JP6256154B2 - Laminated body, touch panel using the laminated body, and method for manufacturing the laminated body - Google Patents

Description

  The present invention relates to a laminate, a touch panel using the laminate, and a method for manufacturing the laminate.

Mobile information terminal devices equipped with a transparent touch panel for information display and information input, which have bidirectional communication functions represented by tablet PCs and smartphones, have been widely spread all over the world.
As a transparent touch panel, there is a resistive film method that excels in cost, but the explosive spread of information terminal equipment is possible because gesture operations such as multi-touch and the image quality of display devices can be maintained by improving the transmittance. As a trigger, the demand for capacitive touch panels, in particular, projected capacitive touch panels, is increasing.

The basic structure of a projected capacitive touch panel usually has a multi-touch function (multi-point detection; simultaneously detects multiple touch positions) on both sides of a transparent plastic panel substrate. A transparent conductive layer made of ITO (Indium Tin Oxide) or the like having a predetermined pattern (line & space, etc.) is laminated at a predetermined position on the surface, and placed on the front of liquid crystal display devices, organic EL display devices, etc. Is being used.
In recent years, the pattern of transparent conductive layers such as ITO layers has been reduced with further reductions in the thickness of transparent substrates due to further weight reduction and thinning of terminal devices, as well as higher definition of display pixels and higher accuracy of touch detection. There are also demands for higher definition and diversification.
Under such circumstances, the transparent conductive layer of the transparent conductive film used for the touch panel and the like mainly has low surface resistivity, high transparency, and tint from the viewpoints of low power consumption, high-speed response, and visibility. Suppression etc. are required.

A transparent conductive film consists of a basic composition which has transparent conductive layers, such as an ITO layer, on the base | substrate which consists of transparent base materials, such as a polyethylene terephthalate film, and a hardened layer. Such a transparent conductive film includes a substrate and a transparent conductive layer in a step of crystallizing the transparent conductive layer at a high temperature and a step of sintering a silver paste (extraction electrode) at a high temperature after forming the transparent conductive layer. Due to the difference in thermal expansion coefficient or thermal contraction ratio, the transparent conductive layer may be peeled off from the substrate or fine cracks may be generated on the surface of the transparent conductive layer.
In Patent Document 1, in order to solve the above problem, before the transparent conductive layer is formed, the polyethylene terephthalate film is preliminarily heat-treated, and the thermal shrinkage rate (longitudinal direction MD and transverse direction TD) of the polyethylene terephthalate film is disclosed. (Shrinkage ratio) of about 0.5% is disclosed.

JP 2007-133839 A JP 2013-89181 A

In the example of Patent Document 1, the transparent conductive layer formed on the substrate is not patterned, but is formed using a solid layer (film). The ratio of the surface area of the transparent conductive layer to the surface area of the substrate is The relationship is 1: 1.
However, in recent years, as the mainstream of touch panels has been switched from the resistive film type to the capacitive type, the transparent conductive layer is often patterned. As the patterning has also been refined, in Patent Document 1, when the transparent conductive layer is patterned in this way, what kind of interaction (distortion due to thermal stress, etc.) occurs between the substrate and the patterned transparent conductive layer. ) Has not been studied at all.
Furthermore, as described above, while there is a demand for a reduction in the thickness of the transparent substrate, as in Patent Document 1, even if the thermal shrinkage rate of the polyethylene terephthalate film has been reduced to 0.5% or less. However, in the above-mentioned problems (in the process of crystallizing the transparent conductive layer at a high temperature and in the process of forming the transparent conductive layer and sintering the extraction electrode at a high temperature, the transparent conductive layer may peel off from the substrate, However, a new problem has occurred, although the problem of generating fine cracks and the like has been solved.

As a new problem, there is a phenomenon in which undulation is generated on the surface of the transparent conductive layer immediately after the patterning of the transparent conductive layer.
The problem of the swell can be solved by attaching a reinforcing base material to the opposite surface of the transparent base material as in Patent Document 2. However, when a reinforcing base material is bonded, the overall weight and thickness increase, and this goes against the trend of weight reduction and thinning that has been demanded in recent years.
Further, as a new problem described above, a washing board that differs from the above-described undulation when subjected to high-temperature and long-time heat treatment (crystallization of the transparent conductive layer or firing of the extraction electrode) on the patterned transparent conductive layer. Such a phenomenon that a rippled uneven surface (hereinafter sometimes referred to as “washboard ripple” or “WBR”) occurs. The washboard ripple may not be eliminated even if a reinforcing base material is bonded as in Patent Document 2. The washboard ripple causes a new problem such as entrapment of bubbles when bonded to, for example, a cover glass constituting a touch panel in a later process, as well as a decrease in appearance properties.
Further, in order to prevent the above-mentioned swell and washboard ripple, if the strength of the substrate is simply increased, cracks are easily generated due to bending or the like.

