KR20170135866A - Transparent conductive sheet, touch panel module and touch panel device - Google Patents

Abstract

Deterioration of electrical properties is suppressed, and transparency, durability and moisture resistance of the pressure-sensitive adhesive layer are excellent.
Wherein the pressure-sensitive adhesive layer contacting the conductive layer comprises an acrylic copolymer, and the acrylic copolymer has a weight average molecular weight (Mw) of more than 100,000 and not more than 2,000,000, and a copolymerizable monomer component (Meth) acrylate having a cyclic alkyl group having 5 to 9 carbon atoms and an alkyl (meth) acrylate having an alkyl group having 10 to 20 carbon atoms, , The total amount of the hydrophobic monomer in the copolymerized monomer component of the acrylic copolymer is 35 wt% or more with respect to the total mass of the acrylic copolymer, and the haze value when the thickness of the pressure- A conductive sheet, and a touch panel module and a touch panel device using the same.

Description

Transparent conductive sheet, touch panel module and touch panel device

The present invention relates to a transparent conductive sheet, a touch panel module, and a touch panel device.

BACKGROUND ART A touch panel type display that allows an operation by being in contact with an image display surface is widely used for smart phones, tablet terminals, notebook computers, ticket machines, and ATMs.

In the touch panel, a resistive film type in which the position of a screen depressed with a finger or a pen is detected by measurement of a voltage change or a weak current that occurs when a finger touches the screen, that is, a change in capacitance (charge) A capacitive sensing method for sensing the position touched by a user, and the like are known.

In the capacitance type touch panel, a configuration in which an ITO film (indium tin oxide) is provided as a transparent conductive film on a transparent resin film or a glass substrate is widely adopted.

However, since the ITO film has a large resistance, there is a problem that the response speed (the time from the contact of the fingertip to the detection of the position thereof) is delayed as the screen size increases.

For this reason, instead of an electrode made of a transparent metal oxide such as an ITO film, by employing an electrode constituted by arranging a plurality of gratings constituted by a band-shaped conductive region formed by using a metal material such as metal fine particles, A method of lowering the resistance has also been proposed (for example, Patent Document 1, etc.).

In the technique exemplified in Patent Document 1 or the like, it is important to prevent corrosion of the strip-shaped conductive region, to secure the cohesive force of the pressure-sensitive adhesive layer (pressure-sensitive adhesive layer), to prevent separation and coloring in a high temperature and high humidity environment.

Therefore, in order to solve such a problem, (meth) acrylate ester (meth) acrylate ester containing a (meth) acrylic acid ester monomer as a main monomer component and not containing a monomer containing a carboxyl group (Meth) acrylic acid ester copolymer (B) containing as a monomer component a copolymerizable monomer containing a (meth) acrylic acid ester monomer and a nitrogen atom and not containing a monomer containing a carboxyl group A transparent conductive film laminate having a pressure-sensitive adhesive layer composed of an acrylic pressure-sensitive adhesive composition has been proposed (Patent Document 2).

Japanese Laid-Open Patent Publication No. 2012-33147 Japanese Unexamined Patent Publication No. 2012-79257

However, as a result of the investigation by the present inventors, it has been found that even in the members exemplified in Patent Document 2, when it is difficult to balance deterioration of electrical characteristics due to corrosion of the conductive region, transparency of the pressure-sensitive adhesive layer, durability and moisture resistance .

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and provides a transparent conductive sheet excellent in transparency, durability and moisture resistance of a pressure-sensitive adhesive layer while suppressing deterioration of electrical properties, and a touch panel module and a touch panel device manufactured using the transparent conductive sheet. .

The above object is achieved by the present invention described below. In other words,

In the transparent conductive sheet of the present invention,

A conductive layer using a metal material as a conductive material

At least a pressure-sensitive adhesive layer which is in contact with the conductive layer and contains one or more kinds of polymers,

Wherein at least one kind of polymer of one or more kinds of polymers is an acrylic copolymer,

The acrylic copolymer is a copolymer

An alkyl methacrylate having a linear or branched alkyl group having 1 to 9 carbon atoms as the copolymerizable monomer component, an alkyl (meth) acrylate having a cyclic alkyl group having 5 to 9 carbon atoms (Meth) acrylate and an alkyl (meth) acrylate having an alkyl group having 10 to 20 carbon atoms, wherein the hydrophobic monomer is selected from the group consisting of

The total amount of the hydrophobic monomers in the copolymerized monomer component of the acrylic copolymer is 35 wt% or more based on the total mass of the acrylic copolymer,

And a haze value when the thickness of the pressure-sensitive adhesive layer is 100 mu m is 1.0 or less.

In the touch panel module of the present invention,

A conductive layer using a metal material as a conductive material

And a pressure-sensitive adhesive layer that contacts the conductive layer,

The pressure-sensitive adhesive layer comprises an acrylic copolymer,

The acrylic copolymer is a copolymer

An alkyl methacrylate having a linear or branched alkyl group having 1 to 9 carbon atoms as the copolymerizable monomer component, an alkyl (meth) acrylate having a cyclic alkyl group having 5 to 9 carbon atoms (Meth) acrylate and an alkyl (meth) acrylate having an alkyl group having 10 to 20 carbon atoms, wherein the hydrophobic monomer is at least one selected from the group consisting of

The total amount of the hydrophobic monomers in the copolymerized monomer component of the acrylic copolymer is 35 wt% or more based on the total mass of the acrylic copolymer,

And a haze value when the thickness of the pressure-sensitive adhesive layer is 100 mu m is 1.0 or less.

In the touch panel device of the present invention,

The image display device

A conductive layer which is provided on the image display surface side of the image display device and which uses a metal material as a conductive material and a pressure-sensitive adhesive layer which is in contact with the conductive layer,

The pressure-sensitive adhesive layer comprises an acrylic copolymer,

The acrylic copolymer is a copolymer

An alkyl methacrylate having a linear or branched alkyl group having 1 to 9 carbon atoms as the copolymerizable monomer component, an alkyl (meth) acrylate having a cyclic alkyl group having 5 to 9 carbon atoms (Meth) acrylate and an alkyl (meth) acrylate having an alkyl group having 10 to 20 carbon atoms, wherein the hydrophobic monomer is at least one selected from the group consisting of

The total amount of the hydrophobic monomers in the copolymerized monomer component of the acrylic copolymer is 35 wt% or more based on the total mass of the acrylic copolymer,

And a haze value when the thickness of the pressure-sensitive adhesive layer is 100 mu m is 1.0 or less.

According to the present invention, it is possible to provide a transparent conductive sheet excellent in transparency, durability and moisture resistance of a pressure-sensitive adhesive layer while suppressing deterioration of electrical characteristics, and a touch panel module and a touch panel device manufactured using the transparent conductive sheet.

1 is a schematic plan view showing an example of the transparent conductive sheet of the present invention.
2 is a schematic plan view showing another example of the transparent conductive sheet of the present invention.
Fig. 3 is an enlarged plan view showing an example in which the conductive regions shown in Figs. 1 and 2 are enlarged.
4 is a schematic cross-sectional view showing an example of the cross-sectional structure of the transparent conductive sheet of the present invention.
5 is a schematic sectional view showing another example of the sectional structure of the transparent conductive sheet of the present invention.
6 is a schematic sectional view showing another example of the sectional structure of the transparent conductive sheet of the present invention.
7 is a schematic sectional view showing another example of the sectional structure of the transparent conductive sheet of the present invention.
8 is a schematic cross-sectional view showing an example of the touch panel device of the present embodiment.

