JP2018018179A - Conductive sheet for touch sensors, method for producing conductive sheet for touch sensors, touch sensor, touch panel laminate, touch panel, and composition for forming transparent insulating layers - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive sheet for touch sensors including a transparent insulating layer, which has excellent leveling properties while having excellent adhesion to an adhesive sheet used for producing a touch panel and the like, at a predetermined position, and a method for producing the same, and a touch sensor, a touch panel laminate, a touch panel and a composition for forming transparent insulating layers.SOLUTION: A conductive sheet for touch sensors 10 includes a base material 12, a patterned conductive part 14 disposed on the base material 12 and composed of metal thin wires, and a transparent insulating layer 18 disposed so as to cover the surface of the base material 12 on the conductive part 14 side and the conductive part. The transparent insulating layer 18 is formed using a composition for forming transparent insulating layers that includes a predetermined compound.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a conductive sheet for a touch sensor, a method for producing a conductive sheet for a touch sensor, a touch sensor, a touch panel laminate, a touch panel, and a composition for forming a transparent insulating layer.

  In recent years, in various electronic devices such as portable information devices, touch panels 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.

Generally, a touch panel is manufactured by bonding each member (a glass substrate, a conductive sheet for a touch sensor, a display device, and the like) via an adhesive film such as an OCA (Optical Clear Additive) film.
The conductive sheet for a touch sensor usually has a conductive part made of a patterned thin metal wire serving as a detection electrode (sensor electrode) or a lead-out wiring (peripheral electrode) on a base material.
In recent years, for the purpose of improving the handling property, or for the purpose of improving the scratch resistance or solvent resistance of the conductive part serving as the detection electrode or lead-out wiring, it is transparent as a protective film on the surface of the conductive part of the conductive sheet for the touch sensor. An insulating layer may be formed. This transparent insulating layer is not peeled off from the surface of the conductive portion, unlike a peelable protective film (peeling film) for temporarily protecting the surface of the touch sensor conductive sheet during the manufacturing process. That is, for example, when a capacitive touch panel is manufactured using a conductive sheet for a touch sensor in which the surface of the conductive portion is protected with a transparent insulating layer, a glass substrate is disposed on the transparent insulating layer via an adhesive layer. .
For example, in Patent Document 1, “a main body including a detection region and a frame region located at an edge of the detection region, and a flexible substrate formed so as to extend from one side of the main body and having a width smaller than the width of the main body. Including a transparent base, a conductive wiring provided on the transparent base, a grid-like first conductive layer including a first conductive wire intersecting each other and provided on one side of the detection region, and a second conductive intersecting each other A grid-like second conductive layer including a wire and provided on one side of the detection region facing the first conductive layer, and provided on one side of the frame region, the first conductive layer and the conduction wiring A first lead wire electrode that electrically connects the second conductive layer and a second lead wire electrode that is provided on the other side of the frame region and electrically connects the second conductive layer and the conductive wiring. Transparent guidance characterized by Film. "Is disclosed. In Patent Document 1, the paragraph [0056] includes at least a first conductive layer 20 and a second conductive layer 30 that serve as detection electrodes when a touch panel is manufactured, a first lead wire electrode 40 and a second lead wire electrode 50 that serve as lead wires, and the like. It describes that a transparent protective layer that partially covers may be provided. Further, as a material for the transparent protective layer, an ultraviolet curable adhesive (UV (ultra violet) adhesive) or the like is cited.

Special table 2015-524961 gazette

  The inventors of the present invention have been studying by producing a conductive sheet for a touch sensor in which a transparent protective layer (transparent insulating layer) is disposed using an ultraviolet curable adhesive as described in Patent Document 1, and in particular, In the case where the conductive part is composed of a mesh pattern made of fine metal wires, the leveling property of the surface of the transparent insulating layer (in other words, “excellent smoothness” and “no spot non-deposition region in the film, It has been found that there is a case where the film covers the entire surface (excelling in repelling property) ”) or the transparent insulating layer cannot be formed at a predetermined position on the mesh pattern.

When applying the transparent insulating layer forming composition, since the conductive portion has a pattern shape, the transparent insulating layer forming composition has a surface on the conductive portion side of the substrate (region where the conductive portion is not formed) and It arrange | positions so that a conductive part may be covered. That is, for example, when the conductive portion is configured with a mesh pattern made of fine metal wires, the area where the mesh pattern made of fine metal wires is formed is a three-dimensional portion (convex portion) with respect to the substrate, and A film | membrane is formed so that it may contact | connect the metal substrate which comprises this mesh pattern, and the base-material surface in which the mesh pattern is not formed. As a result of the study by the present inventors, the surface of the coating film is uneven due to this structure and the difference in surface free energy between the fine metal wire and the base material, or the film is not spot-formed in the coating film due to the repelling. It was confirmed that there was a problem that a film formation region occurred or the coating film contracted and a film was not formed at a predetermined position of the mesh pattern. In particular, it has been clarified that the performance decreases when the thickness of the mesh pattern made of fine metal wires is large.
As a result, the transparent insulating layer obtained by curing such a coating film by exposure is inferior in surface leveling property and has a drawback that a film is not formed at a predetermined position on the mesh pattern.
On the other hand, the present inventors have studied using a surface modifier to eliminate the leveling property of the transparent insulating layer, and although the leveling property is improved, the formed transparent insulating layer is a touch panel or the like. It has been found that there arises a problem that the adhesiveness with the pressure-sensitive adhesive sheet used in the production of is reduced.

Accordingly, the present invention provides a conductive sheet for a touch sensor having a transparent insulating layer in a predetermined position, which is excellent in adhesiveness with an adhesive sheet used at the time of producing a touch panel or the like, and excellent in leveling properties, and a method for manufacturing the same. With the goal.
Moreover, this invention aims at providing the touch sensor, touch-panel laminated body, and touch panel containing the said electrically conductive sheet for touch sensors.
In addition, the present invention provides a transparent insulating layer formation that can provide a conductive sheet for a touch sensor having a transparent insulating layer in a predetermined position, which has excellent leveling properties while being excellent in adhesiveness with an adhesive sheet used when producing a touch panel or the like It is an object to provide a composition for use.

As a result of intensive studies to achieve the above problems, the present inventors have found that the composition for forming a transparent insulating layer for forming a transparent insulating layer can solve the above problems by containing a compound having a specific structure. The headline and the present invention were completed.
That is, it has been found that the above object can be achieved by the following configuration.

(1) a base material;
A conductive part in the form of a pattern made of fine metal wires, disposed on the base material,
A conductive sheet for a touch sensor comprising a transparent insulating layer disposed on the conductive part,
The transparent insulating layer is a layer formed using a composition for forming a transparent insulating layer containing compound A,
Compound A has a siloxane structural unit having a polyoxyethylene chain, a siloxane structural unit having a polyoxypropylene chain, and a dimethylsiloxane structural unit,
The content of the dimethylsiloxane structural unit is 20 with respect to the total of the molar amounts of the siloxane structural unit having a polyoxyethylene chain, the siloxane structural unit having a polyoxypropylene chain, and the dimethylsiloxane structural unit. The content of the siloxane structural unit having a polyoxypropylene chain is not less than mol%, and the siloxane structural unit having the polyoxyethylene chain, the siloxane structural unit having the polyoxypropylene chain, and the dimethylsiloxane structural unit. The conductive sheet for touch sensors which is 20 mol% or more with respect to the total of the respective molar amounts.
(2) The conductive sheet for a touch sensor according to (1), wherein the transparent insulating layer forming composition further includes a polymerizable compound having an acryloyl group or a methacryloyl group and a polymerization initiator.
(3) The conductive sheet for a touch sensor according to (1) or (2), wherein a surface tension of the composition for forming a transparent insulating layer is 35 mN / m or less at 25 ° C.
(4) a base material;
A conductive part in the form of a pattern made of fine metal wires, disposed on the base material,
A conductive sheet for a touch sensor comprising a transparent insulating layer disposed on the conductive part,
The transparent insulating layer contains a compound B;
Compound B has a siloxane structural unit having a polyoxyethylene chain, a siloxane structural unit having a polyoxypropylene chain, and a dimethylsiloxane structural unit,
The content of the dimethylsiloxane structural unit is 20 with respect to the total of the molar amounts of the siloxane structural unit having a polyoxyethylene chain, the siloxane structural unit having a polyoxypropylene chain, and the dimethylsiloxane structural unit. The content of the siloxane structural unit having a polyoxypropylene chain is not less than mol%, and the siloxane structural unit having the polyoxyethylene chain, the siloxane structural unit having the polyoxypropylene chain, and the dimethylsiloxane structural unit. The conductive sheet for touch sensors which is 20 mol% or more with respect to the total of the respective molar amounts.
(5) a base material;
A conductive part in the form of a pattern made of fine metal wires, disposed on the base material,
A conductive sheet for a touch sensor comprising a transparent insulating layer disposed on the conductive part,
The surface of the transparent insulating layer includes a siloxane terminal structural unit, a dimethylsiloxane structural unit, an ethylene oxide structural unit, and a propylene oxide structural unit, and the molar ratio of the dimethylsiloxane structural unit to the siloxane terminal structural unit is 2 or more. The conductive sheet for a touch sensor, wherein the molar ratio of the propylene oxide structural unit to the ethylene oxide structural unit is 0.1 or more.
(6) The conductive sheet for a touch sensor according to any one of (1) to (5), wherein the surface energy of the transparent insulating layer is 30 mN / m or less at 25 ° C.
(7) The conductive sheet for a touch sensor according to any one of (1) to (6), wherein the conductive portions are arranged on both surfaces of the base material and have a mesh pattern made of silver thin wires.
(8) A method for producing a conductive sheet for a touch sensor according to any one of (1) to (7),
The manufacturing method of the conductive sheet for touch sensors which has the transparent insulating layer formation process which forms a transparent insulating layer by the screen printing method on the said base material and the said electroconductive part.
(9) A touch sensor including the touch sensor conductive sheet according to any one of (1) to (7).
(10) A touch panel laminate comprising the conductive sheet for a touch sensor according to any one of (1) to (6), an adhesive sheet, and a release sheet in this order.
(11) A touch panel including the touch sensor according to (9).
(12) A composition for forming a transparent insulating layer, which is used in the production of a conductive sheet for a touch sensor and is applied to the surface of a patterned conductive portion made of a fine metal wire,
The composition for forming a transparent insulating layer contains a compound A, the compound A has a siloxane structural unit having a polyoxyethylene chain, a siloxane structural unit having a polyoxypropylene chain, and a dimethylsiloxane structural unit, Furthermore, it has an acryloyl group or a methacryloyl group,
The content of the dimethylsiloxane structural unit is 20 with respect to the total of the molar amounts of the siloxane structural unit having a polyoxyethylene chain, the siloxane structural unit having a polyoxypropylene chain, and the dimethylsiloxane structural unit. The content of the siloxane structural unit having a polyoxypropylene chain is not less than mol%, and the siloxane structural unit having the polyoxyethylene chain, the siloxane structural unit having the polyoxypropylene chain, and the dimethylsiloxane structural unit. The conductive sheet for touch sensors which is 20 mol% or more with respect to the total of the respective molar amounts.
(13) The composition for forming a transparent insulating layer according to (12), wherein the surface tension of the composition for forming a transparent insulating layer is 35 mN / m or less at 25 ° C.

