, vinyl group, styryl group, acrylamide group, and methacrylamide group.

Preferred embodiments of the compound having a polymerizable group include the following (Component A) to (Component C), and the ultraviolet curable ink includes these (Component A), (Component B) and (Component C). It is preferable that
(Component A) N-vinylcaprolactam (Component B) Monofunctional acrylate having an aromatic ring (Component C) Monofunctional acrylate having an aliphatic hydrocarbon ring

  The ultraviolet curable ink preferably contains 5 to 40% by mass, more preferably 10 to 30% by mass, of Component A with respect to the total mass of the ultraviolet curable ink.

  The monofunctional acrylate having an aromatic ring as component B is not particularly limited as long as it is a compound having one or more aromatic rings and one acrylate group, but is a compound represented by the following formula (B-1) It is preferable that

(In Formula (B-1), Ar ¹ represents an aromatic group, and L ¹ represents a single bond, an alkylene group, an alkyleneoxy group, or a polyalkyleneoxy group.)

What is preferable as an aromatic group in Ar ¹ is a polycyclic aromatic group having 2 to 4 rings in addition to a monocyclic aromatic phenyl group, and is not limited. Of these, a phenyl group is preferred. The aromatic group may have one or more alkyl groups, aromatic groups, halogen atoms, hydroxyl groups, amino groups, thiol groups, siloxane groups, and substituents having 30 or less carbon atoms. For example, you may form the cyclic structure containing hetero atoms, such as O, N, and S, by two or more substituents which an aromatic group has like phthalic anhydride and phthalimide anhydride.
L ¹ is preferably a single bond, an alkyleneoxy group or a polyalkyleneoxy group, more preferably a single bond or an alkyleneoxy group, and particularly preferably an ethyleneoxy group.

Component B may be used alone or in combination of two or more.
The content of Component B is preferably 10 to 70% by mass and more preferably 20 to 50% by mass with respect to the total mass of the ultraviolet curable ink.

  The monofunctional acrylate having an aliphatic hydrocarbon ring as component C is not particularly limited as long as it is a compound having one or more aliphatic hydrocarbon rings and one acrylate group, but the following formula (C-1 It is preferable that it is a compound represented by this.

(In formula (C-1), Cy ¹ represents an aliphatic hydrocarbon ring group, and L ² represents a single bond, an alkylene group, an alkyleneoxy group, or a polyalkyleneoxy group.)

Examples of the aliphatic hydrocarbon ring group in Cy ¹ include a cyclohexyl group, 3,3,5-trimethylcyclohexyl group, 4-t-butylcyclohexyl group, isobornyl group, norbornyl group, dicyclopentanyl group, dicyclopentenyl group, A tricyclodecanyl group is preferred. The aliphatic hydrocarbon ring group may have one or more alkyl groups, halogen atoms, hydroxyl groups, amino groups, thiol groups, siloxane groups, and substituents having 30 or less carbon atoms. For example, a cyclic structure containing a heteroatom such as O, N, and S may be formed by two or more substituents of the aliphatic hydrocarbon ring group. In addition, the aliphatic hydrocarbon ring group may have an ethylenically unsaturated bond.
L ² is preferably a single bond, an alkyleneoxy group or a polyalkyleneoxy group, more preferably a single bond or an alkyleneoxy group, and particularly preferably a single bond.

Component C may be used alone or in combination of two or more.
The content of Component C is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and further preferably 10 to 20% by mass with respect to the total mass of the ultraviolet curable ink. preferable.

  In the ultraviolet curable ink, it is preferable that the content of component A to component C satisfies (content of component C) / (content of component A + content of component B) <0.6 by mass ratio. , (Content of component C) / (content of component A + content of component B) <0.5 is more preferable, (content of component C) / (content of component A + component B) It is particularly preferred that the content of Moreover, it is preferable to satisfy (content of component C) / (content of component A + content of component B)> 0.1, and (content of component C) / (content of component A + component B) Content)> 0.15 is more preferable.

As the polymerization initiator, a photopolymerization initiator is preferably exemplified.
Polymerization initiators include (a) aromatic ketones, (b) acylphosphine compounds, (c) aromatic onium salt compounds, (d) organic peroxides, (e) thio compounds, (f) hexaarylbiphenyls. An imidazole compound, (g) a ketoxime ester compound, (h) a borate compound, (i) an azinium compound, (j) a metallocene compound, (k) an active ester compound, (l) a compound having a carbon halogen bond, and (m ) Alkylamine compounds and the like. These compounds may be used alone or in combination. Further, for example, a plurality of types of (a) aromatic ketones can be used in combination.