The transparent conductive sheet of the present embodiment includes at least a conductive layer using a metal material as a conductive material and a pressure-sensitive adhesive layer in contact with the conductive layer.

Here, the pressure-sensitive adhesive layer includes an acrylic copolymer, and the acrylic copolymer has a weight average molecular weight (Mw) of more than 100,000 and less than 2,000,000, and as the copolymerizable monomer component, a linear or branched alkyl group having 1 to 9 carbon atoms Alkyl (meth) acrylate having a cyclic alkyl group having 5 to 9 carbon atoms and alkyl (meth) acrylate having an alkyl group having 10 to 20 carbon atoms. Wherein the total amount of the hydrophobic monomers in the copolymerized monomer component of the acrylic copolymer is 35 wt% or more based on the total mass of the acrylic copolymer, and the thickness of the pressure-sensitive adhesive layer Is 100 mu m, the haze value is 1.0 or less.

Here, examples of the copolymerizable monomer component of the acrylic copolymer contained in the pressure-sensitive adhesive layer include alkyl methacrylates having a linear or branched alkyl group having 1 to 9 carbon atoms (hereinafter sometimes referred to as "hydrophobic monomer (a1)") (Meth) acrylate having a cyclic alkyl group of 5 to 9 carbon atoms (hereinafter sometimes referred to as "hydrophobic monomer (a2)") and alkyl (meth) acrylate having alkyl group of 10 to 20 carbon atoms And may be referred to as a monomer (b)) is selected from the group consisting of a hydrophobic monomer and a hydrophobic monomer.

Since such a monomer is a hydrophobic monomer having a hydrophobic alkyl group in its molecule, moisture in the air can be prevented from being absorbed into the pressure-sensitive adhesive layer.

Therefore, if the compounding ratio of at least one hydrophobic monomer selected from the group consisting of the hydrophobic monomer (a1), the hydrophobic monomer (a2) and the hydrophobic monomer (b) in the copolymerized monomer component is large, The metal element constituting the pressure-sensitive adhesive layer comes into contact with water molecules absorbed in the pressure-sensitive adhesive layer, making it difficult to ionize.

In this case, ionization and migration attributable to the ionization of the metal element (for example, Ag or the like) constituting the metal thin wire can be suppressed, and as a result, short-circuiting or breakage of the metal thin wire can be suppressed .

In addition to this, wet heat whitening of the pressure-sensitive adhesive layer can also be suppressed.

Since the hydrophobic monomer (a1) has a lower polarity (lower polarity) than that of the acrylic acid ester having a hydrogen atom on the alpha side due to the contribution of the methyl group on the alpha side, the monomer species having an alkyl group of the same carbon number species, the hydrophobicity of the polymer is higher than that of the hydrophilic polymer, so that the resulting polymer can be made more hydrophobic, besides, the polymer chain has a large steric hindrance and permeation of water molecules in the pressure- Diffusion can be suppressed.

In addition, the hydrophobic monomer (a2) can be made more hydrophobic by the contribution of the cyclic alkyl group having a relatively large volume.

In addition, the hydrophobic monomer (b) can be made more hydrophobic by the contribution of its long chain alkyl group having high hydrophobicity.

In order to reliably exhibit the above-mentioned effects, the total mixing ratio of the hydrophobic monomers in the copolymerized monomer component is required to be 35 wt% or more with respect to the total mass of the acrylic copolymer, preferably 40 wt% or more , And more preferably 50 wt% or more.

The upper limit (upper limit) of the blending ratio may be 100 wt%, but it is preferably 97 wt% or less from the viewpoint of balancing both the migration and the suppression of whitening whitening and other properties required as the pressure-sensitive adhesive layer .

Examples of the alkyl methacrylate having a linear or branched alkyl group of 1 to 9 carbon atoms (hydrophobic monomer (a1)) include methyl methacrylate, ethyl methacrylate, Butyl methacrylate, isopropyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, Acrylates such as t-butyl methacrylate, pentyl methacrylate, n-hexyl methacrylate, heptyl methacrylate, n-octyl methacrylate, methacryloyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, isononyl methacrylate and the like. Of these, n-butyl methacrylate re The agent is preferred.

Examples of the alkyl (meth) acrylate having a cyclic alkyl group having 5 to 9 carbon atoms (hydrophobic monomer (a2)) include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate, cycloheptyl (meth) acrylate and the like. Of these, cyclohexyl (meth) acrylate is preferred, cyclohexyl methacrylate, Is particularly preferable.

Examples of the alkyl (meth) acrylate having an alkyl group of 10 to 20 carbon atoms (hydrophobic monomer (b)) include n-decyl (meth) acrylate, (Meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, Tridecyl (meth) acrylate, iso-tridecyl (meth) acrylate, tetradecyl (meth) acrylate, heptadecyl (meth) acrylate, Heptadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, (meth) acrylate, and the like. Of these, iso-decyl methacrylate, lauryl (meth) acrylate, Re (meth) acrylate is preferred.

As the copolymerizable monomer component of the acrylic copolymer, other monomers other than the hydrophobic monomers (a1, a2, b) may be suitably used as needed.

Examples of the other monomer include, but are not limited to, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl (meth) acrylate Acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, (Meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl acrylamide, .

Acrylic acid and the like, but from the viewpoint of metal corrosion resistance, it is required to be 1 wt% or less with respect to the total mass of the acrylic copolymer, preferably 0.5 wt% or less, Is more preferable.

When a hydrophilic monomer having a hydroxyl group, an amide group or the like is used as other monomers such as 2-hydroxyethyl (meth) acrylate and (meth) acrylamide, the hydrophilic monomer in the copolymerized monomer component of the acrylic copolymer Is too large, migration and suppression of whitening of the pressure-sensitive adhesive layer may be insufficient.

For this reason, the blending ratio of the hydrophilic monomer in the copolymerized monomer component of the acrylic copolymer is preferably 15 wt% or less, more preferably 10 wt% or less.

In addition, the weight average molecular weight (Mw) of the acrylic copolymer contained in the pressure-sensitive adhesive layer needs to be more than 100,000, thereby ensuring excellent durability.

The weight average molecular weight (Mw) is preferably 150,000 or more, more preferably 200,000 or more.

On the other hand, from the viewpoint of durability, the upper limit value of the weight average molecular weight (Mw) is not particularly limited, but from the viewpoint of suppressing practical problems such as viscosity increase of the acrylic copolymer, And preferably 1.8 million or less.

In the specification of the present application, the weight average molecular weight (Mw) means a weight average molecular weight determined by Gel Permeation Chromatography (GPC) measurement.

Here, when two or more acrylic copolymers are contained in the pressure-sensitive adhesive layer, the weight average molecular weight (Mw) is determined for each polymer.

As the polymer component contained in the pressure-sensitive adhesive layer, if at least an acrylic copolymer having a weight-average molecular weight (Mw) of more than 100,000 and less than 2,000,000 (hereinafter sometimes referred to as "main component polymer") is contained, Or may be composed of the main component polymer and other polymers.

As the other polymer, an acrylic copolymer different in composition of the main component polymer and a weight average molecular weight (Mw) or a constituent monomer or a non-acrylic polymer different in basic molecular structure from the main component polymer can be given.

However, when the blending ratio of other polymers in the total polymer component is too large, the influence of other polymers is more dominant in determining various properties of the pressure-sensitive adhesive layer than in the main component polymer. Therefore, wt% or less, more preferably 10 wt% or less, and still more preferably 4 wt% or less.

Particularly, the other polymer (for example, an acrylic copolymer or a non-acrylic polymer having a glass transition temperature of 50 DEG C or more different from that of the main component polymer in the composition of the monomer constituting the polymer) has compatibility with the main component polymer (Solubility) of the pressure-sensitive adhesive layer is not sufficient and it may increase the haze of the pressure-sensitive adhesive layer.