  In view of the above problems, the present invention suppresses the generation of washboard ripple and the generation of cracks during bending when the patterned transparent conductive layer is further subjected to heat treatment for a long time at a high temperature. It is an object to provide a laminate and a method for manufacturing the same.

In order to solve the above problems, the present invention provides the following laminates [1] to [11], a touch panel using the laminate, and a method for producing the laminate.
[1] A laminate having a transparent conductive layer patterned on a substrate having a transparent layer on one or both sides of a transparent substrate, the storage elastic modulus Ec (N / m of the substrate at 130 ° C.) ² ) Et (N / m) obtained by multiplying the substrate thickness d (m) is 4.0 × 10 ⁴ ≦ Et ≦ 10.5 × 10 ⁴ .
[2] The laminate according to [1], wherein the storage elastic modulus of the transparent layer is larger than the storage elastic modulus of the transparent substrate.
[3] The laminate according to [1] or [2], which satisfies the following relationship, where d _S (m) is the thickness of the transparent substrate and d _L (m) is the thickness of the transparent layer. .
0.005 ≦ d _L / (d _S + d _L ) ≦ 0.7
[4] The laminate according to any one of [1] to [3], wherein the transparent substrate has a thickness of 15 to 125 μm, and the transparent layer has a total thickness of 2.0 to 24 μm.
[5] The laminate according to any one of [1] to [4], wherein the substrate further includes an optical adjustment layer.
[6] The laminate according to [5], wherein the base includes the transparent layer and the optical adjustment layer on the transparent base material, and the patterned transparent conductive layer is provided on the optical adjustment layer. body.
[7] The optical adjustment layer includes a high refractive index layer and a low refractive index layer, the refractive index of the high refractive index layer is 1.55 to 1.75, and the refractive index of the low refractive index layer is 1. The laminate according to the above [5] or [6], which is 30 to 1.55.
[8] The laminate according to any one of [1] to [7], wherein the transparent layer is a hard coat layer.
[9] A touch panel having the laminate according to any one of [1] to [8] as a constituent member.
[10] The above [9], wherein the laminate includes the hard coat layer and the optical adjustment layer on the transparent substrate, and the patterned transparent conductive layer on the optical adjustment layer. ] The touch panel as described in.
[11] A method for producing a laminate having a patterned transparent conductive layer on a substrate having a transparent layer on one or both sides of a transparent substrate,
Et (N / m) obtained by multiplying the storage elastic modulus Ec (N / m ² ) of the substrate at 130 ° C. by the thickness d (m) of the substrate is 4.0 × 10 ⁴ ≦ Et ≦ 10.5. A substrate forming step for forming the transparent layer on the transparent substrate, a transparent conductive layer forming step for forming the transparent conductive layer on the substrate, and pattern formation for patterning the transparent conductive layer so as to be × 10 ⁴ The manufacturing method of a laminated body including the crystallization process of heating and crystallizing a process and a transparent conductive layer.

  The laminate and the method for producing the laminate of the present invention can suppress the occurrence of washboard ripple when the patterned transparent conductive layer is further subjected to heat treatment for a long time at a high temperature. In addition, since the laminate and the laminate manufacturing method of the present invention can suppress the occurrence of washboard ripple, there is no entrainment of bubbles when bonding with a cover glass or the like constituting the touch panel, and the appearance and visibility are good. Can be. Furthermore, the laminate and the method for producing the laminate of the present invention can suppress the occurrence of cracks during bending.

An example of the laminated body of this invention is shown, (a) shows the structure of a laminated body, an upper side is a top view, a lower side is sectional drawing, (b) is a top view and sectional drawing after patterning a transparent conductive layer (C) is a plan view and a cross-sectional view after pattern printing of a silver paste as an extraction electrode, and (d) is a plan view and a cross-sectional view after firing the silver paste. It is a top view which shows an example of the pattern of the transparent conductive layer used for this invention.