  The content of the polymerization initiator is preferably 0.01 to 35% by weight, more preferably 0.5 to 20% by weight, based on the total mass of the polymerizable compound in the ultraviolet curable ink. 1.0 to 15% by weight is more preferable.

The ultraviolet curable ink may contain components other than the above-described compound having a polymerizable group (polymerizable compound) and a polymerization initiator.
For example, the ultraviolet curable ink preferably contains a polymer having a glass transition temperature (Tg) of 25 ° C to 100 ° C. In addition, it is preferable that the glass transition temperature of the said polymer is 35 to 95 degreeC, and it is more preferable that it is 60 to 90 degreeC.
If the glass transition temperature (Tg) of the polymer is within the above range, it is excellent in inkjet discharge property, adhesion to a substrate and blocking resistance of the resulting decorative printed material, and after trimming after vacuum forming. Processing cracks can be suppressed, and the effects of the present invention are more excellent.

  The weight average molecular weight of the polymer is preferably 3,000 to 100,000, more preferably 3,000 to 80,000, and still more preferably 3,000 to 50,000.

For the molecular weight such as the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer, measured values obtained by actual measurement are applied. Specifically, the polymer molecular weight means a value measured under normal measurement conditions using high performance liquid chromatography.
The measured glass transition temperature (Tg) of the polymer is the measured Tg obtained by actual measurement. Specifically, as the measurement Tg, a value measured under normal measurement conditions using a differential scanning calorimeter (DSC) EXSTAR 6220 manufactured by SII Nanotechnology, Inc. can be used.
However, when measurement is difficult due to polymer decomposition or the like, calculation Tg calculated by the following calculation formula is applied. The calculation Tg is calculated by the following formula (T).
1 / Tg = Σ (Xi / Tgi) (T)
Here, it is assumed that n types of monomer components from i = 1 to n are copolymerized in the polymer to be calculated. Xi is the weight fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. In addition, the value (Tgi) of the homopolymer glass transition temperature of each monomer employ | adopts the value of Polymer Handbook (3rd Edition) (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)).

The type of the polymer is not particularly limited, but is preferably a (meth) acrylic resin.
The (meth) acrylic resin may be a homopolymer of a (meth) acrylate compound or a copolymer, but it is easy to control Tg and has good compatibility with ink. Further, from the viewpoint of being inexpensive, it is preferably a homopolymer or copolymer of a monofunctional (meth) acrylate compound, and more preferably a copolymer of two or more monofunctional (meth) acrylate compounds. Preferably, it is a copolymer of methyl methacrylate and a monofunctional (meth) acrylate compound.
The polymer is preferably an inert (meth) acrylic resin. In the present invention, the “inactive (meth) acrylic resin” means that the (meth) acrylic resin does not have a polymerizable functional group capable of further chain polymerization reaction, and is capable of further sequential crosslinking reaction. And / or a polymer having no crosslinkable functional group. That is, it refers to an acrylic resin that does not substantially cause a polymerization reaction and a crosslinking reaction.

From the viewpoint of easy control of Tg, good compatibility with ink, and low cost, the polymer is methyl methacrylate, n-butyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2 A copolymer of two or more methacrylic compounds selected from the group consisting of ethylhexyl methacrylate, isodecyl methacrylate, methoxypolyethylene glycol methacrylate, n-lauryl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, and t-butyl methacrylate. Preferably there is.
The content of the polymer is preferably 1 to 8% by mass, more preferably 2 to 6% by mass, and further preferably 3 to 5% by mass with respect to the total mass of the ultraviolet curable ink. .

The ultraviolet curable ink contains a polyether-modified silicone compound having a (meth) acrylate group (hereinafter, also simply referred to as “silicone compound”) in that it is excellent in curability, blocking resistance of decorative printed matter, and vacuum moldability. You may do it.
The silicone compound is not particularly limited as long as it is a compound having a (meth) acrylate group, a polyether moiety, and a polysiloxane moiety, but is preferably a compound having a molecular weight of 500 or more, and a molecular weight (weight average) More preferably, the molecular weight is 1,000 or more.
It is preferable that the silicone compound has 4 to 6 (meth) acrylate groups.
The mass ratio of the polyether moiety to the polysiloxane moiety in the silicone compound is preferably in the range of polyether moiety: polysiloxane moiety = 1: 1 to 1: 2.
The bonding position of the (meth) acrylate group in the silicone compound is not particularly limited, and may be a main chain or a side chain.
The position of the polyether modification in the silicone compound is not particularly limited, and may be one end of the main chain, both ends, or a side chain.
It is preferable that the polyether part which a silicone compound has is a polyalkyleneoxy group.
The silicone compound is preferably a polydimethylsiloxane compound.