When the weight average molecular weight (Mw) of the other polymer (i) is 100,000 or less, the durability tends to be lowered. (Ii) When the other polymer has a molecular structure having higher hydrophilicity than the main component polymer, Or suppressing the whitening whitening may become difficult.

Therefore, even when other polymers are used together with the main component polymer, other polymers corresponding to the above-mentioned (i) and (ii) are not used, or the mixing ratio can be made as small as possible .

In addition, the pressure-sensitive adhesive layer may contain a trace amount of a polymerization initiator (residual polymerization initiator) remaining in the polymerization layer without contributing to the polymerization reaction, in addition to the polymer component such as the main component polymer.

If the residual amount of the residual polymerization initiator (residual amount) is large, the heat resistance of the pressure-sensitive adhesive layer tends to be lowered. Therefore, the residual amount is preferably as small as possible.

From this viewpoint, the residual amount of the residual polymerization initiator contained in the pressure-sensitive adhesive layer is preferably 500 ppm or less, more preferably 300 ppm or less, still more preferably 200 ppm or less, practically 0 ppm or detection limit, Or less.

When two or more kinds of remaining polymerization initiators are contained in the pressure-sensitive adhesive layer, the residual amount means the total amount of each remaining polymerization initiator.

As the residual polymerization initiator, a thermal polymerization initiator or a photo polymerization initiator described later can be exemplified.

The method of forming the pressure-sensitive adhesive layer is not particularly limited, but it is usually carried out by applying a coating liquid (coating liquid) containing a polymer component such as a main component polymer to the surface of a support (also referred to as a separator) The pressure-sensitive adhesive layer can be formed by drying the volatile component and curing for a certain period of time as necessary.

The drying conditions and curing conditions are not particularly limited, and conventionally known methods can be employed.

A coating liquid containing a polymer component such as a main component polymer and, if necessary, a reactive diluent is coated on the surface of a support and irradiated with an activation energy ray to form a pressure-sensitive adhesive layer You may.

Further, a solution containing a polymer component such as a main component polymer, a photopolymerization initiator and, if necessary, a solution containing a polyfunctional monomer, a crosslinking agent and an organic solvent is applied to the surface of the support, dried, adhered to an adherend, By applying an energy ray, a pressure-sensitive adhesive layer may be formed.

The reactive diluent is a chemical species having a polymerizable functional group such as a vinyl group, and indicates a chemical species having a relatively small molecular weight such as a monomer or an oligomer.

Specifically, a monomer species constituting the acrylic copolymer used in the transparent conductive sheet of the present embodiment may be used.

Examples of the active energy ray include ultraviolet rays, visible rays, infrared rays and electron rays.

As the irradiation conditions of the active energy ray, usually, the illuminance (illuminance) is 1 mW / cm ² Carried out to investigate the active energy ray ~200 mW / cm ² as the accumulated light quantity (積算光量) 300mJ / cm 2 ~1000 mJ / cm 2.

The polymerization rate (polymerization rate) by irradiation is preferably 90% to 100%.

The polymerization rate can be determined by measuring the amount of the residual monomer by gas chromatography.

The thickness of the pressure-sensitive adhesive layer can be suitably selected, but is usually about 5 to 200 mu m.

As the support, a known support may be used as long as a coating layer can be formed. For example, a support such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, a polyethylene film, a polypropylene film, a cellophane, a diacetyl cellulose film, a triacetyl cellulose film, an acetyl cellulose butyrate film, a poly Polyvinylchloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinylacetate copolymer film, polystyrene film, polyvinyl chloride film, , A polycarbonate film, a polymethylphen A polyether sulfone film, a polymethyl pentene film, a polysulfone film, a polyetheretherketone film, a polyethersulfone film, a polyetherimide film, a polyimide film, A resin film such as a fluororesin film, a nylon film, a cycloolefin polymer film, or an acrylic resin film may be used.

In addition, the surface of the support may have releasability.

When the surface is a support having releasability, a coating layer is formed on the surface having this releasability.

In the case of using the transparent conductive sheet of the present embodiment, the support having a releasable surface is peeled from the pressure-sensitive adhesive layer before use.

The pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer can be produced, for example, in the following order.

First, a raw material monomer containing at least one hydrophobic monomer selected from the group consisting of a hydrophobic monomer (a1), a hydrophobic monomer (a2) and a hydrophobic monomer (b) and an organic solvent are placed in a reaction vessel and an inert gas such as nitrogen gas After heating to a predetermined temperature in an atmosphere, a thermal polymerization initiator is added and reacted for a predetermined time.

Further, it is preferable that the thermal polymerization reaction proceed sufficiently to leave no unreacted raw material monomer.

As the thermal polymerization initiator used in the thermal polymerization reaction, known thermal polymerization initiators can be used, and examples thereof include organic peroxides, organic hydroperoxides, organic peroxyketals peroxy ketal compounds and azo compounds.

Examples of the organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, di-tert- Diacyl peroxides such as diacyl peroxide, dibenzoyl peroxide, diacetyl peroxide, didecanoyl peroxide, diisononanoyl peroxide, 2-methylpentanoyl 2-methyl pentanoyl peroxide, and the like.

Examples of the organic hydroperoxides include tert-butyl hydroperoxide, cumylhydroperoxide, 2,5-dimethyl-2,5-dihydroperoxyhexane (2, 5-dimethyl-2,5-dihydroperoxy hexane, p-methane hydroperoxide, diisopropylbenzene hydroperoxide and the like.

Examples of the organic peroxyketalization include 1,1-bis (tert-hexylperoxy) -3,3,5-trimethylcyclohexane (1,1-bis ), 1,1-bis (tert-hexyl peroxy) cyclohexane, 1,1-bis (tert-butylperoxy) 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane, and the azo compounds may include 2,2'-azobisisobutyronitrile (2,2'- azobisisobutyro nitrile, 2,2'-azobis-2,4-dimethyl valeronitrile, 2,2'-azobiscyclohexyl nitrile (2,2'-azobisisobutyronitrile) -azobis cyclohexylnitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2-phenylazo-4-methoxy- 2-phenylazo-4-methoxy-2,4-dimethyl valeronitrile, dimethyl-2,2'-azobisisobutyrate, and the like.

Such a polymerization initiator can be used in the range of 0.0001 part by mass to 5 parts by mass with respect to 100 parts by mass (parts by mass) of the raw material monomer.

In order to control the weight average molecular weight (Mw) of the main component polymer, the reaction conditions such as the type and amount of the thermal polymerization initiator, the reaction time, and the reaction temperature may be adjusted or appropriately controlled by using a chain transfer agent .

Examples of the chain transfer agent include methyl mercaptan, n-dodecyl mercaptan, 2-mercaptoethanol, mercaptoisobutyl alcohol, thioglycerol thioglycerol, thioglycollic acid methyl, and? -methylstyrene dimer.

As the pressure-sensitive adhesive, a crosslinking agent (curing agent) such as an isocyanate crosslinking agent or an epoxy crosslinking agent may be appropriately used.

The blending amount of the crosslinking agent in the pressure-sensitive adhesive may be in the range of 0.01 to 20.0 parts by mass based on 100 parts by mass of the acrylic copolymer.

Examples of the isocyanate crosslinking agent include tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, isophorone diisocyanate, Isocyanate monomers such as diphenylmethane diisocyanate and hydrogenated diphenylmethane diisocyanate or an addition reaction thereof with an alcohol having two or more hydroxyl groups such as trimethylolpropane, An isocyanate compound, an isocyanurate compound, a biuret type compound and the like.