According to the present invention, there is provided a conductive sheet for a touch sensor having a transparent insulating layer in a predetermined position, which is excellent in adhesion with an adhesive sheet used at the time of producing a touch panel and the like, and in a predetermined position, and a method for producing the same Can do.
Moreover, according to this invention, the touch sensor, touch-panel laminated body, and touch panel containing the said conductive sheet for touch sensors can be provided.
Further, according to the present invention, a transparent insulation that can provide a conductive sheet for a touch sensor having a transparent insulating layer in a predetermined position while having excellent adhesion with an adhesive sheet used at the time of producing a touch panel or the like and also having excellent leveling properties. A layer forming composition can be provided.

It is a partial cross section figure of the 1st embodiment of the electrically conductive sheet for touch sensors of this invention. It is a partial top view of the 1st embodiment of the electrically conductive sheet for touch sensors of this invention. It is sectional drawing of the electrostatic capacitance type touch panel of this invention. It is a top view of one embodiment of a capacitive touch sensor. It is sectional drawing cut | disconnected along the cutting line AA shown in FIG. It is an enlarged plan view of a 1st detection electrode.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

In the description of the group (atom group) in this specification, the description that does not indicate substitution and non-substitution includes those that do not have a substituent and those that have a substituent, as long as the effects of the present invention are not impaired. To do. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). This is synonymous also about each compound.
Moreover, in this specification, light means an actinic ray or radiation. Unless otherwise specified, “exposure” in the present specification is not only exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
In the present specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and “(meth) acryl” represents both and / or acryl and methacryl. “(Meth) acryloyl” represents both or one of acryloyl and methacryloyl.

[Conductive sheet for touch sensor]
The conductive sheet for a touch sensor of the present invention is
A substrate;
A pattern-shaped conductive portion made of fine metal wires disposed on the base material,
A conductive sheet for a touch sensor, comprising a transparent insulating layer disposed so as to cover the surface of the conductive part side of the substrate and the conductive part,
The said transparent insulating layer is a layer formed using the composition for transparent insulating layer formation containing the compound A mentioned later.

  The conductive sheet for a touch sensor according to the present invention has a transparent insulating layer in a predetermined position while having excellent adhesion with an adhesive sheet used at the time of producing a touch panel or the like and having excellent leveling properties by adopting the above configuration.

The characteristic point of the conductive sheet for touch sensors of this invention exists in the point which formed the transparent insulating layer using the composition for transparent insulating layer formation containing the compound A. FIG.
Compound A has a dimethylsiloxane structural unit having a low surface tension of 20 mol% or more based on the total amount of the predetermined structural units, and further has a hydrophilic polyoxyethylene chain and a hydrophobic structure. A siloxane structural unit having a polyoxypropylene chain, wherein the content of the siloxane structural unit having a polyoxypropylene chain is the siloxane structural unit having the polyoxyethylene chain, and the siloxane having the polyoxypropylene chain It has 20 mol% or more with respect to the sum total of each molar amount of a structural unit and the said dimethylsiloxane structural unit. By using such a compound A, the composition for forming a transparent insulating layer is a mesh that becomes a convex part with respect to the base material and the base material even when the conductive part is composed of a mesh pattern made of fine metal wires. It spreads well on both sides of the pattern. As a result, the formed coating film is excellent in repellency, and a transparent insulating layer can be formed at a predetermined position of the mesh pattern by suppressing the shrinkage of the coating film. Moreover, since 20 mol% or more of dimethylsiloxane structural units with low surface tension are contained, it is estimated that the obtained coating film is excellent in smoothness. Moreover, since it contains a certain amount or more of siloxane structural units having a polyoxypropylene chain that is hydrophobic, it is presumed that good compatibility with the paint is easily obtained.
Moreover, the transparent insulation layer (layer containing the compound B mentioned later) formed by hardening | curing the said coating film is excellent in leveling property, and can be arrange | positioned in the predetermined position of a mesh pattern. Moreover, it has confirmed that adhesiveness with the adhesive sheet used in the case of preparation of a touch panel etc. is also favorable.

In addition, the present inventors have recently evaluated the surface state of a formed transparent insulating film (in other words, a transparent insulating film formed by curing a coating film by exposure) to provide an insulating material with excellent leveling properties. It has been found that a membrane can be selected. That is, the surface of the transparent insulating layer includes a siloxane terminal structural unit, a dimethylsiloxane structural unit, an ethylene oxide structural unit, and a propylene oxide structural unit, and the molar ratio of the dimethylsiloxane structural unit to the siloxane terminal structural unit is 2 or more. In addition, when the molar ratio of the propylene oxide structural unit to the potylene oxide structural unit is 0.1 or more, it has been found that the leveling property of the transparent insulating layer is excellent. The transparent insulating layer having the above structure is a structure in which a siloxane structure in which the free energy on the surface is uniformly and effectively reduced is disposed, and is considered to have excellent compatibility. It is estimated that uniform leveling can be realized.
The amount of each structural unit on the surface can be preferably identified by TOF-SIMS (Time-of-Flight Secondary Mass Spectrometry) analysis on the surface of the transparent insulating layer.

Hereinafter, the suitable aspect of the electrically conductive sheet for touch sensors of this invention is demonstrated with reference to drawings.
In FIG. 1, the partial cross section figure of the 1st embodiment of the electrically conductive sheet 10 for touch sensors of this invention is shown. FIG. 2 is a partial plan view of the first embodiment of the touch sensor conductive sheet 10. 1 is a cross-sectional view taken along a cutting line AA in FIG. The conductive sheet 10 for a touch sensor is disposed on the base 12, the conductive portion 16 including a plurality of fine metal wires 14 disposed on the base 12, and in other words, on the conductive portion 16 (in other words, And a transparent insulating layer 18 disposed so as to be in contact with the surface and the conductive portion 16. As shown in FIG. 2, the conductive portion 16 has a mesh pattern composed of fine metal wires 14.

Hereinafter, each member which comprises the conductive sheet for touch sensors is explained in full detail.
<< Base material >>
If the base material can support the electroconductive part, the kind will not be restrict | limited, It is preferable that it is a transparent base material, and a plastic film is more preferable.
Specific examples of the material constituting the substrate include PET (polyethylene terephthalate) (258 ° C.), polycycloolefin (134 ° C.), polycarbonate (250 ° C.), (meth) acrylic resin (128 ° C.), PEN (polyethylene naphthalate). Phthalate) (269 ° C.), PE (polyethylene) (135 ° C.), PP (polypropylene) (163 ° C.), polystyrene (230 ° C.), polyvinyl chloride (180 ° C.), polyvinylidene chloride (212 ° C.), or TAC A plastic film having a melting point of about 290 ° C. or less such as (triacetylcellulose) (290 ° C.) is preferable, (meth) acrylic resin, PET, polycycloolefin, polycarbonate is more preferable, and adhesion with the transparent insulating layer as an upper layer From the viewpoint of properties, (meth) acrylic resins are more preferable. Figures in parentheses are melting points. The total light transmittance of the substrate is preferably 85% to 100%.
Although the thickness in particular of a base material is not restrict | limited, From the point of the application to a touchscreen, it can normally be arbitrarily selected in 25-500 micrometers. In addition, when it serves as the function of a touch surface in addition to the function of a base material, it can also be designed with a thickness exceeding 500 μm.

As another preferred embodiment of the substrate, it is preferable to have an undercoat layer containing a polymer on the surface thereof. By forming the conductive portion on the undercoat layer, the adhesion of the conductive portion is further improved.
The method for forming the undercoat layer is not particularly limited, and examples thereof include a method in which a composition for forming an undercoat layer containing a polymer is applied on a substrate and subjected to heat treatment as necessary. The undercoat layer forming composition may contain a solvent, if necessary. The kind in particular of solvent is not restrict | limited, A well-known solvent is illustrated. Moreover, latex containing polymer fine particles may be used as the composition for forming an undercoat layer containing polymer.
The thickness of the undercoat layer is not particularly limited, but is preferably 0.02 to 0.3 μm, and more preferably 0.03 to 0.2 μm, from the viewpoint that the adhesion of the conductive portion is more excellent.

<< Conductive part >>
The conductive portion 16 is disposed on the substrate 12 and has a mesh pattern composed of a plurality of fine metal wires 14. It is preferable that the conductive part 16 mainly constitutes a sensor part of a touch sensor as will be described later.
As shown in FIG. 2, the conductive portion 16 has a mesh pattern composed of a plurality of fine metal wires 14. That is, it includes a plurality of openings (lattices) 36 formed by intersecting metal thin wires 14.

The line width Wa of the fine metal wire 14 is not particularly limited, but is preferably 30 μm or less, more preferably 15 μm or less, further preferably 10 μm or less, particularly preferably 9 μm or less, most preferably 7 μm or less, and preferably 0.5 μm or more. More preferably, it is 0.0 μm or more. If it is the said range, a low resistance electrode can be formed comparatively easily.
Although the thickness of the fine metal wire 14 is not particularly limited, it can be selected from 0.00001 mm to 0.2 mm from the viewpoint of conductivity and visibility, but is preferably 30 μm or less, more preferably 20 μm or less, and 0.01 to 9 μm is more preferable, and 0.05 to 5 μm is particularly preferable.
As the thickness of the fine metal wire 14 is larger, the leveling property of the transparent insulating layer described later tends to be lowered. For this reason, the effect of this invention can be enjoyed much more when the thickness of the metal fine wire 14 is 0.0002 mm or more, especially 0.0004 mm or more.

The opening 36 is an opening region surrounded by the thin metal wire 14. The length Wb of one side of the opening 36 is preferably 800 μm or less, more preferably 600 μm or less, further preferably 400 μm or less, preferably 5 μm or more, more preferably 30 μm or more, and further preferably 80 μm or more. The arrangement pitch of the thin metal wires 14 is preferably in the numerical range of Wb. In the present specification, the arrangement pitch of the fine metal wires is intended to be the total length of the Wa and the Wb (the total length of the line width of the fine metal wires and the width of the opening).
From the viewpoint of visible light transmittance, the aperture ratio is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more. The aperture ratio corresponds to the ratio of the transmissive portion (opening) excluding the thin metal wires 14 in the conductive portion 16 to the whole.

In FIG. 2, the opening 36 has a substantially rhombus shape. However, other polygonal shapes (for example, a triangle, a quadrangle, a hexagon, and a random polygon) may be used. Further, the shape of one side may be a curved shape or a circular arc shape in addition to a linear shape. In the case of the arc shape, for example, the two opposing sides may have an outwardly convex arc shape, and the other two opposing sides may have an inwardly convex arc shape. The shape of each side may be a wavy shape in which an outwardly convex arc and an inwardly convex arc are continuous. Of course, the shape of each side may be a sine curve.
Furthermore, in FIG. 2, although the mesh-shaped pattern was demonstrated, the pattern shape of a metal fine wire is not limited to this aspect.