[Laminate]
The laminate of the present invention is a laminate having a patterned transparent conductive layer on a substrate having a transparent layer on one or both sides of a transparent substrate, and the storage elastic modulus Ec of the substrate at 130 ° C. Etching (N / m) obtained by multiplying (N / m ² ) and the thickness d (m) of the substrate is 4.0 × 10 ⁴ ≦ Et ≦ 10.5 × 10 ^4. is there.
The above conditions are preferably satisfied in the MD direction of the transparent substrate constituting the laminate, and more preferably satisfied in all directions of the laminate. In addition, MD direction means the direction where the draw ratio of a transparent base material is the largest.
Hereinafter, a laminate having a non-crystallized transparent conductive layer formed on a substrate may be referred to as a laminate precursor.

In the present invention, Et (N / m) obtained by multiplying the storage elastic modulus Ec (N / m ² ) of the substrate at 130 ° C. by the thickness d (m) of the substrate is controlled within a specific range, Mitigates mechanical interaction between the transparent substrate and the patterned transparent conductive layer on the substrate, including thermal stress during heat treatment, and suppresses the generation of washboard ripple due to high-temperature and long-time heat treatment after patterning can do. In the present invention, the swell immediately after patterning of the transparent conductive layer can also be suppressed. The reason for the occurrence of the undulation is unknown, but it is considered that the cause is that the influence of the etching solution during the etching of the transparent conductive layer and the stress balance between the location where the transparent conductive layer is present and the location where the transparent conductive layer is absent are disrupted. Further, even when the undulation does not occur, washboard ripple may occur, and the present invention that can suppress the washboard ripple is extremely useful.

  In FIG. 1, (a) shows an example of a laminate precursor, and the laminate precursor 1 (transparent conductive layer: no pattern; solid film) is laminated on both the transparent substrate 2 and the transparent substrate 2. The substrate 5 is composed of the transparent layers 3a and 3b and the optical adjustment layer 4 laminated on the transparent layer 3a, and the transparent conductive layer 6 is laminated on the substrate 5. Moreover, (d) shows an example after patterning of the transparent conductive layer of the laminate of the present invention. In the laminate 11 (transparent conductive layer: with pattern), the laminate was printed with a transparent conductive layer pattern 6 ′, silver paste, or the like. It has a configuration in which a fired extraction electrode pattern 7 ′ and a fired extraction electrode terminal portion 8 ′ are provided.

<Substrate>
The base | substrate of this invention has a transparent layer on the single side | surface or both surfaces of a transparent base material, and contains functional layers, such as an optical adjustment layer mentioned later as needed.

<Transparent substrate>
As a transparent base material, it is preferable that it is provided with light transmittance, smoothness, and heat resistance, and was excellent in mechanical strength. Such transparent substrates include polyester, triacetyl cellulose (TAC), cellulose diacetate, cellulose acetate butyrate, polyamide, polyimide, polyether sulfone, polysulfone, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal. , Polyether ketone, polymethyl methacrylate, polycarbonate, polyurethane, and amorphous olefin (Cyclo-Olefin-Polymer: COP). The transparent substrate may be a laminate of two or more plastic films.
Among these plastic films, a stretched polyester, particularly a biaxially stretched polyester, for example, polyethylene terephthalate (PET) and polyethylene naphthalate are preferable from the viewpoint of mechanical properties, dimensional stability, chemical resistance, transparency, and the like.
In addition, since polyethylene naphthalate has a large refractive index anisotropy, it can be made to have high retardation by stretching (corresponding to polarized sunglasses). In addition, polyethylene terephthalate stably obtains high transparency, for example, features such as a small difference in refractive index from the hard coat layer, which is one of the transparent layers laminated adjacently, and less influence of the interface. Have
In addition to the physical treatment such as corona discharge treatment and oxidation treatment, the surface of the transparent substrate may be preliminarily coated with a coating material called an anchor agent or a primer.