In addition, an isocyanate compound may be added to a known polyetherpolyol, a polyetherpolyol, an acrylpolyol, a polybutadiene polyol, a polyisoprenepolyol, or the like, Urethane prepolymer type isocyanate, and the like.

Examples of the epoxy crosslinking agent include bisphenol A epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin di Glycerine diglycidyl ether, glycerine triglycidyl ether, 1,6-hexane diol glycidyl ether, trimethylol propane triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidylether, diglycidyl aniline, diamine glycidylamine, N, N, N ', N'-tetraglycidyl-m-xylylenediamine (N, N, N Bis (N, N'-diamine glycidyl aminomethyl) cyclohexane), N'-tetraglycidyl-m-xylylenediamine, 1,3- And the like.

If necessary, various additives such as an ultraviolet absorber, an antioxidant, an anti-foaming agent and other polymers other than the main component polymer may be further added to the pressure-sensitive adhesive.

The layer structure (layer structure) of the conductive layer is not particularly limited as long as the conductive layer has conductivity. For example, the conductive layer may have a thickness of several nanometers to several hundreds of nanometers in diameter, A conductive layer formed from a collection of nanowires, a metal film, or a film formed by patterning a film containing metal components such as metal fine particles having a diameter of several nm to several hundreds of nm in a predetermined shape Layer, and a conductive layer directly using a metal wire having a diameter of several tens of micrometers to several hundreds of micrometers.

When metal nanowires or fine metal particles are used in forming the conductive layer, a solution or paste in which these metal materials are dispersed can be used.

As the metal element constituting the conductive layer, a well-known conductive metal can be suitably used, and Ag, Cu, Au and the like can be exemplified, and Ag is particularly preferable.

In the case where metal nanowires or metal fine particles are used as the metal component constituting the conductive layer, the conductive layer may contain, in addition to such a metal component, a binder component such as a binder component Other components may be further included.

The conductive layer is placed in contact with the pressure-sensitive adhesive layer.

Therefore, the layer structure of the transparent conductive sheet and the touch panel module and the touch panel device manufactured using the transparent conductive sheet can be further simplified and thinned (thinned).

The conductive layer is provided so as to be in contact with at least one surface of the pressure-sensitive adhesive layer (hereinafter referred to as " conductive layer formation surface "), but is not provided so as to substantially cover the entire surface of the conductive layer formation surface, A part of the formation surface is covered so as to form a predetermined pattern.

The pattern shape is not particularly limited as long as it can satisfy the transparency and the sensing function in the entire plane direction necessary for functioning as the touch panel device.

The coating rate of the conductive layer on the conductive layer formation surface can be appropriately selected within a range in which a function as a touch panel device can be ensured. For example, within a range of 0.1% to 70% Can be appropriately selected, and can be appropriately selected within a range of 1% to 50%, and more preferably, it can be appropriately selected within a range of 2% to 40%.

As such a pattern shape, for example, in a planar space constituted by a first direction and a second direction orthogonal to the first direction, a pattern shape exemplified in the following (i) to (iii) .

(i) a conductive region having a substantially square shape is formed so that the vertex of one conductive region and the vertex of another conductive region are electrically connected (for example, two vertices are partially overlapped or a connection portion connecting two vertices is A plurality of conductive region columns (conductive region columns) formed by arranging a plurality of columns in a first direction are formed in a pattern shape in which a plurality of columns are arranged along a second direction (for example, Japanese Patent Laid-Open Publication No. 2012-79257 The pattern shape exemplified in Fig. 6 or the like disclosed in the publication).

(ii) In the pattern shape (i), each conductive region is formed in a pattern shape (for example, Japanese Patent Laid-Open Publication No. 2012-33147) in which band-like wirings (wirings) A pattern shape exemplified in Fig. 3 of the publication).

(iii) a plurality of rows of conductive regions in the form of stripes whose longitudinal direction is parallel to the first direction and a plurality of rows of conductive regions arranged in the second direction, wherein each conductive region is arranged such that the stripe- (For example, a pattern shape exemplified in Figs. 7 and 8 of JP-A-2014-198811).

The method of forming the conductive layer is not particularly limited and a known method may be used as is, or may be arranged in an appropriate manner, or two or more known methods may be used in combination.

For example, a support on which a conductive layer is formed can be produced by a method exemplified in the following (A) to (C).

(A) A metal film is formed on the surface of a support by a known film formation method such as a sputtering method, a vacuum deposition method, or an electroless plating method, and then the metal film is patterned ) How to.

In this case, the patterning is performed by forming a photoresist film on the metal film, exposing and developing the photoresist film to form a resist pattern, and etching the metal film exposed from the resist pattern etching and selectively removing the photoresist film remaining on the patterned metal film (conductive layer). As a result, a support on which a conductive layer is formed can be obtained.

(B) a method of forming a conductive layer by printing a solution or paste containing metal nanowires or metal fine particles on a surface of a support in a predetermined pattern shape (for example, Japanese Patent Application Laid-Open ).

As the printing method, known printing methods such as offset printing, relief printing, intaglio printing, screen printing, inkjet printing, and the like can be used.

After printing, a heating treatment or a pressurizing treatment may be carried out if necessary.

(C) forming a photosensitive layer by applying a photosensitive composition containing a silver halide and a binder on the surface of a support, and then exposing and developing the photosensitive layer to form a conductive layer having a predetermined pattern shape (See, for example, JP-A-2014-198811).

Hereinafter, as an example, a case of manufacturing a support on which a conductive layer is formed by the method shown in (B) above will be described in more detail.

In this case, first, a solution containing the metal nanowires dispersed therein is applied to the surface (releasable surface) of the first support, followed by drying and further pressurization, thereby forming a gapless film Thereby forming a conductive film. Thus, a first support on which a conductive film is formed is obtained.

It is also possible to apply a heat-sensitive adhesive (e.g., a polyurethane-based adhesive) that does not exhibit adhesiveness at room temperature but exhibits adhesiveness by heating, by screen printing or the like, Print on the surface. Thus, a second support on which a heat-sensitive adhesive layer is formed is obtained.

Next, a first support on which a conductive film is formed and a second support on which a heat-sensitive adhesive layer is formed are adhered while being heated and pressed just as a conductive film and a heat-sensitive adhesive layer are closely adhered to each other by a roll laminating method or the like .

Subsequently, by peeling off the second support from the first support, only the portion of the conductive film provided on the surface of the first support corresponding to the pattern shape of the heat-sensitive adhesive layer shifts to the side of the heat-sensitive adhesive layer.

As a result, a conductive film (conductive layer) having a pattern shape obtained by inverting the pattern shape of the heat-sensitive adhesive layer is formed on the surface of the first support.

Here, when the transparent conductive sheet of the present embodiment is produced by using the support provided with the conductive layer having the predetermined pattern shape obtained by the methods exemplified in the above (A) to (C), for example, A transparent conductive sheet can be produced.

First, a support on which a pressure-sensitive adhesive layer having a pressure-sensitive adhesive layer constituting the transparent conductive sheet of the present embodiment is formed is prepared on the surface of a support.

Next, a support on which a conductive layer is formed and a support on which a pressure-sensitive adhesive layer is formed are adhered while being pressed by a roll laminating method or the like.

The adhesive layer may be heated as needed within a range in which the performance of the pressure-sensitive adhesive layer does not deteriorate.

As a result, a laminate (A) in which a support, a conductive layer, a pressure-sensitive adhesive layer, and a support are laminated in this order can be obtained.