Examples of the material for the fine metal wires 14 include metals such as gold (Au), silver (Ag), copper (Cu), and aluminum (Al), alloys, and the like. Especially, it is preferable that it is silver from the reason for which the electroconductivity of the metal fine wire 14 is excellent.
In the metal fine wire 14, it is preferable that the binder is contained from a viewpoint of the adhesiveness of the metal fine wire 14 and the base material 12. As shown in FIG.
As the binder, (meth) acrylic resin, styrene resin, vinyl resin, polyolefin resin, polyester resin, polyurethane resin, polyamide resin are used because the adhesion between the fine metal wire 14 and the substrate 12 is more excellent. At least one resin selected from the group consisting of resins, polycarbonate resins, polydiene resins, epoxy resins, silicone resins, cellulose polymers, and chitosan polymers, or monomers constituting these resins And the like.

  The manufacturing method in particular of the metal fine wire 14 is not restrict | limited, A well-known method is employable. For example, the method using silver halide mentioned later is mentioned. This method will be described in detail later.

<< Transparent insulating layer >>
The transparent insulating layer 18 is disposed on the conductive portion 16. More specifically, the transparent insulating layer 18 is disposed on the surface of the base material 12 (a region where the conductive portion 16 is not provided) and the conductive portion 16 so as to cover them. That is, since the conductive portion 16 has a pattern shape, the transparent insulating layer 18 comes into contact with the surface of the substrate 12 and the pattern portion constituting the conductive portion 16.
When the conductive sheet 10 for a touch sensor is used for, for example, a capacitive touch panel as will be described later, the transparent insulating layer 18 is provided with other members such as a glass substrate via an adhesive sheet (adhesive layer). Be placed.
The transparent insulating layer 18 preferably has solvent resistance, scratch resistance, and bending resistance. Hereinafter, each component which comprises a transparent insulating layer is demonstrated.
The configuration of the transparent insulating layer includes the first embodiment or the second embodiment described below.
Hereinafter, a first embodiment of the transparent insulating layer will be described.

-1st Embodiment of a transparent insulating layer The transparent insulating layer which concerns on 1st Embodiment contains the compound B. FIG.
Compound B has a siloxane structural unit having a polyoxyethylene chain, a siloxane structural unit having a polyoxypropylene chain, and a dimethylsiloxane structural unit.
The content of the dimethylsiloxane structural unit is 20 mol% or more based on the total amount of each of the siloxane structural unit having a polyoxyethylene chain, the siloxane structural unit having a polyoxypropylene chain, and the dimethylsiloxane structural unit. is there. Although an upper limit is not specifically limited, It is preferable that it is 60 mol% or less, and it is more preferable that it is 45 mol% or less.

  In the compound B, the content of the siloxane structural unit having a polyoxypropylene chain is such that each mole of the siloxane structural unit having a polyoxyethylene chain, the siloxane structural unit having a polyoxypropylene chain, and the dimethylsiloxane structural unit. The amount is preferably 20 mol% or more, more preferably 25 mol% or more, based on the total amount. Although an upper limit is not specifically limited, It is preferable that it is 60 mol% or less, and it is more preferable that it is 45 mol% or less.

  In compound B, the content of the siloxane structural unit having a polyoxyethylene chain is the molar amount of each of the siloxane structural unit having a polyoxyethylene chain, the siloxane structural unit having a polyoxypropylene chain, and the dimethylsiloxane structural unit. It may be 5 mol% or more based on the total, and is preferably 10 mol% or more, and more preferably 30 mol% or more from the viewpoint of further improving the effects of the present invention. Although an upper limit is not specifically limited, It is preferable that it is 80 mol% or less, and it is more preferable that it is 60 mol% or less.

  The content in compound B is preferably 0.001 to 10% by mass with respect to the total mass of the transparent insulating layer. By setting the content of Compound B to 0.01% by mass or more in the transparent insulating layer, the leveling property is more excellent. The content of Compound B is more preferably 0.01 to 5% by mass, further preferably 0.01 to 2% by mass, and particularly preferably 0.05 to 1% by mass with respect to the total mass of the transparent insulating layer.

The transparent insulating layer preferably contains a (meth) acrylic resin having a cross-linked structure from the viewpoint of excellent adhesion to the underlying substrate and the conductive part and further excellent weather resistance. Further, the surface energy is preferably 30 mN / m or less, more preferably 28 mN / m or less at 25 ° C., from the viewpoint of forming a film capable of expressing leveling properties. From the viewpoint of adhesion, the surface energy is preferably too low, preferably 10 mN / m or more, and more preferably 20 mN / m.
An easy-adhesive protective film or an optical adhesive (OCA) may be bonded to the surface of the insulating film, but it is preferable that an appropriate value is obtained for the adhesion, and in the case of an easy-adhesive protective film Is preferably 0.1 N / 25 mm or more, and the case of use in a bonded form such as an optical adhesive (OCA) is preferably 10 N / 25 mm or more.

  The thickness of the transparent insulating layer is not particularly limited, but if the thickness is large, cracks are likely to occur when bent. 1-20 micrometers is preferable and 5-15 micrometers is more preferable from a viewpoint which is excellent by the adhesiveness of an electroconductive part, and excellent by film | membrane intensity | strength, suppressing a crack.

The insulative hardness of the transparent insulating layer is preferably 0.01 MPa to 200 MPa, and more preferably 140 MPa or less. By setting it as the said range, even if a transparent insulating layer has a softness | flexibility and bends and uses the electrically conductive sheet for touch sensors, it is hard to produce a crack in a transparent insulating layer.
The indentation hardness of the transparent insulating layer can be measured with a micro hardness tester (picodenter).

The transparent insulating layer preferably has an elastic modulus at 50 to 90 ° C. of 1 × 10 ⁶ Pa or more. When the base material is thermally expanded, a fine metal wire having a lower expansion coefficient than that of the base material formed on the base material extends in the same manner, which may cause a crack in the fine metal wire. In particular, when the touch sensor conductive sheet is used in a folded state, the fine metal wire may be broken. The crack or disconnection can be suppressed by setting the elastic modulus of the transparent insulating layer at 50 to 90 ° C. to 1 × 10 ⁶ Pa or more. The elastic modulus of the transparent insulating layer can be measured with a micro hardness tester (picodenter).

The total light transmittance of the conductive sheet for a touch sensor including the transparent insulating layer is preferably 85% or more, and more preferably 90% or more with respect to the visible light region (wavelength 400 to 700 nm).
The total light transmittance is a value measured with a spectrocolorimeter CM-3600A (manufactured by Konica Minolta, Inc.).
The total light transmittance of the transparent insulating layer itself is preferably adjusted so that the touch sensor conductive sheet exhibits the total light transmittance, and is preferably at least 85% or more.

  Preferably, the difference between the linear expansion coefficient of the transparent insulating layer and the linear expansion coefficient of the substrate is small in order to suppress a decrease in the conductivity due to the difference in linear expansion coefficient of the base material, the conductive part, and the transparent insulating layer. The difference is preferably 300 ppm / ° C. or less, and more preferably 150 ppm / ° C. or less.

The transparent insulating layer is preferably excellent in adhesiveness with the conductive part, and more specifically, it is more preferable that there is no peeling in a tape adhesion evaluation test by “610” manufactured by 3M Company.
Moreover, since the transparent insulating layer is in contact with not only the conductive portion but also the region where the conductive portion of the base material (or undercoat layer or binder layer) is not formed, the transparent insulating layer is not in contact with the base material (or undercoat layer or binder layer). It is preferable that the adhesiveness is excellent. If the adhesion of the transparent insulating layer to the base material (or undercoat layer or binder layer) is poor, the transparent insulating layer adheres only to the conductive part. In some cases, force is applied to the conductive part, and the pattern shape of the conductive part may be deformed. In addition, a binder layer is a layer which consists of a binder arrange | positioned on a base material and between metal fine wires, and is often formed when manufacturing a metal fine wire by a silver halide method.

From the viewpoint of suppressing the surface reflection of the conductive sheet for the touch sensor, it is preferable that the refractive index difference between the refractive index of the transparent insulating layer and the refractive index of the substrate is small.
Moreover, when the binder component is contained in the thin metal wire of the conductive part, the smaller the refractive index difference between the refractive index of the transparent insulating layer and the refractive index of the binder component, the better, and the resin forming the transparent insulating layer More preferably, the component and the binder component are the same material.
Note that the resin component forming the transparent insulating layer and the binder component are the same material as an example when both the binder component and the resin component forming the transparent insulating layer are (meth) acrylic resins. As mentioned.

  Furthermore, when the touch sensor conductive sheet is applied to, for example, a touch panel as described above, an adhesive sheet (adhesive layer) is bonded to the transparent insulating layer of the touch sensor conductive sheet. In order to suppress light scattering at the interface between the transparent insulating layer and the pressure-sensitive adhesive sheet, the smaller the refractive index difference between the refractive index of the transparent insulating layer and the refractive index of the pressure-sensitive adhesive sheet, the better.

The method for forming the transparent insulating layer of the first embodiment described above on the substrate and the conductive part is not particularly limited. For example, a method (coating method) for forming a transparent insulating layer by applying a composition for forming a transparent insulating layer containing a compound A, which will be described later, and various components optionally added onto the base material and the conductive part, or a temporary Examples thereof include a method (transfer method) in which a transparent insulating layer is formed on a substrate and transferred to the surface of the conductive portion. Among these, the coating method is preferable from the viewpoint of easy control of the thickness.
Hereinafter, each component of the composition for transparent insulating layer formation which can form the transparent insulating layer of 1st Embodiment, and the formation method of the transparent insulating layer of 1st Embodiment are explained in full detail.

<Composition for forming transparent insulating layer>
Hereinafter, each component of the composition for transparent insulating layer formation which can form the transparent insulating layer of 1st Embodiment is explained in full detail.
(Compound A)
The composition for forming a transparent insulating layer contains compound A.
Compound A is a compound having a siloxane structural unit having a polyoxyethylene chain, a siloxane structural unit having a polyoxypropylene chain, and a dimethylsiloxane structural unit, and further having an acryloyl group or a methacryloyl group.
In Compound A, the content of the dimethylsiloxane structural unit is the sum of the molar amounts of the siloxane structural unit having a polyoxyethylene chain, the siloxane structural unit having a polyoxypropylene chain, and the dimethylsiloxane structural unit (hereinafter referred to as “total”). It is also referred to as “siloxane structural unit”)). Although an upper limit is not specifically limited, It is preferable that it is 60 mol% or less, and it is more preferable that it is 45 mol% or less.

  In compound A, the content of the siloxane structural unit having a polyoxypropylene chain is the sum of the molar amounts of the siloxane structural unit having a polyoxyethylene chain, the siloxane structural unit having a polyoxypropylene chain, and the dimethylsiloxane structural unit. The amount is preferably 20 mol% or more, more preferably 25 mol% or more. Although an upper limit is not specifically limited, It is preferable that it is 60 mol% or less, and it is more preferable that it is 45 mol% or less.