A silicone compound may be used individually by 1 type, and may use 2 or more types together.
The content of the silicone compound is preferably 0.1 to 10% by mass, more preferably 0.5 to 4% by mass, and more preferably 0.5 to 3% by mass with respect to the total mass of the ultraviolet curable ink. % Is more preferable.

The ultraviolet curable ink may contain a pigment in order to improve the visibility of the formed image portion.
The pigment that can be used is not particularly limited, and can be arbitrarily selected from known pigments. From the viewpoint of not reducing the sensitivity of the curing reaction by actinic radiation, it is preferable to select a compound that does not function as a polymerization inhibitor in the polymerization reaction that is a curing reaction.
Although it does not necessarily limit as a pigment, For example, the organic or inorganic pigment of the number described in a color index can be used. Examples thereof include red or magenta pigments, blue or cyan pigments, green pigments, yellow pigments, black pigments, and white pigments.
The content of the pigment is appropriately selected depending on the color and purpose of use, but is preferably 0.01 to 30% by weight with respect to the total mass of the ultraviolet curable ink.

  The ultraviolet curable ink preferably contains a dispersant in order to stably disperse the pigment in the ink. As the dispersant that can be used in the present invention, a polymer dispersant is preferable. The “polymer dispersing agent” in the present invention means a dispersing agent having a weight average molecular weight of 1,000 or more.

In addition to the components described above, the ultraviolet curable ink contains co-sensitizers, surfactants, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, solvents, basic compounds, and the like. Also good.
In the ultraviolet curable ink, it is possible to use other polymerizable compounds other than the components A to C and the silicone compound, but it is preferable that no other polymerizable compound is contained.

  Such an ultraviolet curable ink is cured by being irradiated with ultraviolet rays after being ejected onto the peripheral region S2 by, for example, an ink jet method. As an ultraviolet ray source, an ultraviolet LED (light emitting diode), an ultraviolet LD (laser) diode) or the like can be used. For example, Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. Where even shorter wavelengths are required, examples of LEDs are those that can emit actinic radiation centered between 300 nm and 370 nm as disclosed in US Pat. No. 6,084,250. it can. Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands.

  It is preferable to irradiate the ultraviolet curable ink from such an ultraviolet source with ultraviolet rays, preferably for 0.01 to 120 seconds, more preferably for 0.1 to 90 seconds. The ultraviolet irradiation condition and the basic irradiation method are disclosed in, for example, Japanese Patent Application Laid-Open No. 60-132767.

  If the decorative layer 2 is formed by ejecting ultraviolet curable ink by, for example, an inkjet method, further processing and modification are unnecessary in the subsequent process, and it is not necessary to attach a peripheral edge member as in the past. It is possible to reduce the thickness of the touch sensor and simplify the manufacturing process.

In the above embodiment, a plurality of first electrodes 11 and a plurality of first peripheral wirings 12 are disposed on the front surface 1A of the transparent substrate 1, and a plurality of second electrodes are disposed on the back surface 1B of the transparent substrate 1. However, the present invention is not limited to this.
For example, a plurality of first electrodes 11 and a plurality of second electrodes 13 are disposed on one surface of the front surface 1A and the back surface 1B of the transparent substrate 1 with an interlayer insulating film interposed therebetween, and the transparent substrate 1 is the same. A plurality of first peripheral wirings 12 and a plurality of second peripheral wirings 14 are arranged on the surface, and the decoration layer 2 may be formed in the peripheral region S2 on the surface 1A of the transparent substrate 1 on the viewing side. it can.
Moreover, it can also be set as the structure of 2 sheets. That is, a plurality of first electrodes 11 and a plurality of first peripheral wirings 12 are arranged on the surface of the first transparent substrate, and a plurality of second electrodes 13 and a plurality of second peripherals are arranged on the surface of the second transparent substrate. It is also possible to use the first transparent substrate and the second transparent substrate by arranging the wiring 14 so as to overlap each other. In this case, the decorating layer 2 may be formed in the peripheral region S2 of the transparent substrate located on the viewing side of the first transparent substrate and the second transparent substrate.

Furthermore, in the above embodiment, the decorative layer 2 is formed only in the peripheral region S2 in which the peripheral wiring portion including the plurality of first peripheral wirings 12 and the plurality of second peripheral wirings 14 is disposed. However, the present invention is not limited to this, and the decorative layer 2 can be formed in at least a part of the active area S1 and the peripheral region S2. That is, the decorative layer 2 is formed not only on the peripheral wiring part but also on a part of the detection electrode part composed of the plurality of first electrodes 11 and the plurality of second electrodes 13 or on the whole detection electrode part. May be.
When the decorative layer 2 formed of an opaque ultraviolet curable resin is formed only in the peripheral region S2 as in the above embodiment, the touch sensor should be used in combination with a display device such as a liquid crystal display device. Thus, the entire active area S1 can be overlaid on the display screen of the display device, and the entire detection electrode section can act as detection means in the display screen.