The conductive layer, the pressure-sensitive adhesive layer, and the support are stacked in this order by transferring the conductive layer from the layered product (A) to the surface of the pressure-sensitive adhesive layer by peeling the support abutting on the conductive layer Whereby the layered product (B) can be obtained.

It is also possible to obtain a layered product (C) provided with a protective layer on the side of the layered product (B) on which the conductive layer is provided.

Further, the support, which is in contact with the pressure-sensitive adhesive layer, is peeled off from the layered product (A), and then adhered to the support on which the conductive layer is further formed, whereby the first support, the first conductive layer, And a second support are stacked in this order to obtain a layered product (D).

Here, as the support or the protective layer used for forming the conductive layer, a member made of the same material as the support used for forming the pressure-sensitive adhesive layer can be used.

In this case, the layered product (A), the layered product (B), the layered product (C), or the layered product (D) can be used as the transparent conductive sheet of the present embodiment.

The support on which the pressure-sensitive adhesive layer is formed may be used as a support of the method exemplified in (A) to (C) above, and a conductive layer may be formed directly on the surface of the pressure-sensitive adhesive layer.

In this case, however, it is preferable to select a conductive layer forming process in which the adhesive property of the surface of the pressure-sensitive adhesive layer does not significantly deteriorate in the process of forming the conductive layer.

As described above, a transparent conductive sheet having various layer structures can be obtained by appropriately combining various manufacturing processes and intermediate members.

Next, the transparent conductive sheet of the present embodiment will be described more specifically with reference to the drawings.

Figs. 1 and 2 are schematic plan views showing an example of the transparent conductive sheet of the present embodiment, specifically showing an example of a pattern shape of a conductive layer. Fig.

Further, in the drawing, the X direction and the Y direction indicated by arrows are directions orthogonal to each other.

The transparent conductive sheet 10A (10) shown in Fig. 1 has a structure in which the square conductive regions 100A (100) are formed so that the vertices of one conductive region 100A and the vertices of the conductive regions 100A, (20A (20)) in which a plurality of rows of conductive region rows (110A (110)) are arranged in the X direction so as to overlap with each other in the Y direction.

In the example shown in Fig. 1, a lead-out electrode portion (lead-out electrode portion) 112 is further provided at both ends of the conductive region row 110A (110) in the X direction.

The transparent conductive sheet 10B (10) shown in Fig. 2 has a patterned shape in which a plurality of rows of conductive regions 100B (100) in which the longitudinal direction is parallel to the X direction are arranged along the Y direction Of the conductive layer 20B (20).

In the example shown in Fig. 2, one conductive region 100B constitutes one conductive region row 110B (110).

1 and 2, the respective conductive region rows 110 are not connected but electrically isolated.

In addition, in the touch panel module or the touch panel device described later, each of the conductive region rows 110 shown in Figs. 1 and 2 is electrically connected to a printed wiring (not shown) through unillustrated lead- And is connected to a sensor section constituted by a substrate or the like.

The conductive region 100 shown in Figs. 1 and 2 may be a transparent gapless film member, but may further include a secondary structure as illustrated in Fig.

Fig. 3 is an enlarged plan view showing an example in which the conductive region 100 shown in Figs. 1 and 2 is enlarged.

In the example shown in Fig. 3, the conductive region 100 has a secondary structure in which band-shaped wirings 102 are arranged in a lattice pattern.

1 and 2, the conductive layer 20 generally includes a plurality of conductive regions 100, and at least two conductive regions 100 selected from the plurality of conductive regions 100 Are electrically isolated from each other without being connected to each other.

For this reason, the line width (line width) of the connection portion 120 of the two adjacent conductive regions 100A shown in Fig. 1, such as the Y direction length, the Y direction length of the conductive region 100B shown in Fig. 2, The migration of the metal material constituting the conductive layer 20 tends to cause a broken line.

It is to be noted that a peak on the second row of conductive region columns 110A of the conductive region 100A constituting the first row of conductive region columns 110A shown in Fig. 1 and a peak on the second row of conductive region columns 110A The length (gap length G1) between the vertexes of the conductive region 110A side of the first row of the conductive region 100A and the length between the vertexes of the conductive region row 110B of the first row and the second row In the portion having the shortest distance between the two electrically isolated electrically conductive regions 100, such as the length (gap length G2) between the region columns 110B, the metal material constituting the conductive layer 20 The migration is likely to cause a short circuit.

However, in the transparent conductive sheet 10 of the present embodiment, migration due to moisture in the atmosphere is suppressed as described above, and it is extremely easy to prevent disconnection or short-circuiting.

The line width at the narrowest line width is not particularly limited, but may be in the range of 10 nm to 1000 m, for example.

The lower limit value (lower limit value) of the line width is preferably 100 nm or more, more preferably 500 nm or more, still more preferably 1 mu m or more, and more preferably 200 mu m or less, And even more preferably 10 μm or less.

The length of the gap in the shortest distance between two electrically isolated conductive regions 100 is not particularly limited, but may be in the range of 1 m to 5000 m, for example.

The lower limit of the shortest distance is preferably 5 占 퐉 or more, more preferably 10 占 퐉 or more, even more preferably 50 占 퐉 or more, and the upper limit of the shortest distance is preferably 1000 占 퐉, more preferably 500 占 퐉 or less, And even more preferably 10 μm or less.

The thickness of the conductive layer 20 is not particularly limited. However, from the viewpoint of conductivity and transparency, it is possible to select the thickness from 10 nm to 1000 m, for example.

The lower limit of the thickness is preferably 50 nm or more, more preferably 100 nm or more, and the upper limit of the thickness is preferably 100 占 퐉 or less, more preferably 10 占 퐉 or less and most preferably 5 占 퐉 or less.

Figs. 4 to 7 are schematic cross-sectional views showing an example of the cross-sectional structure of the transparent conductive sheet of the present embodiment. More specifically, in Figs. 1 to 1, Sectional structure in a portion in which the substrate 20 is present.

The transparent conductive sheet 10C (10) shown in Fig. 4 has a layer structure in which the base material 40, the pressure-sensitive adhesive layer 30 and the conductive layer 20 are laminated in this order, The layered structure in which the first base material 40A (40), the pressure sensitive adhesive layer 30, the conductive layer 20 and the second base material 40B (40) 6, the first base material 40A (40), the first conductive layer 20C (20), the pressure-sensitive adhesive layer 30, the second base material 40A (40) In the transparent conductive sheet 10F (10) shown in Fig. 7, the first base material 40A (20A) and the second base material 40B have a layer structure in which the conductive material layer 20D The first adhesive layer 30A (30), the first conductive layer 20C (20), the third base material 40C (40), and the second conductive layer 20D (20) The second pressure-sensitive adhesive layer 30B (30), and the second base material 40B are stacked in this order.

The transparent conductive sheet 10 of the present embodiment is not limited to the layer structure exemplified in Figs. 4 to 7 as far as it includes at least one conductive layer 20 and at least one pressure-sensitive adhesive layer 30, As shown in Fig. 7, the conductive layer 20 and / or the pressure-sensitive adhesive layer 30 may include two or more layers.

The transparent conductive sheet 10 of the present embodiment may be composed only of the conductive layer 20 and the pressure-sensitive adhesive layer 30. In view of practicality such as handling property of the transparent conductive sheet 10, It is particularly preferable to include one or more layers of the substrate 40.

The substrate 40 is formed by applying a support used for forming the conductive layer 20 or the pressure-sensitive adhesive layer 30 at the time of manufacturing the transparent conductive sheet 10, applying a solution for forming a protective layer, A protective layer and the like.