  In compound A, the content of the siloxane structural unit having a polyoxyethylene chain may be 5 mol% or more based on the total siloxane structural unit, and is 10 mol from the viewpoint of further improving the effects of the present invention. % Or more, more preferably 30 mol% or more. Although an upper limit is not specifically limited, It is preferable that it is 80 mol% or less, and it is more preferable that it is 60 mol% or less.

The chain length of the polyoxyethylene chain is not particularly limited, but preferably 1 to 200 oxyethylene units, more preferably 1 to 100.
The chain length of the polyoxypropylene chain is not particularly limited, but preferably 1 to 200 oxypropylene units, more preferably 1 to 100.

  In compound A, the position of the (meth) acryloyl group is not particularly limited, but it is preferably introduced into the side chain.

  As compound A, what has a siloxane structural unit shown by following formula (1)-formula (3) especially is preferable.

Formula (1)-Formula (3)

In the above formulas (2) and (3), A ¹ and A ² each independently represent a single bond or a divalent organic group, EO represents an oxyethylene group, and m represents the number of oxyethylene groups. PO represents an oxypropylene group, n represents the number of oxypropylene groups, and R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or a (meth) acryloyl group.

In the above formulas (2) and (3), the divalent organic group represented by A ¹ and A ² is a substituted or unsubstituted divalent aliphatic hydrocarbon group (for example, having 1 to 8 carbon atoms. For example, An alkylene group such as a methylene group, an ethylene group, or a propylene group), a substituted or unsubstituted divalent aromatic hydrocarbon group (for example, having 6 to 12 carbon atoms, for example, a phenylene group), -O-, -S. —, —SO ₂ —, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof (eg, alkyleneoxy group, alkylene Oxycarbonyl group or alkylenecarbonyloxy group).

In the above formula (2) and formula (3), m and n are each independently preferably 1 to 200, and more preferably 1 to 100.
The oxypropylene group (PO) may be either linear or branched.

The alkyl group represented by R ¹ and R ² preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Examples of the alkyl group represented by R ¹ and R ² include a methyl group or an ethyl group.

  Compound A may further have structural units other than the siloxane structural units represented by the above formulas (1) to (3), but the structures represented by the above formulas (1) to (3). The total content of units is preferably 50 mol% or more with respect to all structural units, more preferably 80 mol% or more with respect to all structural units, and 90 mol% or more with respect to all structural units. More preferably.

  Specific examples of the compound A that can be used in the present invention include BYK-3455.

The content of Compound A in the composition for forming a transparent insulating layer is not particularly limited, but is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass with respect to the total solid content. 01-0.5 mass% is further more preferable, and 0.05-0.15 mass% is especially preferable.
Compound A may be used alone or in combination of two or more.

(Polymerizable compound having (meth) acryloyl group)
The composition for forming a transparent insulating layer preferably contains a polymerizable compound having a (meth) acryloyl group. However, the above-mentioned compound A is not included in the polymerizable compound having the (meth) acryloyl group.
The polymerizable compound (polymerizable group-containing compound) is not particularly limited as long as it has an acryloyl group or a methacryloyl group as the polymerizable group, and may be any form selected from monomers, oligomers and polymers. That is, the polymerizable compound may be an oligomer having a polymerizable group or a polymer having a polymerizable group.
The monomer is preferably a compound having a molecular weight of less than 1,000.
The oligomer and polymer are polymers in which a finite number of monomers (generally 5 to 100) are bonded. An oligomer is a compound having a weight average molecular weight of 3000 or less, and a polymer is a compound having a weight average molecular weight of 3000.
The polymerizable compound may be one kind or a combination of plural kinds.
In addition, the polymerizable compound may be monofunctional or polyfunctional.

  Examples of monofunctional (meth) acrylates include butyl (meth) acrylate, amyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, and lauryl. Long chain alkyl (meth) acrylates such as (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) ) Acrylate, tetrahydrofurfuryl (meth) acrylate, nonylphenoxyethyl tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrafurfuryl (meth) acrylate Rate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, propylene oxide modified nonylphenol ( (Meth) acrylate having a cyclic structure such as meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate , 2- (meth) acryloyloxyethyl acid phosphate, and diethylethylaminoethyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, Examples include 4-hydroxybutyl (meth) acrylate, isobornyl (meth) acrylate, and an ester of (meth) acrylic acid and a polyhydric alcohol.

  Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and 1,4-butane. Diol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, neopentyl glycol di (meth) acrylate, 3-methyl -1,5-pentanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanedi (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, propylene glycol di (meth) acrylate, dip Pyrene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, 1,3 butanediol di (meth) acrylate, di Methylol dicyclopentane diacrylate, hexamethylene glycol diacrylate, hexaethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, 2,2 ' -Bis (4-acryloxydiethoxyphenyl) propane, bisphenol A tetraethylene glycol diacrylate and the like.

  Examples of the trifunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, and tris (acryloxyethyl). ) Isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, tetramethylolmethanetri (meth) Acrylate, ethylene oxide modified glycerol triacrylate, propylene oxide modified glycerol triacrylate, epsilon caprolactone Sex trimethylolpropane triacrylate, and pentaerythritol triacrylate, and the like.

  Examples of the tetrafunctional (meth) acrylate include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, and pentaerythritol tetra (meth) acrylate.

  Examples of the pentafunctional or higher functional (meth) acrylate compound include dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa ( And (meth) acrylate and polypentaerythritol polyacrylate.

Furthermore, as described above, the polymerizable compound may be an oligomer or polymer having a (meth) acryloyl group. The number of polymerizable groups may be one or may be 2 or more, and is preferably 2 or more from the viewpoint of further improving the effect of the present invention.
The oligomer or polymer having a (meth) acryloyl group functions as a prepolymer. In other words, it can be polymerized with other monomers or polyfunctional compounds.
The method for producing the prepolymer is not particularly limited, and examples thereof include a method of polymerizing in a solution obtained by mixing the above-described monofunctional (meth) acrylate, a photopolymerization initiator or a thermal polymerization initiator, and a solvent. . The formation method of the prepolymer is preferably thermal polymerization.

  Among the polymerizable compounds having a (meth) acryloyl group, a urethane (meth) acrylate compound or an epoxy (meth) acrylate compound is preferable. From the viewpoint of weather resistance, a urethane (meth) acrylate compound is more preferable. From the viewpoint of suppressing yellowing, an aliphatic urethane (meth) acrylate compound is preferable.

Specifically, the urethane (meth) acrylate compound includes two or more photopolymerizable groups selected from the group consisting of an acryloyloxy group, an acryloyl group, a methacryloyloxy group, and a methacryloyl group, and a urethane bond. It is preferable that it is a compound which contains 1 or more in 1 molecule. Such a compound can be produced, for example, by a urethanization reaction between an isocyanate and a hydroxy group-containing (meth) acrylate compound. The urethane (meth) acrylate compound may be a so-called oligomer or polymer.
The photopolymerizable group is a radically polymerizable group. A polyfunctional urethane (meth) acrylate compound containing two or more photopolymerizable groups in one molecule is useful for forming a transparent insulating layer having high hardness.
The number of photopolymerizable groups contained in one molecule of the urethane (meth) acrylate compound is preferably at least 2, for example, 2 to 10 is more preferable, and 2 to 6 is more preferable. The two or more photopolymerizable groups contained in the urethane (meth) acrylate compound may be the same or different.
Among them, an acryloyloxy group and a methacryloyloxy group are preferable as the photopolymerizable group.

The number of urethane bonds contained in one molecule of the urethane (meth) acrylate compound may be one or more, and two or more are preferable in that the hardness of the formed transparent resin layer becomes higher. ~ 5 are more preferred.
In the urethane (meth) acrylate compound containing two urethane bonds in one molecule, the photopolymerizable group may be bonded to only one urethane bond directly or via a linking group. Each may be bonded directly or via a linking group.
In one embodiment, it is preferable that one or more photopolymerizable groups are bonded to two urethane bonds bonded via a linking group.

As described above, in the urethane (meth) acrylate compound, the urethane bond and the photopolymerizable group may be directly bonded, and a linking group may be present between the urethane bond and the photopolymerizable group. . The linking group is not particularly limited, and examples thereof include a linear or branched saturated or unsaturated hydrocarbon group, a cyclic group, and a group composed of a combination of two or more thereof. The number of carbon atoms of the hydrocarbon group is, for example, about 2 to 20, but is not particularly limited. Examples of the cyclic structure contained in the cyclic group include an aliphatic ring (such as a cyclohexane ring) and an aromatic ring (such as a benzene ring and a naphthalene ring). The above group may be unsubstituted or may have a substituent.
In the present specification, unless otherwise specified, the group described may have a substituent or may be unsubstituted. When a certain group has a substituent, examples of the substituent include an alkyl group (for example, an alkyl group having 1 to 6 carbon atoms), a hydroxy group, an alkoxyl group (for example, an alkoxyl group having 1 to 6 carbon atoms), a halogen atom ( For example, fluorine atom, chlorine atom, bromine atom), cyano group, amino group, nitro group, acyl group, carboxyl group and the like can be mentioned.

The urethane (meth) acrylate compound can be synthesized by a known method. Moreover, it is also possible to obtain as a commercial item.
As an example of the synthesis method, for example, a method of reacting an alcohol, a polyol, and / or a hydroxyl group-containing compound such as a hydroxyl group-containing (meth) acrylate with isocyanate. Moreover, the method of esterifying the urethane compound obtained by the said reaction with (meth) acrylic acid as needed can be mentioned. In addition, (meth) acrylic acid shall be used in the meaning including acrylic acid and methacrylic acid.

  Examples of the isocyanate include aromatic, aliphatic, and alicyclic polyisocyanates, such as tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, and modified diphenylmethane. Diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, phenylene diisocyanate, lysine Diisocyanate, lysine triisocyanate, and naphthalene diisocyanate Sulfonates, and the like. These may be used alone or in combination of two or more.

  Examples of the hydroxy group-containing (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethylacryloyl phosphate, and 2-acryloyloxyethyl. 2-hydroxypropyl phthalate, glycerin diacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, caprolactone-modified 2-hydroxyethyl acrylate, cyclohexane dimethanol monoacrylate, etc. Is mentioned. These may be used alone or in combination of two or more.