On the other hand, the decorative layer 2 formed of an opaque ultraviolet curable resin is formed so as to cover not only the peripheral region S2 but also a part of the detection electrode portion in the active area S1, and is covered with the decorative layer 2. If the remaining part of the non-detecting electrode part is arranged so as to overlap the display screen of the display device, the remaining part of the detecting electrode part acts as a detecting means in the display screen and is covered with the decorative layer 2 It is possible to act as a detection means in the periphery of the display screen.
In addition, since it is not necessary to form a transparent region in order to use the touch sensor alone without being combined with the display device, the entire active area S1 and the peripheral region S2 of the touch sensor are made of an opaque ultraviolet curable resin. The decorative layer 2 can be formed on the peripheral wiring portion disposed in the peripheral region S2 and the detection electrode portion disposed in the active area S1.

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

Example 1
<Preparation of pigment dispersion>
A composition other than the pigment described in Table 1 below is mixed and stirred with a mixer manufactured by SILVERSON (10-15 minutes, 2,000-3,000 rpm), and a uniform transparent liquid (dispersant diluent) is prepared. Obtained. The pigment described in Table 1 below is added to this transparent liquid (dispersant diluent), and further stirred with a mixer (10 to 20 minutes, 2,000 to 3,000 revolutions / minute). A mass part was obtained. Then, the dispersion process was implemented using the circulation type bead mill apparatus (SL-012C1) by a Dispermat company. Dispersion conditions were such that 200 parts by mass of zirconia beads having a diameter of 0.65 mm were filled, and the peripheral speed was 15 m / sec. The dispersion time was 1 to 6 hours.

Details of the raw materials listed in Table 1 are shown below. Moreover, each numerical value of Table 1 represents a mass part.
Cyan pigment: C.I. I. Pigment Blue 15: 4, HELIOGEN BLUE D 7110 F, manufactured by BASF,
Magenta pigment: Mixed quinacridone pigment, CINQUASIA MAGENTA L 4540, manufactured by BASF,
Yellow pigment: C.I. I. Pigment Yellow 155, INK JET YELLOW 4GC, manufactured by Clarinat,
Black pigment: Carbon black, MOGUL E, manufactured by CABOT,
White pigment: TiO ₂ , KRONOS 2300, manufactured by KRONOS,
Dispersant A: SOLPERSE 32000, manufactured by Luburizol,
Dispersant B: SOLPERSE 41000, manufactured by Luburizol,
Inhibitor: Nitroso polymerization inhibitor, Tris (N-nitroso-N-phenylhydroxylamine) aluminum salt, FLORSTAB UV12, manufactured by Kromachem,
Monomer: 2-phenoxyethyl acrylate, SR339C, manufactured by Sartomer.

<Synthesis of Polymer 1>
20 g of a mixture of 10 g of n-butyl methacrylate and 10 g of methyl methacrylate and 30 g of methyl ethyl ketone were introduced into a nitrogen-substituted three-necked flask and stirred with a stirrer (three-one motor manufactured by Shinto Kagaku Co., Ltd.). The mixture was heated to 65 ° C. while flowing.
First stage: Add 80 mg of 2,2-azobis (2,4-dimethylvaleronitrile (V-65, manufactured by Wako Pure Chemical Industries, Ltd.)) to the above mixture and stir at 65 ° C. for 30 minutes. went.
Second stage: Only 80 mg of V-65 was added, and the mixture was further heated and stirred at 65 ° C. for 1 hour.
The obtained reaction liquid was poured into 1,000 mL of hexane with stirring, and the resulting precipitate was heated and dried to obtain polymer 1. The glass transition temperature (Tg) of polymer 1 is 70 ° C. As a result of measuring the weight average molecular weight (polystyrene conversion) of the polymer 1 by GPC, it was in the range of 30,000 to 35,000.

<Preparation of ink set N1 (monomer composition)>
Among the compositions shown in Table 2 below, components other than the polymerization initiator and the pigment dispersion are stirred with a mixer manufactured by SILVERSON (60 minutes, 3,000 to 5,000 rpm) to obtain a uniform transparent liquid. It was. To this transparent liquid, a polymerization initiator (ITX, TPO, Irg819) and a pigment dispersion are added and stirred (10 to 20 minutes, 2,000 to 3,000 rpm) to obtain a solvent-based ink set N1. It was.