In the case where the base material 40 is a member located on the outermost surface of the transparent conductive sheet 10, in other words, the base material 40 in Fig. 4, the base material 40 in Figs. 40A and 40B, the surface of the base material 40 in contact with the pressure-sensitive adhesive layer 30 or the conductive layer 20 may have releasability.

In this case, at the time of assembling the touch panel device or the touch panel module, the transparent conductive sheet 10 is used in a state in which the substrate 40 having the releasable surface is peeled off.

In assembling the touch panel device or the touch panel module, the base material 40 to be peeled off may be either a transparent or opaque member, but in other cases, a transparent member is used as the base material 40.

When the touch panel device or the touch panel module is assembled by using the transparent conductive sheet 10A having the patterned conductive layer 20A shown in Fig. 1, the two layers are combined at the time of assembly.

In this case, the second conductive layer 20A is rotated by 90 degrees in the XY plane with respect to the first conductive layer 20A, and each conductive region 100A, which constitutes the second conductive layer 20A, Conductive non-conductive region 130 surrounded by the four conductive regions 100A in the first-layer conductive layer 20A.

When the touch panel device or the touch panel module is assembled by using the transparent conductive sheet 10B having the patterned conductive layer 20B shown in Fig. 2, the conductive layers 20B of two layers are used in combination.

In this case, the second-layer conductive layer 20B is disposed on the first-layer conductive layer 20B while being rotated by 90 degrees in the XY plane.

Therefore, when the touch panel device or the touch panel module is assembled by using two transparent conductive sheets 10C shown in Fig. 4, the conductive layer 20 of the first transparent conductive sheet 10C and the second transparent conductive sheet 10C, The conductive layer 20 of the first electrode 10C may be arranged in the above-described arrangement relationship. This is also true of the transparent conductive sheet 10D shown in Fig.

When the touch panel device or the touch panel module is assembled by using the transparent conductive sheet 10E shown in Fig. 6, the first conductive layer 20C and the second conductive layer 20D are arranged in the above-described arrangement relationship . This is also true of the transparent conductive sheet 10F shown in Fig.

The touch panel device of this embodiment includes an image display device, a conductive layer using a metal material as a conductive material provided on the image display surface side of the image display device, and a pressure-sensitive adhesive layer The touch panel module of the present embodiment is not particularly limited as long as it includes a conductive layer using a metal material as a conductive material and a pressure-sensitive adhesive layer in contact with the conductive layer, It is not limited.

In the touch panel device and the touch panel module, the conductive layer and the pressure-sensitive adhesive layer are the same as those of the transparent conductive sheet of the present embodiment.

8 is a schematic cross-sectional view showing an example of the touch panel device of the present embodiment. Specifically, Fig. 8 is a schematic cross-sectional view showing an example of a touch panel device manufactured using the transparent conductive sheet 10F shown in Fig.

In the touch panel device 200 shown in Fig. 8, a transparent conductive sheet 10F is adhered to the image display surface 212 side of the image display device 210 through the first fixing adhesive layer 220. Fig.

A transparent protective layer 240 is adhered to the transparent conductive sheet 10F on the side opposite to the side where the image display device 210 is disposed through the second fixing adhesive layer 230. [

Here, as the image display apparatus, a known image display apparatus such as a liquid crystal display apparatus, an organic EL display apparatus, a plasma display apparatus, or the like can be used.

Examples of the transparent protective layer 240 include a hard plastic substrate such as a glass substrate and a polycarbonate substrate, a soft resin layer having a hard coating on the surface thereof, sapphire substrates, and the like have.

As the fixing adhesive layers 220 and 230, a publicly known pressure sensitive adhesive can be suitably used, but a pressure sensitive adhesive having a high transmittance to a wavelength in the visible light range is used.

The touch panel module of the present embodiment is a member capable of substantially assembling the touch panel device by bonding or fixing the touch panel device to the image display surface of the image display device.

The touch panel module is also provided with a sensor portion formed of a printed wiring board or the like connected to the conductive layer 20 as shown in Figs. 1 to 7, or a sensor portion including lead wirings Lead-out wiring) and the like may be further included.

For example, in the touch panel device 200 shown in Fig. 8, a transparent conductive sheet 10F, a second fixing adhesive layer 230, and a transparent protective layer 240 are laminated in this order, The touch panel module 300, and the like.

In the case of manufacturing the touch panel device of the present embodiment, the transparent conductive sheet of the present embodiment may be used to sequentially form the layers functioning as the touch panel on the image display surface of the image display device.

However, if the touch panel module of this embodiment, which is a modular member as described above, is prepared in advance, the touch panel device can be manufactured by a simple operation of installing the touch panel module substantially on the image display surface of the image display device .

The touch panel device of the present embodiment is particularly preferably a touch panel device of an electrostatic capacity type, but may be a touch panel device of another type.

In addition, the touch panel device of the present embodiment can be applied to all screen sizes from a small screen of several inches to several tens of inches or a large screen of more than 100 inches, such as a smart phone, .

The use of the touch panel device of the present embodiment is not particularly limited and may be applied to a display device such as a smart phone, a mobile phone, a notebook computer, a PC display monitor, a tablet terminal, ATMs, various kinds of office apparatuses and industrial apparatuses, as well as for use in home or business televisions having a screen size of about 20 to 100 inches, and furthermore, a screen size of 20 inches (Digital signage), an information display device, an office device having an image display device such as a table conference system or a whiteboard, and an amusement device, And the like.

However, the touch panel device of the present embodiment realizes a function as a touch panel by using a conductive layer that uses a metal material having a lower resistance (lower resistance) than ITO, rather than a conductive layer using a metal oxide such as ITO as a conductive material Therefore, it is suitable for applications requiring display of a large screen.

From this viewpoint, the diagonal length of the transparent conductive sheet, touch panel module, and touch panel device of the present embodiment is preferably 8 inches or more, more preferably 12 inches or more, and still more preferably 15 inches or more.

The upper limit of the length of the diagonal line is not particularly limited, but is preferably 500 inches or less, and more preferably 300 inches or less, from the practical viewpoint of handleability and the like.

<Examples>

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

( The conductive layer Of the formed support  making)

One. metal Nanowire  Ready

Examples of the metal nanowires used for forming the conductive layer include those described in Y.Sun, B. Gates, B. Meyers, and Y. Xia, "Crystalline silver nanowires by soft solution processing", Nano Letters, 2002 (2) The silver nanowires synthesized by dissolving silver sulphate in ethylene glycol in the presence of polyvinylpyrrolidone (PVP) and reducing the silver sulphate in the presence of polyvinyl pyrrolidone (PVP) (silver nanowire).

Namely, silver nano wires synthesized by the modified polyol process described in Cambrios Technologies Corporation U.S. Patent Application No. 60/815, 627 were used.

2. Conductive film  Fabrication of the formed support

(Manufactured by Cambrios Technologies Corporation, ClearOhm 占 (manufactured by Cambrios Technologies Corporation) containing 0.5% w / v of silver nano wire synthesized by the above method as a metal nanowire having a minor axis diameter of about 70 nm to 80 nm and an aspect ratio of 100 or more , Ink-AAQ) was coated on the hard coat side of a first support (188 m thick, high-transparency PET film (HF1C 22-188) hard coated on one side) using a slot die coating machine After coating with a wet film thickness of 20 탆 and drying, a pressure treatment was performed at a pressure of 2000 kN / m ² to form a uniform conductive film. Thus, a support on which a conductive film was formed was obtained.