As a commercial item of a urethane (meth) acrylate compound, although not limited to the following, for example, Kyoeisha Chemical Co., Ltd. UA-306H, UA-306I, UA-306T, UA-510H, UF-8001G, UA-101I, UA-101T, AT-600, AH-600, AI-600, Shin-Nakamura Chemical U-4HA, U-6HA, U-6LPA, UA-32P, U-15HA, UA-1100H, Japan Violet UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, Synthetic Chemical Industries, Ltd. Same UV-7640B, Same UV-6630B, Same UV-7000B, Same UV-7510B, Same UV-7461 E, same UV-3000B, same UV-3200B, same UV-3210EA, same UV-3310EA, same UV-3310B, same UV-3500BA, same UV-3520TL, same UV-3700B, same UV-6100B, same UV- 6640B, UV-2000B, UV-2010B, and UV-2250EA. In addition, purple light UV-2750B manufactured by Nippon Synthetic Chemical Industry Co., Ltd., UL-503LN manufactured by Kyoeisha Chemical Co., Ltd., Unidic 17-806 manufactured by Dainippon Ink & Chemicals, Inc., 17-813 Examples include EB-1290K manufactured by UCB, Hicorp AU-2010 and AU-2020 manufactured by Tokushi.
Examples of the hexafunctional or higher urethane (meth) acrylate compounds include, for example, Art Resin UN-3320HA, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-904, Nippon Synthetic Chemical (Negami Kogyo Co., Ltd.) Violet UV-1700B, Violet UV-7605B, Violet UV-7610B, Violet UV-7630B, Violet UV-7640B, NK Oligo U-6PA, NK Oligo U-10HA manufactured by Shin-Nakamura Chemical Co., Ltd. NK Oligo U-10PA, NK Oligo U-1100H, NK Oligo U-15HA, NK Oligo U-53H, NK Oligo U-33H, KRM8452, EBECRYL1290, KRM8200, EBECRYL5129, KRM8904, manufactured by Daicel Cytec Co., Ltd. Made by Yakuhin Co., Ltd. UX-5000, or the like can be mentioned.
Moreover, as a 2-3 trifunctional urethane (meth) acrylate compound, Nagase UV self-healing by Nagase Co., Ltd., EXP DX-40 by DIC, etc. can be mentioned.

  The molecular weight (weight average molecular weight Mw) of the urethane (meth) acrylate compound is preferably in the range of 300 to 10,000. If the molecular weight is within this range, a transparent insulating layer having excellent flexibility and surface hardness can be obtained.

  The epoxy (meth) acrylate compound is obtained by addition reaction of polyglycidyl ether and (meth) acrylic acid, and often has at least two (meth) acryloyl groups in the molecule. .

  The polymerizable compound having a (meth) acryloyl group is bifunctional as a polyfunctional compound and a urethane (meth) acrylate compound or an epoxy (meth) acrylate compound from the viewpoint of solvent resistance, adhesion, leveling properties, or hardness. It is preferable to contain at least the above (meth) acrylate monomer (however, the urethane (meth) acrylate compound or epoxy (meth) acrylate compound is not included), and further, as a diluting monomer, a monofunctional (meth) acrylate monomer It is also preferable to contain. In addition, solvent resistance here means not changing in quality (whitening) at the time of solvent adhesion. It is presumed to be a characteristic that suppresses a phenomenon in which the polymer component positively moves in the transparent insulating layer due to the solvent expansion to cause film quality modification.

The total content of the urethane (meth) acrylate compound and the epoxy (meth) acrylate compound in the transparent insulating layer forming composition is not particularly limited, but in the transparent insulating layer forming composition, the effect of the present invention is more excellent. 10-70 mass% is preferable with respect to the total solid of, and 30-65 mass% is more preferable.
The urethane (meth) acrylate compound and the epoxy (meth) acrylate compound can be used singly or in combination of two or more. In addition, when these 2 or more types are contained, it is preferable that the total amount is contained in the said range.

  When the polymerizable compound contains a bifunctional or higher (meth) acrylate monomer as a polyfunctional compound, the content of the bifunctional or higher (meth) acrylate monomer with respect to the total mass of the polymerizable compound is not particularly limited. % By mass is preferable, and 20 to 45% by mass is more preferable.

Among the polyfunctional compounds, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or dipentaerythritol penta (meth) acrylate, or a mixture thereof, It is preferable from the viewpoint of scratch resistance.
The said polyfunctional compound can be used individually by 1 type or in combination of 2 or more types.

  When the polymerizable compound contains a monofunctional monomer as a diluting monomer, the content of the monofunctional monomer with respect to the total mass of the polymerizable compound is not particularly limited, but is preferably less, more preferably 40% by mass or less, More preferably, it is 10 mass% or less.

Among the dilutable monomers, from the viewpoint of adhesion and curing speed, long-chain alkyl (meth) acrylate or (meth) acrylate having a cyclic structure is preferable, among which lauryl (meth) acrylate or hexadecyl (meth) acrylate is preferable. (Meth) acrylate having a cyclic structure such as long-chain alkyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, or dicyclopentenyl (meth) acrylate is more preferable.
The said diluting monomer can be used individually by 1 type or in combination of 2 or more types.

(Polymerization initiator)
The composition for forming a transparent insulating layer preferably contains a polymerization initiator. The polymerization initiator may be either a photopolymerization initiator or a thermal polymerization initiator, but is preferably a photopolymerization initiator.
The kind in particular of photoinitiator is not restrict | limited, A well-known photoinitiator (a radical photoinitiator, a cationic photoinitiator) can be used. For example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2, 2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl)) Phenyl) propanone), 2- Droxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine Oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) Phenyl phosphinate, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-ben) Yloxime)], methylbenzoylformate, 4-methylbenzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 1- [4- (4-benzoyl) Carbonyl compounds such as phenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one and sulfur such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, tetramethylthiuram disulfide Compounds and the like.
A polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

  In the composition for forming a transparent insulating layer, the content of the polymerization initiator is not particularly limited, but is 0.1 to 10% by mass with respect to the total mass of the composition from the viewpoint of curability of the transparent insulating layer. Preferably, it is 2-5 mass%. In addition, when 2 or more types of polymerization initiators are used, it is preferable that total content of a polymerization initiator exists in the said range.

(Other additives)
In addition to the above, the composition for forming a transparent insulating layer includes a surface lubricant, an antioxidant, a corrosion inhibitor, a light stabilizer, an ultraviolet absorber, a polymerization inhibitor, a silane coupling agent, and an inorganic or organic filler. In addition, various conventionally known additives such as powders such as metal powders and pigments, particulates, and foils can be added as appropriate according to the use. For details thereof, see paragraphs 0032 to 0034 of JP2012-229212A, for example. However, the present invention is not limited thereto, and various additives that can be generally used for the photopolymerizable composition can be used. Moreover, what is necessary is just to adjust the addition amount of the additive to a composition suitably, and is not specifically limited.

<Method for Forming Transparent Insulating Layer of First Embodiment>
The composition for forming a transparent insulating layer capable of forming the transparent insulating layer of the first embodiment preferably contains at least a polymerizable compound having a (meth) acryloyl group and a photopolymerization initiator in addition to the compound A. .
The composition for forming a transparent insulating layer may contain a solvent from the viewpoint of handleability, but from the viewpoint of suppressing VOC (volatile organic compound) and reducing the tact time, it should be a solvent-free system. Is preferred. The composition for forming a transparent insulating layer comprises a polymerizable compound having a (meth) acryloyl group and a photopolymerization initiator, even if it does not contain a solvent, due to the hydrophobic polyoxypropylene chain contained in the compound A Excellent compatibility.
In addition, when the composition for transparent insulating layer formation contains a solvent, the solvent which can be used is not specifically limited, For example, water and an organic solvent are mentioned.

In the case of the coating method, the method for coating the transparent insulating layer forming composition on the substrate and the conductive part is not particularly limited, and known methods (for example, gravure coater, comma coater, bar coater, knife coater, die coater). Alternatively, a coating method such as a roll coater, an ink jet method, or a screen printing method can be used. In particular, when the screen printing method is used, the effects of the present invention can be enjoyed more. In the screen printing method, as compared with bar coating or the like, irregularities are formed on the surface of the coating film in principle during printing. According to the composition for forming a transparent insulating layer containing Compound A, a coating film having high leveling properties can be formed even when a screen printing method is used.
Further, from the viewpoint of further improving the wettability to the base material and the conductive part and further improving the effect of the present invention, the surface tension of the composition for forming a transparent insulating layer is 35 mN / m or less at 25 ° C. It is preferable that it is 30 mN / m or less. Although a minimum in particular is not restrict | limited, 15 mN / m or more is preferable.
From the viewpoint of handleability and production efficiency, an embodiment in which the composition is applied onto the substrate and the conductive part, and if necessary, a drying treatment is performed to remove the remaining solvent to form a coating film.
In addition, although the conditions of a drying process are not restrict | limited in particular, It is preferable to implement for 1 to 30 minutes (preferably 1 to 10 minutes) at room temperature-220 degreeC (preferably 50-120 degreeC) by the point which productivity is more excellent. . From the viewpoint of productivity, the transparent insulating layer forming composition preferably does not contain a solvent component and does not have a drying step.

It is preferable to perform exposure after the drying treatment.
Although the method to expose is not specifically limited, For example, the method of irradiating actinic light or a radiation is mentioned. As the irradiation with actinic light, UV (ultraviolet) lamps, light irradiation with visible light, or the like is used. Examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. By exposing a coating film, the polymeric group contained in the compound in a coating film is activated, the bridge | crosslinking between compounds arises, and hardening of a layer advances. The exposure energy may be about 10 to 8000 mJ / cm ² and is preferably in the range of 50 to 3000 mJ / cm ² .

-2nd Embodiment of a transparent insulating layer Hereinafter, 2nd Embodiment of a transparent insulating layer is described.
The transparent insulating layer according to the second embodiment includes a siloxane terminal structural unit, a dimethylsiloxane structural unit, a siloxane structural unit having a polyoxypropylene chain, an ethylene oxide structural unit, and a propylene oxide structural unit. The molar ratio of the dimethylsiloxane structural unit to the siloxane terminal structural unit is 2 or more, and the molar ratio of the propylene oxide structural unit to the ethylene oxide structural unit is 0.1 or more.
As described above, the amount of each structural unit on the surface can be preferably identified by TOF-SIMS (Time-of-Flight Secondary Mass Spectrometry) analysis on the surface of the transparent insulating layer.

  The molar ratio of the dimethylsiloxane structural unit to the siloxane terminal structural unit is preferably 2 or more, and more preferably 5 or more, from the viewpoint of further improving the leveling property. Further, the molar ratio of the propylene oxide structural unit to the ethylene oxide structural unit is preferably 0.12 or more, and more preferably 0.15 or more, from the viewpoint of further improving the leveling property.

The transparent insulating layer as described above can be formed, for example, by using the transparent insulating layer forming composition containing the compound A described in the first embodiment. For example, when the transparent insulating layer of the second embodiment is formed using a composition for forming a transparent insulating layer containing compound A, examples of the siloxane terminal structural unit include a structure represented by the following formula (4). .
Further, the composition for forming a transparent insulating layer capable of forming the transparent insulating layer of the second embodiment may contain a component other than the compound A. For example, the transparent insulating layer capable of forming the transparent insulating layer of the first embodiment may be included. Ingredients other than compound A contained in the composition for insulating layer formation are mentioned, The suitable aspect is also the same.

  Formula (4)

Although the 1st embodiment of the conductive sheet for touch sensors was explained in full detail in FIG. 1, the structure of the conductive sheet for touch sensors is not limited to this aspect.
In FIG. 1, the conductive sheet for a touch sensor in which the conductive portion 16 is disposed only on one surface on the base material 12 has been described. However, the conductive sheet for a touch sensor of the present invention has a conductive portion 16 on both surfaces on the base material 12. And the transparent insulating layer 18 may be arrange | positioned.