Although the manufacturing method of a transparent base material is not restrict | limited in particular, Usually, it can manufacture by well-known methods, such as a melt extrusion method. From the viewpoints of heat resistance, transparency, mechanical strength, surface smoothness, etc., a transparent substrate (particularly a PET film) produced by biaxial stretching is preferred.
As a biaxial stretching method, an unstretched transparent substrate is stretched in the longitudinal direction (flow direction) or the transverse direction (perpendicular to the flow direction), and then in a direction perpendicular to any of the preceding stretching directions. There are sequential biaxial stretching for stretching and simultaneous biaxial stretching for stretching in the longitudinal direction and transverse direction at the same time, but in the present invention, it is not particularly limited, and any transparent substrate produced by either biaxial stretching may be used. Can be used.
As described above, the biaxially stretched film is produced by being stretched in the longitudinal direction and the transverse direction, and therefore tends to be greatly contracted during heating due to residual stress during stretching. For this reason, for example, when using a biaxially stretched PET film as a substrate, it is preferable to perform a predetermined heat treatment in advance to reduce the shrinkage rate to 0.7% or less.

The thickness of the transparent substrate used in the present invention is preferably 10 to 200 μm, more preferably 15 to 125 μm, and still more preferably 20 to 70 μm. If the transparent substrate is less than 10 μm, the strength as a support may be insufficient, or handling during production may be hindered. On the other hand, when the thickness exceeds 200 μm, the material cost increases or the effect of reducing the device thickness and weight when used as a product is reduced.
Further, when the transparent substrate having a thin thickness as described above is used, as described above, during the high-temperature and long-time heat treatment after the patterning of the transparent conductive layer (for example, 10 to 125 to 160 ° C. (~ 60 minutes), washboard ripple occurs in the transparent conductive layer patterned on the substrate of the laminate. However, a transparent layer having a storage elastic modulus larger than the storage elastic modulus of the transparent substrate described later is laminated, and the storage elastic modulus Ec (N / m ² ) of the obtained substrate at 130 ° C. and the thickness d (m of the substrate). ) Is controlled to a specific range of the present invention, the occurrence of washboard ripple on the patterned transparent conductive layer can be prevented.
Furthermore, in the manufacturing process of the laminate of the present invention, if the thickness of the transparent substrate is thin, even if the roll diameter is small, the winding length is long, and from the viewpoint of increasing the film formation (sputtering) efficiency of the transparent conductive layer, The thickness of the transparent substrate is preferably as thin as possible within the above range.
As a result, the material cost of the transparent substrate is reduced, and when used for, for example, an electrode plate for a touch panel, it greatly contributes to reducing the thickness and weight of the device.

<Transparent layer>
The transparent layer has a role of adjusting the Et of the substrate to the above-described range.
The storage elastic modulus of the transparent layer is not particularly limited as long as it is larger than the storage elastic modulus of the transparent substrate and within a range in which the flexibility of the laminate can be ensured.
When the oligomer component remains in the transparent substrate, the oligomer is precipitated from the transparent substrate during the crystallization of the transparent conductive layer and the heat treatment for the extraction electrode, and the cloudiness is caused, so that the visibility is increased. May be adversely affected. In particular, when the transparent substrate is a polyester-based film such as PET, oligomer precipitation is significant. Therefore, it is preferable that the transparent layer can prevent oligomer precipitation.
In order to prevent oligomer precipitation, the transparent layer is preferably a hard coat layer. The hard coat layer is also preferable in that it can improve the mechanical properties (abrasion resistance, scratch resistance, high pencil hardness, etc.) of the substrate.

As the hard coat layer, Et (N / m) obtained by multiplying the storage elastic modulus Ec (N / m ² ) of the substrate at 130 ° C. by the thickness d (m) of the substrate is a specific range of the present invention. Therefore, it is preferable to form an ionizing radiation curable resin composition containing an ionizing radiation curable resin.
Examples of the ionizing radiation curable resin include acrylate compounds having one or two or more unsaturated bonds. Examples of the compound having one unsaturated bond include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone and the like. Examples of the compound having two or more unsaturated bonds include polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, penta Multifunctional compounds such as erythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, modified products thereof, and these The reaction product (for example, poly (meth) acrylate ester of polyhydric alcohol) of a polyfunctional compound and (meth) acrylate etc. can be mentioned. In the present specification, (meth) acrylate means methacrylate and acrylate.

  In addition to the above compounds, relatively low molecular weight polyester resins having unsaturated double bonds, polyether resins, acrylic resins, epoxy resins, urethane resins, polybutadiene resins, and the like can also be used as the ionizing radiation curable resins. .

Among the above-mentioned ionizing radiation curable resin, without extremely thick hard coat layer, the storage elastic modulus Ec at 130 ° C. of the base body (N / m ^2), and said storage modulus Ec (N / m ²⁾ From the viewpoint that Et (N / m) obtained by multiplying the thickness d (m) of the substrate easily falls within the scope of the present invention, dipentaerythritol hexa (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetra Acrylate and trimethylolpropane triacrylate are preferred.
The ionizing radiation curable resin may be used alone or in combination of two or more.