3. Thermal Adhesive Layer Of the formed support  making

Further, 100 parts by mass (parts by mass) of CRISVON NT-810-45 (polyurethane resin, 45% solution manufactured by DIC Corporation) were mixed with 62.5 parts by mass of methyl ethyl ketone and 62.5 parts by mass of toluene To prepare a solution of the heat-sensitive adhesive dissolved therein.

Then, this heat-sensitive adhesive solution was applied onto a second support having a surface-releasable surface (a PET film having a thickness of 23 占 퐉 (manufactured by Teijin DuPont Flims Company) by a gravure printing method (Teijin Tetoron Film G2)), and the coating film was dried to form a heat-sensitive adhesive layer having a thickness of about 0.5 to 0.8 mu m.

The pattern shape of the heat-sensitive adhesive layer formed by pattern printing was a pattern shape (negative pattern shape) obtained by reversing the pattern shape shown in Fig.

Here, the negative pattern shape is a pattern shape of the conductive layer 20A shown in Fig. 1 finally formed, in which the length of one side of the square conductive area 100A is 4 mm and the length of the conductive area 100A ) Of the connection portion 120 was 350 mu m.

4. The conductive layer Of the formed support  making

Next, a first support having a conductive film formed thereon and a second support having a heat-sensitive adhesive layer patterned in a negative pattern are laminated in such a manner that the conductive film and the thermosensitive adhesive layer are opposed to each other, (A metal heating roll and a heat-resistant silicone roll) which constitute a pair of opposing rolls, and a support having a conductive film formed thereon and a support having a heat-sensitive adhesive layer .

The laminate conditions at this time were as follows: the temperature of the heating roll made of metal was 110 占 폚, the roll nip pressure (linear pressure) was 30 kN / m, and the two superposed supports (Conveying speed) of 5 m / min.

Subsequently, at the time when the temperature of the laminate obtained by attachment was lowered to room temperature, the second support was peeled off from the laminate to form a patterned conductive film (conductive layer 20A) was left on the support.

The conductive layer of the support (first support) having the obtained conductive layer was observed by a microscope.

As a result, in both of the supporting members on which the conductive layers were formed, the conductive layers were not damaged by the peeling step of peeling off the second supporting member, and all the conductive films in the region in contact with the heat- On the support side of the first support, and remained on the first support side.

The resistance value (resistance value) and the light transmittance were measured in order to quantitatively judge defective products resulting from the peeling process for the support on which each conductive layer was formed, and the respective values were measured within ± 10% Was used for the production of the transparent conductive sheet of each of Examples and Comparative Examples described later.

( For the pressure-sensitive adhesive layer Of polymer  synthesis)

The following monomers were used for the synthesis of the polymer used in the production of the pressure-sensitive adhesive layer.

&Lt; Hydrophobic monomer (a1) &gt;

MMA: methyl methacrylate

BMA: butyl methacrylate

2 EHMA: 2-ethylhexyl methacrylate

&Lt; Hydrophobic monomer (a2) &gt;

CHA: cyclohexyl acrylate

CHMA: cyclohexyl methacrylate

&Lt; Hydrophobic mono (b) &gt;

LA: Lauryl acrylate

SA: stearyl acrylate

IDMA: iso-decyl methacrylate

LMA: Lauryl methacrylate

SMA: stearyl methacrylate

<Other monomers>

BA: n-butyl acrylate

2 EHA: 2-ethylhexyl acrylate

2 HEA: 2-hydroxyethyl acrylate

2 HEMA: 2-hydroxyethyl methacrylate

< The polymer (A1)  Synthesis>

70 parts by mass of LA, 25 parts by mass of 2 EHA, 5 parts by mass of 2 HEA and 100 parts by mass of ethyl acetate were placed in a reaction apparatus equipped with a stirrer, a reflux condenser (reflux condenser), a thermometer and a nitrogen- And the temperature was raised to 70 캜 while nitrogen gas was introduced.

Then, 0.1 part by mass of a thermal polymerization initiator AIBN (azobisisobutyronitrile) was added with stirring, and the mixture was reacted for 10 hours, and diluted with 150 parts by weight of ethyl acetate to obtain an acrylic copolymer (polymer A1) Of an ethyl acetate solution.

Table 1 shows the weight average molecular weight (Mw) of the polymer (A1), the composition of the monomer used for the synthesis, and the main polymerization conditions.

< Polymer (A2 to A17), (B1 to B4) and (C1)

Synthesis was carried out in the same manner as in Synthesis Example of Polymer (A1), except that the composition of the monomer used for the synthesis of the polymer was changed to that shown in Table 1. [

Table 1 shows the weight average molecular weight (Mw) of these polymers, the composition of the monomers used in the synthesis, and the main polymerization conditions.

&Lt; Measurement of weight average molecular weight (Mw)

The weight average molecular weight (Mw) of each polymer shown in Table 1 was determined as a weight average molecular weight (Mw) in terms of standard polystyrene using gel permeation chromatography (GPC).

Measurement conditions are shown below.

-Measuring conditions-

Apparatus: HLC-8120 (manufactured by TOSOH CORPORATION)

Column: G7000HXL (manufactured by TO SOO Co., Ltd.)

GMHXL (manufactured by Tohto Corporation)

G2500HXL (manufactured by TO SOO Co., Ltd.)

Sample concentration: 1.5 mg / ml (diluted with tetrahydrofuran) Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Temperature of column: 40 ° C

[Table 1]

(Transparent conductive sheet of  making)

< Example 1 >

A tolylene diisocyanate crosslinking agent (Coronate L: manufactured by Nippon Polyurethane Industry Co., Ltd.) to which trimethylolpropane was added was added to the polymer (A1) (Solid content ratio) (relative to 100 parts by mass of the polymer component of the polymer (A1)) was applied onto a third support (polyethylene terephthalate (PET) film having a thickness of 100 μm) Dried to a thickness of 50 mu m and dried. Then, a PET separator (PET film having a thickness of 25 mu m) was laminated to prepare a support having a pressure-sensitive adhesive layer formed thereon.

Next, a separator of the support on which the pressure-sensitive adhesive layer is formed is peeled off to expose the pressure-sensitive adhesive layer, and a support on which the support having the conductive layer formed thereon and the pressure- And the surface of the formed support on which the pressure-sensitive adhesive layer was formed was adhered to face each other.

The lamination was carried out using the same laminator used for the production of the support on which the conductive layer was formed. The lamination condition at this time was a roll nip pressure (line pressure) of 30 kN / m, and the conveying speed of the two overlapped supports passing between the pair of rolls is 5 m / min.

1 and the layer structure shown in Fig. 5 (the first base material 40A (third support) / the pressure-sensitive adhesive layer 30 / the conductive layer 20A / the second base material 40B ) (First support)) was obtained.

< Example  2 ~ Example  17, Comparative Example  1 ~ Comparative Example  6>

A transparent conductive sheet was obtained in the same manner as in Example 1, except that the polymer component used for forming the pressure-sensitive adhesive layer was changed to the contents shown in Table 2. [

(evaluation)

The appearance of the transparent conductive sheet of each of the examples and comparative examples was visually observed. As a result, all the other transparent conductive sheets except for Comparative Examples 5 and 6 were transparent.

The transparent conductive sheet of each of the examples and the comparative examples and the pressure-sensitive adhesive layer used for the production of the transparent conductive sheet were evaluated for resistance value change rate, transparency of the pressure-sensitive adhesive layer, durability and anti-wet heat whitening resistance .

The details are given below.

&Lt; Evaluation of rate of change of resistance value &

In order to evaluate the change in the resistance value due to the migration of the metal material constituting the conductive layer, one conductive region row (FIG. 1) was formed on one side of the transparent conductive sheet in each example and each comparative example 110A were connected to a tester to measure a line resistance (k?).