Details of the raw materials described in Table 2 are shown below. Moreover, each numerical value of Table 2 represents a mass part.
PEA (2-phenoxyethyl acrylate, SR339C, manufactured by Sartomer),
IBOA (isobornyl acrylate, SR506D, manufactured by Sartomer),
NVC (N-vinylcaprolactam, manufactured by BASF),
OH-TEMP (4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-HYDROXY TEMPO, manufactured by Evonik),
ITX (Isopropylthioxanthone, SPEEDCURE ITX, manufactured by Lambson),
TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide, LUCIRIN TPO, manufactured by BASF),
Irg819 (bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, IRGACURE 819, manufactured by BASF),
TEGORAD 2010 (polyether-modified silicone compound acrylate group number = 5, manufactured by Evonik).

<Preparation of decoration layer>
The obtained ink set N1 was placed on the surface of a transparent substrate (polycarbonate (PC) film, film thickness 500 μm, manufactured by Teijin Chemicals Ltd., trade name: Panelite), a commercially available inkjet printer (Fuji A so-called solid image in which the entire surface of the transparent substrate was drawn with five colors of full-color ink was formed.
The ink supply system was composed of an original tank, a supply pipe, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head. The ink supply tank to the inkjet head portion were insulated and heated. Temperature sensors were arranged in the vicinity of the nozzles of the ink supply tank and the inkjet head, respectively, and temperature control was performed so that the nozzle portions were always 40 ° C. ± 2 ° C. The piezo-type inkjet head was driven so that 1 to 10 pl multi-size dots could be ejected at a resolution of 600 × 600 dpi (dots / inch).

Then, the FineArt Lamp intensity was set to 5, and the ink was irradiated with ultraviolet rays to cure the ink.
Then, the ink image was fixed by performing a drying process, and a decorative layer having an average film thickness of 30 μm was formed by drawing the entire surface of the transparent substrate in five colors. The drying process is a drying process at 60 ° C. for 5 minutes from the non-image-forming surface of the transparent substrate (the surface opposite to the side where the ink image is formed). ) To 90 ° C. for 5 minutes.
Thereby, the transparent substrate with a decoration layer of Example 1 was produced.

Example 2
<Preparation of ink set N2 (monomer composition)>
Among the compositions shown in Table 3 below, components other than the polymerization initiator and the pigment dispersion are stirred with a mixer manufactured by SILVERSON (60 minutes, 3,000 to 5,000 rpm) to obtain a uniform transparent liquid. It was. To this transparent liquid, a polymerization initiator and a pigment dispersion were added and stirred (10 to 20 minutes, 2,000 to 3,000 rpm) to obtain a solvent-based ink set N2.
A transparent substrate with a decorative layer of Example 2 was produced in the same manner as in Example 1 except that the ink set N2 was used instead of the ink set N1.

Of the raw materials listed in Table 3, details of TEGORAD 2200 are shown. Moreover, each numerical value of Table 3 represents a mass part.
TEGORAD 2200 (polyether-modified silicone compound, acrylate group number = 2, manufactured by Evonik).

Example 3
Except for using a transparent substrate made of polyethylene terephthalate (PET, thickness: 1.00 mm, Falcon Petg, manufactured by Robert Horne) instead of a transparent substrate made of polycarbonate (PC) film, the same procedure as in Example 1 was performed. A transparent substrate with a decorative layer of Example 3 was produced.

Example 4
Except for using a transparent substrate made of a cycloolefin polymer film (COP, thickness 100 μm, ZEONOR film ZF14-100, manufactured by Nippon Zeon Co., Ltd.) instead of a transparent substrate made of a polycarbonate (PC) film, the same as in Example 1, A transparent substrate with a decorative layer of Example 4 was produced.

Example 5
By exposing and developing a photosensitive material having a photosensitive silver salt-containing layer using a so-called silver salt method, on the front and back surfaces of the transparent substrate made of the polycarbonate (PC) film used in Example 1, Each conductive layer having a mesh pattern made of fine metal wires was formed. The specific operation of the silver salt method is described in detail in paragraphs 0163 to 0241 of JP-A-2009-4348.
On the surface of the transparent substrate on which the conductive layer is formed, the ink set N1 used in Example 1 is applied using a commercially available inkjet printer (Acity 350 manufactured by Fuji Film Co., Ltd.) having a piezo-type inkjet nozzle. Then, the decoration layer was formed by performing a drying process and the conductive laminated body for touch sensors of Example 5 was produced.

Example 6
A conductive laminate for a touch sensor of Example 6 was produced in the same manner as Example 5 except that the ink set N2 used in Example 2 was used instead of the ink set N1.

Example 7
Instead of the conductive layer formed by the silver salt method, for example, silver nanowires described in paragraphs 0048 to 0060 of JP2013-77234A are used, and the conductive material is respectively formed on the surface and the back surface of the transparent substrate. A conductive laminate for a touch sensor of Example 7 was produced in the same manner as Example 5 except that the layer was formed.