Note that Et (N / m) obtained by multiplying the storage elastic modulus Ec (N / m ² ) of the substrate at 130 ° C. and the storage elastic modulus Ec (N / m ² ) by the thickness d (m) of the substrate. When it is too high, Ec and Et can be controlled by mixing a soft component with the ionizing radiation curable composition. The blending of the soft component can prevent curling and layer brittleness.
Examples of the soft component include a urethane acrylate oligomer and an acrylic polymer.
The resin component constituting the ionizing radiation curable resin composition may be a resin in which a plurality of components are used in combination.

  Examples of the solvent used for preparing the ionizing radiation curable resin composition include alcohols such as methanol, ethanol, n-propanol, and ethylene glycol; ketones such as acetone or methyl ethyl ketone; and aromatics such as toluene and xylene. Hydrocarbon, methyl cellosolve, ethyl cellosolve, carbitol, glycol ethers such as propylene glycol monoethyl ether, and acetates such as ethyl acetate, butyl acetate, and cellosolve acetate can be used as appropriate.

When the ionizing radiation curable resin is not electron beam curable but photocurable, a photopolymerization initiator is added to the ionizing radiation curable resin composition.
Although it does not specifically limit as a photoinitiator, For example, acetophenones, benzophenones, Michler benzoyl benzoate, (alpha) -amino oxime ester, tetramethyl thiuram monosulfide, thioxanthones, etc. are mentioned.
Although content of a photoinitiator is not specifically limited, 1-10 mass% in an ionizing radiation curable resin composition is preferable, and 3-7 mass% is more preferable.

  The hard coat layer may be formed on one side of the transparent substrate or may be formed on both sides. Moreover, when a hard-coat layer is formed in both surfaces of a transparent base material, as a forming material, it may be the same or may differ. From the viewpoint of manufacturing efficiency, cost, and performance, it is preferable to form the same material.

A transparent layer typified by a hard coat layer is formed on one side of a transparent substrate, and the thickness of the transparent substrate is 15 to 125 μm (preferably 20 to 70 μm) (for example, 3a in FIG. 1A). Only), the thickness of the transparent layer is preferably 2 to 12 μm, more preferably 4 to 12 μm, and still more preferably 8 to 12 μm. If the thickness of the transparent layer is 2 μm or more, Et (N / m) can be easily controlled within the range of the present invention, and if it is 12 μm or less, it is easy to prevent the occurrence of cracks and peeling due to a decrease in flexibility. Can do. If the thickness of the transparent layer is within this range, Et (N / m) obtained by multiplying the storage elastic modulus Ec (N / m ² ) of the substrate at 130 ° C. by the thickness d (m) of the substrate is obtained. It can be easily controlled within the scope of the present invention.

When the transparent layer represented by the hard coat layer is formed on both surfaces of a transparent substrate having a thickness of 15 to 125 μm (preferably 20 to 70 μm), and the transparent layer is formed of the same material (for example, (a) in FIG. 1) 3a and 3b), the total thickness of the transparent layer is preferably 2 to 24 μm, more preferably 4 to 24 μm, still more preferably 8 to 24 μm. The thickness of each of the transparent layers formed on both surfaces is within the range of the total thickness, and is less affected by the curling of the laminate, and the transparent layer has an oligomer component from the transparent substrate. The thickness may be adjusted as appropriate within a range in which precipitation suppression can be ensured, and the thicknesses thereof may be the same or different. The thickness of the transparent layer on the surface of one transparent substrate on the side where the transparent conductive layer is disposed is 1 to 12 μm, and the thickness of the transparent layer on the surface of the other transparent substrate on the side where the transparent conductive layer is not disposed is 1-12 micrometers is preferable, More preferably, the thickness on the surface of this one transparent base material is 2-12 micrometers, and the thickness on the surface of this other transparent base material is 2-12 micrometers. If the thickness of the transparent layer is within this range, Et (N / m) obtained by multiplying the storage elastic modulus Ec (N / m ² ) of the substrate at 130 ° C. by the thickness d (m) of the substrate is the present invention. It can be easily controlled within this range, and there is no occurrence of cracks or peeling due to a decrease in flexibility.
In the above, when the material for forming the transparent layer is different between both surfaces, the storage elastic modulus Ec (N / m ² ) of the substrate at 130 ° C. and the thickness are adjusted by appropriately adjusting the total thickness and the thickness of each surface. Et (N / m) obtained by multiplying the thickness d (m) of the substrate can be within the scope of the present invention.