[Touch sensor, touch panel laminate, touch panel]
Moreover, the conductive sheet for touch sensors is applied to a touch panel. When the touch sensor conductive sheet is applied to a touch panel, the touch sensor conductive sheet functions as a part of the touch sensor. As a suitable aspect of the touch panel containing the said conductive sheet for touch sensors, a capacitive touch panel as shown in FIG. 3 is mentioned. The capacitive touch panel 100 illustrated in FIG. 3 includes a protective substrate 20, an adhesive sheet 15, a capacitive touch sensor 180, an adhesive sheet 15, and a display device 50. As will be described later, the capacitive touch sensor 180 is configured by the conductive sheet for a touch sensor of the present invention, and the conductive portion functions as a detection electrode.
Hereinafter, various members used in the capacitive touch panel 100 will be described in detail.
In the following, a capacitive touch panel will be described, but the conductive sheet for a touch sensor of the present invention may be applied to other types of touch panels.

FIG. 4 shows a plan view of the capacitive touch sensor 180. FIG. 5 is a cross-sectional view taken along the cutting line AA in FIG. The capacitive touch sensor 180 includes a base material 22, a first detection electrode 24 disposed on one main surface (on the surface) of the base material 22, a first lead wire 26, and the other of the base material 22. The second detection electrode 28, the second lead wiring 30, the flexible printed wiring board 32, the first detection electrode 24, and the first lead wiring 26 are arranged so as to cover the main surface (on the back surface). A first transparent insulating layer 40, and a second transparent insulating layer 42 disposed so as to cover the second detection electrode 28 and the second lead-out wiring 30. The region where the first detection electrode 24 and the second detection electrode 28 are provided constitutes an input region E _I (an input region (sensing unit) capable of detecting contact of an object) that can be input by the user, and is input. A first lead wiring 26, a second lead wiring 30 and a flexible printed wiring board 32 are arranged in the outer region E _O located outside the region E _I.
The base material 22 of the capacitive touch sensor 180 corresponds to the base material of the conductive sheet for the touch sensor described above, and the first detection electrode 24 and the second detection electrode 28 of the capacitive touch sensor 180 are described above. The first transparent insulating layer 40 and the second transparent insulating layer 42 of the capacitive touch sensor 180 correspond to the transparent insulating layer of the touch sensor conductive sheet described above.
Below, the said structure is explained in full detail.

The base material 22 plays a role of supporting the first detection electrode 24 and the second detection electrode 28 in the input region E _I and also plays a role of supporting the first lead wiring 26 and the second lead wiring 30 in the outer region E _O. It is a member to bear.
The definition and preferred embodiment of the base material 22 are synonymous with the base material 12 described above.

  The first detection electrode 24 and the second detection electrode 28 are sensing electrodes that sense a change in capacitance, and constitute a sensing unit (sensor unit). That is, when the fingertip is brought into contact with the touch panel, the mutual capacitance between the first detection electrode 24 and the second detection electrode 28 changes, and the position of the fingertip is calculated by an IC circuit (integrated circuit) based on the change amount. To do.

First detection electrode 24, which has a role to detect the input position in the X direction of the finger of the user in proximity to the input region E _I, has the function of generating an electrostatic capacitance between the finger ing. The first detection electrodes 24 are electrodes that extend in a first direction (X direction) and are arranged at a predetermined interval in a second direction (Y direction) orthogonal to the first direction. Contains a pattern.
The second detection electrode 28 has a role of detecting the input position in the Y direction of the user's finger approaching the input area E _I and has a function of generating a capacitance between the second detection electrode 28 and the finger. ing. The second detection electrodes 28 are electrodes that extend in the second direction (Y direction) and are arranged at a predetermined interval in the first direction (X direction), and include a predetermined pattern as will be described later. In FIG. 4, five first detection electrodes 24 and five second detection electrodes 28 are provided, but the number is not particularly limited and may be plural.

In FIG. 4, the 1st detection electrode 24 and the 2nd detection electrode 28 are comprised by the metal fine wire. FIG. 6 shows an enlarged plan view of a part of the first detection electrode 24. As shown in FIG. 6, the first detection electrode 24 is constituted by a thin metal wire 34, and includes a plurality of openings 36 by the intersecting thin metal wires 34. Note that, similarly to the first detection electrode 24, the second detection electrode 28 also includes a plurality of openings 36 formed by intersecting metal thin wires 34. That is, the 1st detection electrode 24 and the 2nd detection electrode 28 correspond to the electroconductive part which has the mesh pattern which consists of a several metal fine wire mentioned above.
The first detection electrode 24 and the second detection electrode 28 correspond to the conductive portion 16 described above, and have a mesh pattern composed of a plurality of fine metal wires. The definition and preferred embodiments of the fine metal wires 34 constituting the first detection electrode 24 and the second detection electrode 28 are the same as the fine metal wires 14 described above. The definition of the opening 36 is as described above.

The first lead wiring 26 and the second lead wiring 30 are members that play a role in applying a voltage to the first detection electrode 24 and the second detection electrode 28, respectively.
The first lead-out wiring 26 is disposed on the base material 22 in the outer region E _O , one end thereof is electrically connected to the corresponding first detection electrode 24, and the other end is electrically connected to the flexible printed wiring board 32. Is done.
The second lead wiring 30 is disposed on the base material 22 in the outer region E _O , one end thereof is electrically connected to the corresponding second detection electrode 28, and the other end is electrically connected to the flexible printed wiring board 32. Is done.
In FIG. 4, five first extraction wirings 26 and five second extraction wirings 30 are illustrated, but the number is not particularly limited, and a plurality of the first extraction wirings are usually arranged according to the number of detection electrodes. The

Examples of the material constituting the first lead wiring 26 and the second lead wiring 30 include metals such as gold (Au), silver (Ag), and copper (Cu), tin oxide, zinc oxide, cadmium oxide, and oxide. Examples thereof include metal oxides such as gallium or titanium oxide. Among these, silver is preferable because of its excellent conductivity. Alternatively, a metal paste such as a silver paste or a copper paste may be used. Furthermore, it may be made of a metal such as aluminum (Al) or molybdenum (Mo), or an alloy thin film. In the case of a metal paste, a screen printing or ink jet printing method is used, and in the case of a metal or alloy thin film, a patterning method such as a photolithography method is suitably used for the sputtered film.
In addition, it is preferable that the binder is contained in the 1st extraction wiring 26 and the 2nd extraction wiring 30 from the point which adhesiveness with the base material 22 is more excellent. The kind of binder is as above-mentioned.

  The flexible printed wiring board 32 is a board in which a plurality of wirings and terminals are provided on a substrate, and is connected to the other end of each of the first lead-out wirings 26 and the other end of each of the second lead-out wirings 30 and electrostatically It plays a role of connecting the capacitive touch sensor 180 and an external device (for example, a display device).

The first transparent insulating layer 40 is a layer disposed on the base material 22 so as to cover the first detection electrode 24 and the first lead wiring 26. The second transparent insulating layer 42 is a layer disposed on the base material 22 so as to cover the second detection electrode 28 and the second lead wiring 30.
The definition of the 1st transparent insulating layer 40 and the 2nd transparent insulating layer 42 is synonymous with the transparent insulating layer mentioned above.
In addition, the 1st transparent insulating layer 40 and the 2nd transparent insulating layer 42 are arrange | positioned on the base materials 22 other than the area | region where the flexible printed wiring board 32 mentioned above is arrange | positioned.

[Manufacturing method of capacitive touch sensor]
The manufacturing method of the capacitive touch sensor 180 is not particularly limited, and a known method can be adopted.
First, as a method of forming the detection electrode and the lead wiring on the base material, for example, a photoresist film on the metal foil formed on both main surfaces of the base material is exposed and developed to form a resist pattern. And a method of etching the metal foil exposed from the resist pattern. Moreover, the method of printing the paste containing a metal microparticle or metal nanowire on both main surfaces of a base material, and performing metal plating to a paste is mentioned.
Furthermore, in addition to the above method, a method using silver halide can be mentioned. More specifically, a method described in paragraphs 0056 to 0114 of JP-A-2014-209332 is exemplified.

The base material which has the pattern-shaped electroconductive part which consists of metal fine wires by the said procedure is manufactured. Next, a transparent insulating layer is arrange | positioned so that the obtained electroconductive part may be covered.
Examples of the method for forming the transparent insulating layer include the above-described methods using the transparent insulating layer forming composition.

<< Adhesive sheet >>
The pressure-sensitive adhesive sheet (adhesive layer) 15 is disposed for bonding the capacitive touch sensor 180 to the protective substrate 20 or the display device 50. It does not specifically limit as the adhesive sheet (adhesion layer) 15, A well-known adhesive sheet can be used.

<< Protection board >>
The protective substrate 20 is a substrate disposed on the adhesive sheet, and serves to protect a capacitive touch sensor 180 described later from the external environment, and its main surface constitutes a touch surface.
The protective substrate 20 is preferably a transparent substrate, and a plastic film, a plastic plate, a glass plate, or the like is used. It is desirable that the thickness of the substrate is appropriately selected according to each application.
Examples of the raw material for the plastic film and plastic plate include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyethylene (PE), polypropylene (PP), polystyrene, EVA (vinyl acetate copolymer polyethylene). Polyolefins such as: vinyl resins; in addition, polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC), cycloolefin resin (COP), and the like can be used.
Further, as the protective substrate 20, a polarizing plate, a circular polarizing plate, or the like may be used.

<< Display device >>
The display device 50 is a device having a display surface for displaying an image, and each member is arranged on the display screen side.
The type of the display device 50 is not particularly limited, and a known display device can be used. For example, cathode ray tube (CRT) display, liquid crystal display (LCD), organic light emitting diode (OLED) display, vacuum fluorescent display (VFD), plasma display panel (PDP), surface field display (SED), field emission display (FED), electronic paper (E-Paper), etc. are mentioned.

As mentioned above, although an example of the touch panel which functioned and used the conductive sheet for touch sensors of this invention as a part of touch sensor was demonstrated, the conductive sheet for touch sensors of this invention may be comprised as a touchscreen laminated body. . As a touch panel laminated body, the structure provided with the conductive sheet for touch sensors, the adhesive sheet, and the peeling sheet is mentioned, for example. The release sheet functions as a protective sheet for preventing the touch sensor conductive sheet from being damaged when the touch panel laminate is conveyed.
Moreover, the conductive sheet for touch sensors of this invention may be handled with the form of the composite body which has the conductive sheet for touch sensors, an adhesive sheet, and a protective substrate in this order, for example.

[Composition for forming transparent insulating layer]
The composition for forming a transparent insulating layer of the present invention is a composition for forming a transparent insulating layer that is used for the production of a conductive sheet for a touch sensor and is applied to the surface of a patterned conductive portion made of fine metal wires. including.
The configuration of the composition for forming a transparent insulating layer of the present invention is the same as the configuration of the composition for forming a transparent insulating layer described in the configuration of the conductive sheet for a touch sensor, and the preferred embodiment thereof is also the same.

  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.