Example 8
Instead of the conductive layer formed by the silver salt method, for example, using carbon nanotubes (CNT) described in paragraph 0066 of JP2013-77234A, on the front surface and the back surface of the transparent substrate, respectively, A conductive laminate for a touch sensor of Example 8 was produced in the same manner as Example 5 except that the conductive layer was formed.

Example 9
Implementation was performed in the same manner as in Example 5 except that a transparent substrate made of polyethylene terephthalate (PET, thickness: 1.00 mm, Falcon Petg, manufactured by Robert Horne) was used instead of a transparent substrate made of a polycarbonate (PC) film. A conductive laminate for the touch sensor of Example 9 was produced.

Example 10
Except for using a transparent substrate made of a cycloolefin polymer film (COP, thickness 100 μm, ZEONOR film ZF14-100, manufactured by Nippon Zeon Co., Ltd.) instead of a transparent substrate made of a polycarbonate (PC) film, the same as in Example 5, A conductive laminate for a touch sensor of Example 10 was produced.

Comparative Example 1
<Synthesis of Polymer 2>
20 g of t-butyl methacrylate and 30 g of methyl ethyl ketone were introduced into a three-necked flask substituted with nitrogen, stirred with a stirrer (three-one motor manufactured by Shinto Kagaku Co., Ltd.), heated while flowing nitrogen into the flask, and heated to 65 ° C. Warm up.
First stage: Add 80 mg of 2,2-azobis (2,4-dimethylvaleronitrile (V-65, manufactured by Wako Pure Chemical Industries, Ltd.)) to the above mixture and stir at 65 ° C. for 30 minutes. went.
Second stage: Only 80 mg of V-65 was added, and the mixture was further heated and stirred at 65 ° C. for 1 hour.
The obtained reaction solution was poured into 1,000 mL of hexane with stirring, and the resulting precipitate was heated and dried to obtain polymer 2. The glass transition temperature (Tg) of polymer 2 is 107 ° C.

<Preparation of ink set N3 (monomer composition)>
Among the compositions shown in Table 4 below, components other than the polymerization initiator and the pigment dispersion are stirred with a mixer manufactured by SILVERSON (60 minutes, 3,000 to 5,000 rpm) to obtain a uniform transparent liquid. It was. To this transparent liquid, a polymerization initiator and a pigment dispersion were added and stirred (10 to 20 minutes, 2,000 to 3,000 rotations / minute) to obtain a solvent-based ink set N3. The concentration of the polymer 2 in each color ink composition of the ink set N3 is 2% by mass.
A transparent substrate with a decorative layer of Comparative Example 1 was produced in the same manner as in Example 1 except that the ink set N3 was used instead of the ink set N1.

Comparative Example 2
<Synthesis of Polymer 3>
N-butyl methacrylate 20 g and methyl ethyl ketone 30 g were introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (three-one motor manufactured by Shinto Kagaku Co., Ltd.), heated while flowing nitrogen into the flask, and heated to 65 ° C. Warm up.
First stage: Add 80 mg of 2,2-azobis (2,4-dimethylvaleronitrile (V-65, manufactured by Wako Pure Chemical Industries, Ltd.)) to the above mixture and stir at 65 ° C. for 30 minutes. went.
Second stage: Only 80 mg of V-65 was added, and the mixture was further heated and stirred at 65 ° C. for 1 hour.
The obtained reaction liquid was poured into 1,000 mL of hexane while stirring, and the resulting precipitate was heated and dried to obtain polymer 3. The glass transition temperature (Tg) of the polymer 3 is 20 ° C.

  The decoration of Comparative Example 2 is the same as Comparative Example 1, except that the solvent-based ink set N4 is prepared using the polymer 3 instead of the polymer 2, and the ink set N4 is used instead of the ink set N3. A transparent substrate with a layer was produced.

Comparative Example 3
Ink set N3 used in Comparative Example 1 was used instead of ink set N1, and polyethylene terephthalate (PET, thickness: 1.00 mm, Falcon Petg, Robert Horne) was used instead of a transparent substrate made of a polycarbonate (PC) film. A conductive laminate for a touch sensor of Comparative Example 3 was produced in the same manner as in Example 5 except that a transparent substrate made of (manufactured by Komatsu) was used.

Comparative Example 4
Ink set N4 used in Comparative Example 2 was used instead of ink set N1, and polyethylene terephthalate (PET, thickness: 1.00 mm, Falcon Petg, Robert Horne) was used instead of a transparent substrate made of a polycarbonate (PC) film. A conductive laminate for a touch sensor of Comparative Example 4 was produced in the same manner as in Example 5 except that a transparent substrate made of Co., Ltd. was used.