Here, the line resistance (line resistance) is obtained by measuring the initial resistance value Ri and the resistance value Ri of the transparent conductive sheet after the transparent conductive sheet is manufactured in a high temperature and high humidity environment (temperature 80 deg. C, humidity 80% (Resistance value Rd) after 240 hours of standing in a high temperature and humidity environment (temperature 80 占 폚, humidity 10%) of the transparent conductive sheet after measurement of the resistance value Rw and resistance value Ri .

Then, the resistance value change ratio RCw (%) when the transparent conductive sheet is left in a high-temperature and high-humidity environment by the following formula (1) And the resistance value change rate RCd (%) was obtained. The results are shown in Table 2.

(1) RCw = 100 x (Rw- Ri ) / Ri

Equation (2) RCd = 100 x (Rd- Ri ) / Ri

The evaluation criteria of the results shown in Table 2 are as follows.

?: The resistance value change rate RC is 1% or less.

?: The resistance change rate RC is more than 1% and not more than 2%.

?: The resistance value change rate RC is more than 2% and not more than 5%.

X: Resistance value change rate RC exceeds 5%.

< The pressure-  Evaluation of transparency>

In order to evaluate the transparency of the transparent conductive sheet due to the pressure-sensitive adhesive layer, a coating liquid for forming the pressure-sensitive adhesive layer in each of the examples and the comparative examples was used, and on one surface of a glass substrate having a thickness of 1 mm, An evaluation sample having a layer formed thereon was prepared.

The transparency was evaluated by measuring the haze (%) in accordance with JIS K 7361 using a haze meter (manufactured by MURAKAMI COLOR RESEARCH LABORATORY, HM-150 type). The results are shown in Table 2.

The evaluation criteria of the results shown in Table 2 are as follows.

Haze less than 1.0: Good

Haze greater than 1.0 and less than 1.5: slightly poor

Haze greater than 1.5: bad

&Lt; Evaluation of durability &

A PET separator of a test piece (test piece) cut into a size of 50 mm x 60 mm was peeled off from the support on which the pressure-sensitive adhesive layer used in the production of the transparent conductive sheet of each example and each comparative example was cut, An evaluation sample adhered to the surface of a glass substrate whose surface was polished with isopropyl alcohol was prepared.

Next, the evaluation sample was autoclaved at a temperature of 50 DEG C and a pressure of 5 atm for 20 minutes.

Thereafter, the evaluation sample after the autoclave treatment was allowed to stand at room temperature for 1 hour, then left at a temperature of 85 占 폚 and a humidity of 85% for 500 hours, then at a temperature of 23 占 폚 and a humidity of 65% We watched this with the naked eye.

The evaluation criteria of the results shown in Table 2 are as follows.

?: No bubbling, moxibustion, or peeling occurred after the test.

X: There are foaming, moxibustion and peeling after the test.

< Wet heat whitening  Evaluation>

The PET separator of the test piece cut into a size of 50 mm x 60 mm was peeled off from the support on which the pressure-sensitive adhesive layer used in the production of the transparent conductive sheet of each example and each comparative example was formed and the exposed adhesive surface was cleaned with isopropyl alcohol An evaluation sample adhered to the surface of the substrate was produced.

Next, the evaluation sample was autoclaved at a temperature of 50 DEG C and a pressure of 5 atm for 20 minutes.

Thereafter, the evaluation sample after the autoclave treatment was allowed to stand at room temperature for 1 hour, then left under the environment of 85 占 폚 and 85% humidity for 500 hours, and then left to stand at 23 占 폚 and 65% humidity for 1 hour.

The haze value of the evaluation sample before and after the series of these tests was measured in accordance with JIS K 7361 using a haze meter HM-150 (manufactured by MURAKAMI COLOR RESEARCH LABORATORIES CO., LTD.).

Thus, whitening of the pressure-sensitive adhesive layer was evaluated. The results are shown in Table 2.

The evaluation criteria of the results shown in Table 2 are as follows.

?: Difference in haze value before and after the humid heat test is 3.0 or less.

?: Difference in haze value before and after wet heat is 3.0 or more and 5.0 or less.

X: Difference in haze value before and after moist heat exceeds 5.0.

[Table 2]

10, 10A, 10B, 10C, 10D, 10E, 10F: transparent conductive sheet
20, 20A, 20B, 20C and 20D: conductive layers
30, 30A, 30B: pressure-sensitive adhesive layer
40, 40A, 40B, 40C: substrate
100, 100A, 100B: conductive region
102: Wiring
110, 110A, and 110B: conductive region columns
112: lead electrode portion
120:
130: non-conductive region
200: touch panel device
210: Image display device
212: image display surface
220 and 230: fixing adhesive layer
240: transparent protective layer
300: Touch panel module

Claims (3)

A conductive layer (conductive layer) using a metal material as the conductive material; And
And a pressure-sensitive adhesive layer (pressure-sensitive adhesive layer) containing one or more kinds of polymers that are in contact with the conductive layer,
Wherein at least one polymer of the one or more kinds of polymers is an acrylic copolymer, and the acrylic copolymer has a weight average molecular weight (Mw) of more than 100,000 and not more than 2,000,000, and a copolymerizable monomer component (Meth) acrylate having a cyclic alkyl group having 5 to 9 carbon atoms and an alkyl (meth) acrylate having an alkyl group having 10 to 20 carbon atoms, alkyl (meth) acrylates having a branched alkyl group Hydrophobic monomers of more than one species,
The total amount of the hydrophobic monomer in the copolymerized monomer component of the acrylic copolymer is 35 wt% or more based on the total mass of the acrylic copolymer,
Wherein a haze value when the thickness of the pressure-sensitive adhesive layer is 100 mu m is 1.0 or less,
Transparent conductive sheet. A conductive layer using a metal material as the conductive material; And
And a pressure-sensitive adhesive layer in contact with the conductive layer,
Wherein the pressure-sensitive adhesive layer comprises an acrylic copolymer,
In the acrylic copolymer,
An alkyl methacrylate having a linear or branched alkyl group having 1 to 9 carbon atoms as the copolymerizable monomer component, an alkyl (meth) acrylate having a cyclic alkyl group having 5 to 9 carbon atoms (Meth) acrylate and an alkyl (meth) acrylate having an alkyl group having 10 to 20 carbon atoms, wherein the hydrophobic monomer is at least one selected from the group consisting of
The total amount of the hydrophobic monomer in the copolymerized monomer component of the acrylic copolymer is 35 wt% or more based on the total mass of the acrylic copolymer,
And a haze value when the thickness of the pressure-sensitive adhesive layer is 100 mu m is 1.0 or less,
Touch panel module. The image display device
A conductive layer provided on the image display surface side of the image display device and using a metal material as a conductive material and a pressure-sensitive adhesive layer in contact with the conductive layer,
Wherein the pressure-sensitive adhesive layer comprises an acrylic copolymer,
In the acrylic copolymer,
An alkyl methacrylate having a linear or branched alkyl group having 1 to 9 carbon atoms as the copolymerizable monomer component, an alkyl (meth) acrylate having a cyclic alkyl group having 5 to 9 carbon atoms (Meth) acrylate and an alkyl (meth) acrylate having an alkyl group having 10 to 20 carbon atoms, wherein the hydrophobic monomer is at least one selected from the group consisting of
The total amount of the hydrophobic monomer in the copolymerized monomer component of the acrylic copolymer is 35 wt% or more based on the total mass of the acrylic copolymer,
And a haze value when the thickness of the pressure-sensitive adhesive layer is 100 mu m is 1.0 or less,
Touch panel device.

Images