[Example 1]
<< Preparation of conductive sheet for touch sensor >>
<Formation of conductive part>
(Preparation of silver halide emulsion)
To the following 1 liquid maintained at 38 ° C. and pH 4.5, an amount corresponding to 90% of each of the following 2 and 3 liquids was added simultaneously over 20 minutes with stirring to form 0.16 μm core particles. Subsequently, the following 4 liquid and 5 liquid were added over 8 minutes, and the remaining 10% of the following 2 liquid and 3 liquid were further added over 2 minutes to grow the particles to 0.21 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete the grain formation.

1 liquid:
750 ml of water
8.6g gelatin
Sodium chloride 3g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
Two liquids:
300 ml of water
150 g silver nitrate
3 liquids:
300 ml of water
Sodium chloride 38g
Potassium bromide 32g
5 ml of potassium hexachloroiridium (III) (0.005% KCl 20% aqueous solution)
Ammonium hexachlororhodate
(0.001% NaCl 20% aqueous solution) 7 ml
4 liquids:
100ml water
Silver nitrate 50g
5 liquids:
100ml water
Sodium chloride 13g
Potassium bromide 11g
Yellow blood salt 5mg

  Then, it washed with water by the flocculation method according to a conventional method. Specifically, the temperature of the solution obtained above was lowered to 35 ° C., and the pH was lowered using sulfuric acid until silver halide precipitated (the pH was in the range of 3.6 ± 0.2). Next, about 3 liters of the supernatant was removed (first water washing). Further, 3 liters of distilled water was added, and sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second water wash). The same operation as the second water washing was further repeated once (third water washing) to complete the water washing and desalting steps. The emulsion after washing and desalting was adjusted to pH 6.4 and pAg 7.5, and 2.5 g gelatin, 10 mg sodium benzenethiosulfonate, 3 mg sodium benzenethiosulfinate, 15 mg sodium thiosulfate and 10 mg chloroauric acid were added. Chemical sensitization was performed to obtain optimum sensitivity at ° C. Thereafter, 100 mg of 1,3,3a, 7-tetraazaindene as a stabilizer and 100 mg of proxel (trade name, manufactured by ICI Co., Ltd.) as a preservative were further added. The finally obtained emulsion contains 0.08 mol% of silver iodide, and the ratio of silver chlorobromide is 70 mol% of silver chloride and 30 mol% of silver bromide. It was a silver iodochlorobromide cubic grain emulsion having a coefficient of 9%.

(Preparation of photosensitive layer forming composition)
1,3,3a, 7-tetraazaindene 1.2 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻⁴ mol / Mol Ag, 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 0.90 g / mol Ag, a trace amount of hardener was added, and the coating solution pH was adjusted to 5.6 using citric acid. Adjusted.
Polymer latex containing a polymer represented by the following formula (P-1) and a dialkylphenyl PEO (polyethylene glycol) sulfate ester with respect to gelatin contained in the coating solution (mass of dispersant / polymer) The ratio was 2.0 / 100 = 0.02) and polymer / gelatin (mass ratio) = 0.5 / 1.
Furthermore, EPOXY RESIN DY 022 (trade name: manufactured by Nagase ChemteX Corporation) was added as a crosslinking agent. In addition, the addition amount of the crosslinking agent was adjusted so that the amount of the crosslinking agent in the silver halide-containing photosensitive layer described later was 0.09 g / m ² .
A photosensitive layer forming composition was prepared as described above.
The polymer represented by the following formula (P-1) was synthesized with reference to Japanese Patent No. 3305459 and Japanese Patent No. 3754745.

(Photosensitive layer forming step)
The polymer latex was applied to a polyethylene terephthalate (PET) film having a thickness of 100 μm to provide an undercoat layer having a thickness of 0.05 μm.
Next, a silver halide-free layer forming composition in which the polymer latex and gelatin were mixed was applied onto the undercoat layer to provide a 1.0 μm-thick silver halide-free layer. The mixing mass ratio of polymer and gelatin (polymer / gelatin) was 2/1, and the polymer content was 0.65 g / m ² .
Next, the photosensitive layer forming composition was applied on the silver halide-free layer to provide a silver halide-containing photosensitive layer having a thickness of 2.5 μm. The mixing mass ratio (polymer / gelatin) of the polymer and gelatin in the silver halide-containing photosensitive layer was 0.5 / 1, and the polymer content was 0.22 g / m ² .
Next, a protective layer-forming composition in which the polymer latex and gelatin were mixed was applied onto the silver halide-containing photosensitive layer to provide a protective layer having a thickness of 0.15 μm. The mixing mass ratio of polymer to gelatin (polymer / gelatin) was 0.1 / 1, and the polymer content was 0.015 g / m ² .

(Exposure and development processing)
The photosensitive layer prepared above was exposed using parallel light using a high-pressure mercury lamp as a light source through a photomask capable of providing a developed silver image having a mesh pattern shown in FIG. Specifically, a lattice (square) photomask was used in which the conductive part had a thickness of 1 μm and the conductive thin wire / non-conductive part gave a conductive pattern of 4 μm / 300 μm. After exposure, the film was developed with the following developer, developed with a fixer (trade name: N3X-R for CN16X: manufactured by Fuji Film), rinsed with pure water, and then dried.

(Developer composition)
The following compounds are contained in 1 liter (L) of the developer.
Hydroquinone 0.037mol / L
N-methylaminophenol 0.016 mol / L
Sodium metaborate 0.140 mol / L
Sodium hydroxide 0.360 mol / L
Sodium bromide 0.031 mol / L
Potassium metabisulfite 0.187 mol / L

(Heat treatment)
Furthermore, it heat-processed by leaving still for 130 second in a 120 degreeC superheated steam tank.

(Gelatin decomposition treatment)
Further, it was immersed in a gelatin decomposition solution (40 ° C.) prepared as described below for 120 seconds, and then immersed in warm water (liquid temperature: 50 ° C.) for 120 seconds for washing.

Preparation of gelatin degradation solution:
Triethanolamine and sulfuric acid were added to an aqueous solution of proteolytic enzyme (Biolase 30L manufactured by Nagase ChemteX) (proteolytic enzyme concentration: 0.5% by mass) to adjust the pH to 8.5.

(Polymer crosslinking treatment)
Furthermore, it was immersed in a 1% aqueous solution of Carbodilite V-02-L2 (trade name: manufactured by Nisshinbo Co., Ltd.) for 30 seconds, taken out from the aqueous solution, immersed in pure water (room temperature) for 60 seconds and washed.
In this way, a film A having a conductive part formed on a PET film was obtained.

<Formation of transparent insulating layer>
PETA (pentaerythritol (tri / tetra) acrylate, (trade name KAYARAD PET = 30) manufactured by Nippon Kayaku Co., Ltd.) 39.84% by mass as a bifunctional or higher polyfunctional compound, NATCO UV self-healing as a (meth) acrylate oligomer (Manufactured by Nagase Co., Ltd.) The liquid mixture was applied onto the silver mesh pattern, which is the conductive part of the film A produced above, by screen printing to form a coating film. Next, the coating film was allowed to stand at 25 ° C. for 15 minutes, and then exposed to an irradiation intensity of 160 mW / cm ² and an integrated illuminance of 1000 mJ / cm ² using a Fusion D bulb, with a thickness of 10 μm. A transparent insulating layer, which is a cured film, was formed.

  In Table 1, “Si unit” means a dimethylsiloxane structural unit, “EO unit” means a siloxane structural unit having a polyoxyethylene chain, and “PO unit” means a siloxane structural unit having a polyoxypropylene chain. “Si unit amount”, “EO unit amount” and “PO unit amount” are the contents of each structural unit relative to the sum of the molar amounts of the above “Si unit”, “EO unit” and “PO unit” ( Mol%).

<< Measurement of physical properties >>
<Identification of leveling agent>
The composition of the leveling agent (Compound A) was identified by NMR (nuclear magnetic resonance) measurement of the leveling agent. Moreover, the composition of the leveling agent in the transparent insulating layer was identified by measuring the surface of the transparent insulating layer by the SIMS method (Secondary Ion Mass Spectrometry).
Various identification methods are as follows.
NMR (nuclear magnetic resonance) measurement of leveling agent (compound A): The number of moles is calculated from the peak intensity ratio attributed to Si unit, EO unit, and PO unit by NMR.
Measurement of compound B in the transparent insulating layer by SIMS method: For TOF-SIMS apparatus, using Bi ³⁺ primary ions, the signal intensity of each secondary ion of each structural unit is determined as the total ion intensity (or suitable for normalization) It was measured by normalizing with the signal intensity of the mass peak derived from the component. The identification results are shown in the column “Compositions of compounds A and B contained in transparent insulating layer (first embodiment)” in Table 1.
Measurement of transparent insulating layer surface by SIMS method: For TOF-SIMS apparatus, using Bi ³⁺ primary ion, each of siloxane terminal structural unit, ethylene oxide structural unit, propylene oxide structural unit structural unit and dimethylsiloxane structural unit. The signal intensity of the secondary ion was measured by normalizing with the total ion intensity (or the signal intensity of the mass peak derived from the component suitable for normalization). The identification results are shown in the column “Surface condition of transparent insulating layer (second embodiment)” in Table 1.

<Surface tension of transparent insulating layer forming composition>
The surface tension of the composition for forming a transparent insulating layer was measured at 25 ° C. using a contact angle meter FTA1000 manufactured by FTA.

<Surface energy of transparent insulating layer>
The surface energy of the transparent insulating layer was measured at 25 ° C. using an automatic contact angle meter DM-300 manufactured by Kyowa Interface Science Co., Ltd.

<Total light transmittance>
The total light transmittance with respect to the visible light region (wavelength 400 to 700 nm) of the obtained conductive sheet for touch sensor was measured (note that the measurement position is a region where a transparent insulating layer is formed). For the measurement, a spectrocolorimeter CM-3600A (manufactured by Konica Minolta Co., Ltd.) was used. As a result, the total light transmittance of the conductive sheet for a touch sensor of Example 1 was 95%. Moreover, the same measurement was performed also about Examples 2-11 and Comparative Examples 1-5, and it confirmed that the total light transmittance was about 95% also in any conductive sheet for touch sensors.

<< Evaluation >>
Various evaluation was performed about the obtained conductive sheet for touch sensors.
<Evaluation of leveling properties>
The leveling property is evaluated by observing the coating film before exposure of the composition for forming a transparent insulating layer (coating liquid) disposed on the film A in the process of producing the conductive sheet for a touch sensor described above. ”And“ repellency ”. Hereinafter, each evaluation method will be described.

(1) Smoothness After applying the transparent insulating layer forming composition (coating liquid) to the film A by the above-described procedure to form a coating film, the film was allowed to stand at room temperature for 10 minutes. After standing, the smoothness of the coating film was visually observed and judged according to the following evaluation criteria. The results are shown in Table 1. In practice, the smoothness is preferably “4” or more.
“5”: almost smooth “4”: slight unevenness is observed “3”: clear unevenness is observed.
“2”: Large unevenness is observed.
“1”: Very large unevenness is observed.