  With respect to the transparent substrate with a decorative layer produced in Examples 1 to 4 and Comparative Examples 1 and 2, the curability of the decorative layer, adhesion, and stretchability during heating were evaluated. The evaluation results are shown in Table 5 below.

For curability, the ink composition prepared in each of Examples 1 to 4 and Comparative Examples 1 and 2 was filled in a commercially available inkjet printer (Acity 350 manufactured by Fuji Film Co., Ltd.) and irradiated with ultraviolet rays with a FineArt Lamp intensity of 5. Then, printed materials were produced and evaluated by the presence or absence of stickiness of the printed materials.
The evaluation result A indicates that there is no stickiness at a FineArt Lamp intensity of 5.
In any of Examples 1 to 4 and Comparative Examples 1 and 2, the evaluation result of curability was A, and it was confirmed that the curability was sufficient without causing stickiness.

As for adhesion, a printed matter is produced with a Lamp strength of 5 using the above-mentioned commercially available inkjet printer (Acuity 350 manufactured by Fuji Film Co., Ltd.) and left at room temperature (25 ° C.) for 24 hours, and then a cross-cut test is performed. Evaluated by.
The evaluation result A indicates 0 point based on JIS K5600-5-6 (ISO 2409), and the evaluation result B indicates 1 point based on JIS K5600-5-6 (ISO 2409).
In any of Examples 1 to 4 and Comparative Examples 1 and 2, the adhesion evaluation result was A or B, and it was confirmed that excellent adhesion or good adhesion was exhibited.

  About the stretchability at the time of heating, a tensile tester (Tensilon) was used for test pieces prepared by cutting out the transparent substrates with decorative layers of Examples 1 to 4 and Comparative Examples 1 and 2 to a size of 5 cm × 2 cm. (Trade name) manufactured by Shimadzu Corporation) was measured at a temperature of 180 ° C. and a pulling speed of 50 mm / min, and the length of the test piece was measured when the decorative layer was broken. The length of the test piece at the time and the length before the test, that is, the length before stretching, were evaluated by the stretching ratio R calculated by substituting into the above formula (1).

  The evaluation result AA has a drawing ratio R of greater than 400%, the evaluation result A has a drawing ratio R of 200% to 400%, the evaluation result B has a drawing ratio R of 10% to less than 200%, and the evaluation result C is The drawing ratio R is less than 10%. If the evaluation result is either A or B, it is evaluated that it has excellent stretchability under heating conditions at a temperature of 180 ° C. and good heat processing suitability, and if the evaluation result is C, it is molded into a three-dimensional shape. When the decorative layer is heated, the stretchability during heating is insufficient, and there is a risk of breakage of the conductive layer, cracking and peeling of the decorative layer, etc. If the evaluation result is AA, the stretchability of the decorative layer Is too large, and it is evaluated that there is a problem in forming a three-dimensional shape with a non-uniform film thickness.

In each of Examples 1 to 4, the evaluation result was A or B, and it was confirmed that the decorative layer had suitable stretchability during heating when it was molded into a three-dimensional shape.
In Comparative Example 1, the evaluation result is C, and the decoration layer is cracked. In Comparative Example 2, the evaluation result is AA, and the heating layer has a stretchability exceeding 400%. It can be seen that the thickness is in a non-uniform state, and both Comparative Examples 1 and 2 have problems in forming into a three-dimensional shape.

  Moreover, with respect to the conductive laminate for a touch sensor produced by the above Examples 5 to 10 and Comparative Examples 3 and 4, the curability of the decorative layer, the adhesion, the stretchability upon heating, and the resistance value of the conductive layer Evaluation was performed. The evaluation results are shown in Table 6 below.

The stretchability upon heating is the same as in Example 1 for a test piece prepared by cutting out a conductive layer and a decorative layer sequentially formed on the entire surface of a transparent substrate into a size of 5 cm × 2 cm. This was evaluated by conducting a tensile test.
Moreover, about the resistance value of a conductive layer, it forms on the surface of the transparent substrate which is the same side as the decoration layer in the conductive laminated body for touch sensors produced by said Examples 5-10 and Comparative Examples 3 and 4. The resistance values at both ends of the plurality of first electrodes were measured for all the electrodes, and evaluated by the rate of change in resistance value before and after heating and stretching under conditions of a temperature of 200 ° C. and a stretching ratio of 20%.