If the thickness of the transparent substrate is within the range of the present invention and the thickness of the transparent layer typified by the hard coat layer is within the above range, when the transparent layer is laminated on the transparent substrate to form the substrate, Et (N / m) obtained by multiplying the storage elastic modulus Ec (N / m ² ) at 130 ° C. by the thickness d (m) of the substrate can be easily controlled.
Thereby, even if the patterned transparent conductive layer has a high-temperature heat treatment step, generation of washboard ripple can be prevented.

In the present invention, Et (N / m) obtained by multiplying the storage elastic modulus Ec (N / m ² ) of the substrate at 130 ° C. by the thickness d (m) of the substrate is 4.0 × 10 ⁴ ≦ Et. ≦ 10.5 × 10 ⁴ . Et (N / m) is preferably 4.1 × 10 ^{4 to} 10.3 × 10 ^{4, and} more preferably 6.0 × 10 ^{4 to} 10.2 × 10 ⁴ .
When Et is less than 4.0 × 10 ⁴ (N / m), the substrate tends to be plastically deformed, and is easily deformed by the stress generated during the heating process, and the patterned transparent conductive layer is washed with the washboard. Ripple occurs. When Et exceeds 10.5 × 10 ⁴ (N / m), the stress balance between the patterned transparent conductive layer and the substrate tends to be maintained, and the washboard ripple can be further suppressed, but the flexibility is lowered. When used for a touch panel or the like, the transparent layer is easily cracked or peeled off by a number of touch operations. When Et is in the above range, mechanical interaction including thermal stress during heat treatment between the substrate and the patterned transparent conductive layer is relaxed, and washboard ripple occurs in the patterned transparent conductive layer. And flexibility is maintained at the same time.
Although the storage elastic modulus Ec of a base | substrate is described in the Example mentioned later, it measured using the dynamic-viscoelasticity measuring apparatus (The product made from UBM, apparatus name: Rheogel-E4000).
The Et ₁₅₀ (N / m) obtained by multiplying the storage elastic modulus Ec ₁₅₀ (N / m ² ) of the substrate at 150 ° C. by the thickness d (m) of the substrate is 2.5 × 10 ⁴ to 10 0.0 × 10 ⁴ is preferable, 3.0 × 10 ^{4 to} 9.0 × 10 ⁴ is more preferable, and 4.5 × 10 ^{4 to} 9.0 × 10 ⁴ is more preferable.

From the viewpoint of easily obtaining an effect of the present invention, the storage elastic modulus Ec at 130 ° C. of the transparent layer (N / m ^2), and the storage elastic modulus Ec at 130 ° C. of the transparent base material (N / m ²⁾ The ratio [the storage elastic modulus of the transparent layer at 130 ° C./the storage elastic modulus of the transparent substrate at 130 ° C.] is preferably 2.0 to 5.0, more preferably 2.5 to 4.5. preferable.
The storage elastic modulus at x ° C. of the transparent layer can be approximated by the following formula when the substrate is composed of a transparent substrate and a transparent layer. The “thickness of the transparent layer” in the following formula is the total thickness of the transparent layer when there are two transparent layers.
X ° C. storage elastic modulus of transparent layer = (x ° C. storage elastic modulus of substrate × thickness of substrate−x ° C. storage elastic modulus of transparent base material × thickness of transparent base material) / thickness of transparent layer from the viewpoint of easily obtained, and the storage elastic modulus Ec at 0.99 ° C. of the transparent layer (N / m ^2), at 0.99 ° C. ratio [transparent layer of the storage elastic modulus Ec at 130 ° C. of the transparent layer (N / m ²⁾ The storage elastic modulus / storage elastic modulus of the transparent layer at 130 ° C.] is preferably 0.80 or more, and more preferably 0.85 or more.

0.005 ≦ d _L / (d _S ) where d _S (m) is the thickness of the transparent base material of the substrate, and d _L (m) is the total thickness of the transparent layer (when formed on both sides). + D _L ) ≦ 0.700 is preferably satisfied. Even in the case of a thin transparent substrate, it is easy to secure Et if the value of d _L / (d _S + d _L ) is 0.005 or more, and if it is 0.700 or less, the flexibility is maintained. Be drunk. d _L / (d _S + d _L ) is more preferably 0.030 or more and 0.500 or less, and further preferably 0.100 or more and 0.350 or less.