(2) Evaluation of repellency According to the procedure described above, the composition for forming a transparent insulating layer (coating solution) was applied to film A to form a coating film, and then allowed to stand at room temperature for 10 minutes. After standing, the repellency of the coating film was visually observed and judged according to the following evaluation criteria. The results are shown in Table 1. Practically, the repelling property is preferably “3” or more.
“5”: No repelling “4”: There is a little splashing, but no spot-like non-film formation region is formed “3”: There are many splashes, but a spot-like non-film-forming region is formed Not “2”: A spot-like non-deposition region is partially seen “1”: A spot-like non-deposition region is seen on one side.

<Evaluation of film shrinkage>
The film shrinkability of the conductive sheet for touch sensor is evaluated by observing the coating film before exposure of the composition for forming a transparent insulating layer (coating liquid) disposed on film A in the above-mentioned conductive sheet manufacturing process for touch sensor. It was done by doing.
Specifically, the film A was coated with the composition for forming a transparent insulating layer (coating solution) by the procedure described above to form a coating film, and then allowed to stand at room temperature for 10 minutes. After standing, the film shrinkage of the coating film was observed with a ruler and visually, and judged according to the following evaluation criteria. The results are shown in Table 1. Practically, the film contractility is preferably “3” or more.
“5”: No contraction is observed at all. “4”: Slight bulge is observed at the end, but there is no dimensional change. “3”: Swell is observed at the end, but there is no dimensional change. “2”: Dimensional change is observed at a part of the end part “1”: Dimensional change is observed at the entire end part

<Adhesion evaluation>
On the transparent insulating layer of the obtained conductive sheet for touch sensor, a peeling film (trade name “SRL-0753”, manufactured by Lintec Corporation), which is a protective film with an adhesive layer, was attached. Specifically, the release film is bonded onto the transparent insulating layer of the conductive sheet for the touch sensor using a 2 kg roller, treated for 20 minutes in an autoclave (40 ° C., 0.5 MPa), and left for 24 hours. did. Subsequently, one end of the release film was gripped using an autograph manufactured by Shimadzu Corporation, a 180 degree peel test (tensile speed of 300 mm / min) was performed, and an adhesion force (N / mm) was measured. The results are shown in Table 1. Practically, the adhesion is preferably 0.12 N / mm or more.

[Examples 2-11, Comparative Examples 1-5]
As shown in Table 1 below, touches of Examples 2 to 11 and Comparative Examples 1 to 5 were performed in the same manner as in Example 1 except that the composition or formulation of the conductive part material or the transparent insulating layer forming composition was changed. A sensor conductive sheet was prepared and evaluated in the same manner. The results are shown in Table 1.

Hereinafter, various materials used in Examples 1 to 11 and Comparative Examples 1 to 5 are shown.
(Polymerizable compound having (meth) acryloyl group)
As the polymerizable compound having a (meth) acryloyl group, those shown below were used.
Bifunctional or higher polyfunctional compound “PETA”: Pentaerythritol (tri / tetra) acrylate (trade name KAYARAD PET = 30) manufactured by Nippon Kayaku Co., Ltd. “DPHA”: Dipentaerythritol hexaacrylate (trade name KAYARAD DPHA) Japan Made by Kayaku Co., Ltd.

Urethane (meth) acrylate compound “NATOCO UV self-healing”: urethane acrylate compound, manufactured by Nagase “EXP DX-40”: urethane acrylate compound, manufactured by DIC “AH-300”: urethane acrylate compound, manufactured by Kyoei Chemical Co., Ltd. UA-300H ": urethane acrylate compound, manufactured by Kyoei Chemical Co., Ltd.

-Monofunctional (meth) acrylate monomer for dilution "HDDA": 1,6-hexanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. "IBXA": Isobonyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.

(Leveling agent)
As a leveling agent (compound A), the following were used. The “Si unit amount”, “EO unit amount” and “PO unit amount” contained in each leveling agent were identified by ¹ H-NMR (nuclear magnetic resonance method). As a result, the amount of various units contained in the leveling agent is determined by the SIMS method of the film of the transparent insulating layer shown in the table (“Composition of compounds A and B contained in the transparent insulating layer (first embodiment)” column). ) Was confirmed to be almost identical with the identification value obtained.
・ "BYK-UV3455": (Bic Chemie Japan)
・ "BYK-302": (Bic Chemie Japan)
・ "BYK-UV3510": (Bic Chemie Japan)

(Photopolymerization initiator)
As the photopolymerization initiator, those shown below were used.
・ Irgacure 184: (BASF)

(Conductive material)
As the conductive part material, the following materials were used.
“Ag mesh pattern”: The Ag mesh pattern is as described in detail in the conductive sheet for a touch sensor of Example 1.

・ "Cu mesh pattern":
First, a Ni layer having a thickness of 5 nm was formed on a polyethylene terephthalate (PET) film by a sputtering method, and then a copper flat film having a thickness of 2 μm was formed by a vacuum evaporation method using resistance heating. Subsequently, the same patterning as the Ag mesh pattern produced in Example 1 was performed by a normal photolithography method, and a film having a conductive portion made of a Cu mesh pattern on the substrate was produced.

・ "Ag nanowire":
In accordance with the method described in JP-A-2009-215594, an Ag nanowire was produced, and a coating film having a thickness of 1 μm was formed. Subsequently, the same patterning as the Ag mesh pattern produced in Example 1 was implemented by the normal photolithography method, and the film which has the electroconductive part which consists of Ag wires on a base material was produced.

(Table 1)

(Table 1 continued)

(Table 1 continued)

From the results in Table 1, it is confirmed that the transparent insulating layer of the touch panel conductive sheet of the example is formed at a predetermined position of the conductive portion by being excellent in leveling property and suppressing shrinkage during coating. It was done. Moreover, it was confirmed that adhesiveness with an adhesive sheet is also favorable.
On the other hand, all of the transparent insulating layers of the touch panel conductive sheet of the comparative example had poor leveling properties, and there were portions that were not covered at predetermined positions of the conductive portion due to shrinkage during coating.

10 Conductive sheet for touch sensor 12, 22 Base material 14, 34 Metal fine wire 15 Adhesive layer (adhesive sheet)
16 Conductive portions 18, 40, 42 Transparent insulating layer 20 Protective substrate 24 First detection electrode 26 First extraction wiring 28 Second detection electrode 30 Second extraction wiring 32 Flexible printed wiring board 36 Opening 50 Display device 100 Capacitive type Touch panel 180 capacitive touch sensor

Claims (13)

A substrate;
A conductive part in the form of a pattern made of fine metal wires, disposed on the base material,
A conductive sheet for a touch sensor comprising a transparent insulating layer disposed on the conductive part,
The transparent insulating layer is a layer formed using a composition for forming a transparent insulating layer containing compound A,
Compound A has a siloxane structural unit having a polyoxyethylene chain, a siloxane structural unit having a polyoxypropylene chain, and a dimethylsiloxane structural unit,
The content of the dimethylsiloxane structural unit is 20 with respect to the total of the molar amounts of the siloxane structural unit having a polyoxyethylene chain, the siloxane structural unit having a polyoxypropylene chain, and the dimethylsiloxane structural unit. The content of the siloxane structural unit having a polyoxypropylene chain which is not less than mol% is the siloxane structural unit having the polyoxyethylene chain, the siloxane structural unit having the polyoxypropylene chain, and the dimethylsiloxane structural unit. The conductive sheet for touch sensors which is 20 mol% or more with respect to the total of the respective molar amounts.   The conductive sheet for a touch sensor according to claim 1 or 2, wherein the transparent insulating layer forming composition further comprises a polymerizable compound having an acryloyl group or a methacryloyl group and a polymerization initiator.   The conductive sheet for a touch sensor according to claim 1 or 2, wherein a surface tension of the composition for forming a transparent insulating layer is 35 mN / m or less at 25 ° C. A substrate;
A conductive part in the form of a pattern made of fine metal wires, disposed on the base material,
A conductive sheet for a touch sensor comprising a transparent insulating layer disposed on the conductive part,
The transparent insulating layer contains a compound B;
Compound B has a siloxane structural unit having a polyoxyethylene chain, a siloxane structural unit having a polyoxypropylene chain, and a dimethylsiloxane structural unit,
The content of the dimethylsiloxane structural unit is 20 with respect to the total of the molar amounts of the siloxane structural unit having a polyoxyethylene chain, the siloxane structural unit having a polyoxypropylene chain, and the dimethylsiloxane structural unit. The content of the siloxane structural unit having a polyoxypropylene chain is not less than mol%, and the siloxane structural unit having the polyoxyethylene chain, the siloxane structural unit having the polyoxypropylene chain, and the dimethylsiloxane structural unit. The conductive sheet for touch sensors which is 20 mol% or more with respect to the total of the respective molar amounts. A substrate;
A conductive part in the form of a pattern made of fine metal wires, disposed on the base material,
A conductive sheet for a touch sensor comprising a transparent insulating layer disposed on the conductive part,
The surface of the transparent insulating layer includes a siloxane terminal structural unit, a dimethylsiloxane structural unit, an ethylene oxide structural unit, and a propylene oxide structural unit, and the molar ratio of the dimethylsiloxane structural unit to the siloxane terminal structural unit is 2 or more. The conductive sheet for a touch sensor, wherein the molar ratio of the propylene oxide structural unit to the ethylene oxide structural unit is 0.1 or more.   The conductive sheet for a touch sensor according to any one of claims 1 to 5, wherein the surface energy of the transparent insulating layer is 30 mN / m or less at 25 ° C.   The conductive sheet for a touch sensor according to any one of claims 1 to 6, wherein the conductive portions are arranged on both surfaces of the base material and have a mesh pattern made of silver thin wires. It is a manufacturing method of the conductive sheet for touch sensors according to any one of claims 1 to 7,
The manufacturing method of the conductive sheet for touch sensors which has the transparent insulating layer formation process which forms a transparent insulating layer by the screen printing method on the said base material and the said electroconductive part.   The touch sensor containing the conductive sheet for touch sensors of any one of Claims 1-8.   A touch panel laminate comprising the conductive sheet for a touch sensor according to claim 1, an adhesive sheet, and a release sheet in this order.   A touch panel including the touch sensor according to claim 9. A composition for forming a transparent insulating layer, which is used for the production of a conductive sheet for a touch sensor and is applied to the surface of a patterned conductive portion made of a fine metal wire,
The composition for forming a transparent insulating layer contains a compound A, the compound A has a siloxane structural unit having a polyoxyethylene chain, a siloxane structural unit having a polyoxypropylene chain, and a dimethylsiloxane structural unit, Furthermore, it has an acryloyl group or a methacryloyl group,
The content of the dimethylsiloxane structural unit is 20 with respect to the total of the molar amounts of the siloxane structural unit having a polyoxyethylene chain, the siloxane structural unit having a polyoxypropylene chain, and the dimethylsiloxane structural unit. The content of the siloxane structural unit having a polyoxypropylene chain is not less than mol%, and the siloxane structural unit having the polyoxyethylene chain, the siloxane structural unit having the polyoxypropylene chain, and the dimethylsiloxane structural unit. The composition for transparent insulating layer formation which is 20 mol% or more with respect to the sum total of each molar amount of.   The composition for forming a transparent insulating layer according to claim 12, wherein the surface tension of the composition for forming a transparent insulating layer is 35 mN / m or less at 25 ° C.