  The ratio of the resistance value after the heat stretching is calculated with respect to the resistance value before the heat stretching, and when the ratio is 1.0 to 1.2, the evaluation result A, the ratio exceeds 1.2 and is 2.0 or less. The case was evaluated as evaluation result B, and the case where the ratio exceeded 2.0 was defined as evaluation result C. Evaluation result A shows that almost no change in conductivity due to stretching was observed, and good characteristics were maintained. Evaluation result B indicates that a slight change in conductivity due to stretching is recognized and a slight touch correction is required, but a normal touch function can be provided by the correction. The evaluation result C indicates that even if the setting of the integrated circuit (IC) that controls the touch sensor is corrected for each electrode, a malfunction occurs and a practical problem occurs.

In any of Examples 5 to 10 and Comparative Examples 3 and 4, the curability evaluation result was A, and it was confirmed that the curability was sufficient without causing stickiness.
Moreover, in any of Examples 5 to 10 and Comparative Examples 3 and 4, the evaluation result of adhesion was A or B, and it was confirmed that excellent adhesion or good adhesion was exhibited.
Regarding the stretchability during heating, the evaluation results of Examples 5 to 10 were all A or B, and it was confirmed that the decorative layer had sufficient stretchability during heating when it was molded into a three-dimensional shape.
In Comparative Example 3, the evaluation result is C, and the decorative layer is cracked. In Comparative Example 4, the evaluation result is AA, and the decorating layer has a heating stretchability of more than 400%. It can be seen that the thickness is in a non-uniform state, and both Comparative Examples 3 and 4 have problems in forming into a three-dimensional shape.

About the resistance value of the conductive layer, the evaluation results of Examples 5 to 10 were all A or B. That is, when the conductive laminate for touch sensor of Examples 5 to 10 was used, good characteristics were maintained even when stretched, or a slight change in conductivity due to stretching was observed, but normality was corrected by correction. A touch function can be provided, and a highly reliable and high-quality three-dimensional touch sensor can be configured without causing disconnection of the conductive layer, cracking and peeling of the decorative layer, and the like. .
In contrast, the evaluation results regarding the resistance values of the conductive layers of Comparative Examples 3 and 4 were all C. That is, when the conductive laminate for a touch sensor of Comparative Examples 3 and 4 is used, malfunctions occur even if the settings are corrected for a plurality of electrodes, and it is difficult to construct a practical touch sensor. I know that there is.

  DESCRIPTION OF SYMBOLS 1 Transparent substrate, 1A The surface of a transparent substrate, 1B The back surface of a transparent substrate, 2 Decorating layer, 11 1st electrode, 11A 1st metal fine wire, 12 1st peripheral wiring, 13 2nd electrode, 13A 2nd metal fine wire, 14 Second peripheral wiring, S1 active area, S2 peripheral region, D1 first direction, D2 second direction.

Claims (7)

A conductive laminate for a touch sensor molded into a three-dimensional shape,
A transparent substrate,
A conductive layer formed on at least one surface of the substrate;
A decorative layer made of an ultraviolet curable resin formed on the conductive layer, and the decorative layer is subjected to a tensile test in an atmosphere at a temperature of 180 ° C. R (%) = [(when broken Length-length before stretching) / length before stretching] A stretching ratio R represented by x100 is 10 to 400%, and a conductive laminate for a touch sensor. The conductive layer has a detection electrode part and a peripheral wiring part connected to the detection electrode part,
The conductive laminate for a touch sensor according to claim 1, wherein the decorative layer is formed on the peripheral wiring portion. The conductive layer has a detection electrode part and a peripheral wiring part connected to the detection electrode part,
The conductive laminate for a touch sensor according to claim 1, wherein the decoration layer is formed on at least a part of the detection electrode part and the peripheral wiring part. The conductive layers are respectively formed on both sides of the substrate,
The conductive decorative body for a touch sensor according to any one of claims 1 to 3, wherein the decorative layer is formed on the conductive layer on one surface of the substrate. A method for producing a conductive laminate for a touch sensor molded into a three-dimensional shape,
Forming a conductive layer on at least one surface of a transparent substrate;
Forming a decorative layer made of an ultraviolet curable resin on the conductive layer;
Forming the substrate on which the conductive layer and the decorative layer are formed into a three-dimensional shape, wherein the decorative layer is subjected to a tensile test in an atmosphere at a temperature of 180 ° C. R (%) = [(Length at break-Length before stretching) / Length before stretching] × 100 The stretch ratio R represented by 100 is 10 to 400%, Production method. The step of forming the decorative layer includes:
A step of ejecting an ultraviolet curable ink containing a compound having a polymerizable group and a polymerization initiator on the conductive layer; and
The method for producing a conductive laminate for a touch sensor according to claim 5, further comprising: curing the ultraviolet curable ink that has been ejected.   The said ultraviolet curable ink is a manufacturing method of the conductive laminated body for touch sensors of Claim 6 containing the polymer whose glass transition temperature is 25 to 100 degreeC.