The thickness of the transparent layer is a value obtained by observing the cross section with an electron microscope (SEM, TEM) or the like.
Further, the refractive index of the transparent layer is preferably within 0.15 of the difference in refractive index from the transparent substrate or a primer layer formed on the transparent substrate as necessary from the viewpoint of preventing interference fringes. , More preferably within 0.10, and even more preferably within 0.08. However, even if the refractive index of the transparent layer does not satisfy the above conditions, the interference between the transparent substrate and the primer layer can be prevented by making the interface between the transparent substrate and the transparent layer uneven, or by infiltrating the components of the transparent layer into the transparent substrate or primer layer. Stripes can be reduced.

<Functional layer>
The substrate may further have a functional layer. It does not restrict | limit especially as a functional layer, It can use in the range which does not impair the characteristic of a laminated body, For example, an optical adjustment layer is mentioned. The functional layer may be provided directly on the transparent substrate.

<Optical adjustment layer>
For example, the optical adjustment layer can be provided between the transparent layer and the transparent conductive layer in order to make the pattern of the transparent conductive layer difficult to see. Further, an optical adjustment layer can be provided on the surface of the laminate that does not have the transparent conductive layer for antireflection.

  Examples of the optical adjustment layer include a two-layer structure of a high refractive index layer and a low refractive index layer, a three-layer structure of a high refractive index layer, a medium refractive index layer and a low refractive index layer, or a multilayer structure of four or more layers. However, from the viewpoint of cost effectiveness, a two-layer structure of a high refractive index layer and a low refractive index layer is preferable.

Methods for forming the low refractive index layer can be broadly classified into wet methods and dry methods. The wet method is excellent in terms of production efficiency.
As a wet method, a method of forming by a sol-gel method using a metal alkoxide, a method of forming by applying a low refractive index binder such as a fluororesin, a composition containing low refractive index particles in a binder resin The method of coating and forming is mentioned. Examples of the dry method include a method in which particles having a desired refractive index are selected from low-refractive-index particles described later and formed by physical vapor deposition or chemical vapor deposition.

  Examples of the material used for the sol-gel method include metal alkoxide, and the low refractive index layer is formed by hydrolysis and condensation polymerization of the metal alkoxide. Examples of the metal alkoxide include titanium alkoxide, zirconium alkoxide, or alkoxysilane from the viewpoint of excellent mechanical strength and stability, and adhesion to a transparent conductive layer, a base material, and the like. Preferably used.

Examples of the material used as the binder resin include an ionizing radiation curable resin and a thermosetting resin.
Examples of the ionizing radiation curable resin are the same as those used for the hard coat layer described above.
Examples of the thermosetting resin include urethane thermosetting resins, melamine thermosetting resins, phenoxy thermosetting resins, and epoxy thermosetting resins. Among these, urethane thermosetting resins are preferably used from the viewpoint of easy toughness and good durability.
The most preferable binder in the present invention is an ionizing radiation curable resin having good production efficiency and good physical properties and dispersibility of low and high refractive index fine particles described later.

Examples of the low refractive index particles include MgF ₂ , LiF, or SiO ₂ made of a metal fluoride, and SiO ₂ is preferably used from the viewpoint of moist heat resistance.
The primary particle size of the low refractive index particles is 100 nm or less, preferably 5 to 60 nm. If it is the said range, a favorable optical interference layer can be formed, without a coating film whitening. The amount added is appropriately adjusted according to the desired refractive index.

Methods for forming the high refractive index layer can be broadly classified into wet methods and dry methods. The wet method is excellent in terms of production efficiency.
Examples of the wet method include a method of forming by a sol-gel method using a metal alkoxide or the like, as in the case of the low refractive index layer, and a method of forming by applying a composition containing a high refractive index particle in a binder resin. Examples of the dry method include a method in which a material having a desired refractive index is selected from high-refractive index particles to be described later and formed by physical vapor deposition or chemical vapor deposition.

Examples of the material used for the sol-gel method include metal alkoxide, and the high refractive index layer is formed by hydrolysis and condensation polymerization of the metal alkoxide. Examples of the metal alkoxide include titanium alkoxide and zirconium alkoxide from the viewpoint of excellent mechanical strength and stability, and adhesion to a transparent conductive layer and a substrate. Among these, zirconium alkoxide is preferably used from the viewpoint of refractive index.
Examples of the material used as the binder resin include ionizing radiation curable resins and thermosetting resins, and the same materials as those used in the low refractive index layer can be used.

As high refractive index particles, zinc oxide (1.90), titanium oxide (2.3 to 2.7), cerium oxide (1.95), tin-doped indium oxide (1.95 to 2.00), antimony doped Examples thereof include tin oxide (1.75 to 1.85), yttrium oxide (1.87), and zirconium oxide (2.10). It has a moderately high refractive index and high durability stability such as light resistance. From the viewpoint, zirconium oxide is preferably used. The parentheses indicate the refractive index of the material of each particle.
The primary particle diameter of the high refractive index particles is 100 nm or less, and preferably 10 to 60 nm. If it is the said range, a favorable optical interference layer can be formed, without a coating film whitening. The amount added is appropriately adjusted according to the desired refractive index.

The high refractive index layer preferably has a thickness of 200 nm or less and a refractive index of 1.55 to 1.75. The low refractive index layer has a thickness of 200 nm or less, and the refractive index is preferably lower than the refractive index of the high refractive index layer and is 1.30 to 1.55. The refractive index of the high refractive index layer is more preferably 1.58 to 1.70, and the refractive index of the low refractive index layer is more preferably 1.35 to 1.51. Further, in order to make the pattern of the transparent conductive layer more difficult to see, it is more preferable that the thickness of the low refractive index layer is 3 to 100 nm, the thickness of the high refractive index layer is 10 to 100 nm, and the thickness of the low refractive index layer is More preferably, the thickness is 10 to 40 nm and the thickness of the high refractive index layer is 10 to 70 nm. If the refractive index and thickness are in the above ranges, it has an excellent antireflection effect and at the same time, an effect as an invisible layer.
<Additive>
The transparent layer and the optical adjustment layer described above may contain additives such as an antistatic agent, an antifouling agent, an antiblocking agent, and an ultraviolet absorber as long as the effects of the present invention are not impaired.

Examples of the substrate described above include the following (A) and (B). As the transparent layer, a hard coat layer is preferable. The optical adjustment layer preferably has a two-layer structure of a high refractive index layer and a low refractive index layer.
(A) Transparent layer / Transparent substrate / Transparent layer / Optical adjustment layer (B) Optical adjustment layer / Transparent layer / Transparent substrate / Transparent layer / Optical adjustment layer

<Transparent conductive layer>
The transparent conductive layer used in the present invention is laminated on the substrate of the present invention. If necessary, an inorganic layer made of SiO ₂ or the like is formed between the substrate and the transparent conductive layer within a range that does not affect the optical characteristics, and the gas, oligomer components, etc. generated or deposited from the substrate in the manufacturing process are sealed. You may stop.
Although it does not restrict | limit especially as a transparent conductive layer used by this invention, A metal oxide is mentioned. Among these, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), phosphorus-doped tin oxide (PTO), fluorine-doped tin oxide (FTO), and indium-doped zinc oxide (IZO) are exemplified. Among these, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), and indium-doped zinc oxide (IZO) are preferable. In particular, tin-doped indium oxide (ITO) is preferable because both transparency and conductivity are excellent.

  The heat shrinkage in the longitudinal direction (MD) and the transverse direction (TD) after heating the laminated body precursor at 150 ° C. for 30 minutes is preferably 0.7% or less, more preferably 0.6% or less. More preferably, it is 0.5% or less, More preferably, it is 0.4% or less. If the heat shrinkage is in the above range, peeling of the transparent conductive layer and generation of cracks can be suppressed under a high temperature environment.

  There are various methods for forming a transparent conductive layer, such as a physical vapor deposition method such as sputtering, vacuum vapor deposition, ion plating, or chemical vapor deposition, other printing methods, coating methods, etc. From the viewpoint of characteristics, physical vapor deposition and chemical vapor deposition are preferable, and physical vapor deposition that can be processed at a lower temperature is more preferable than chemical vapor deposition.

  Usually, tin-doped indium oxide (ITO) formed by sputtering is amorphous, but the crystallization can be promoted by heating at a temperature of 100 to 150 ° C. within the heat resistant temperature range of the laminate. It is possible to crystallize 50% or more by appropriately adjusting the heating time and the like. By this crystallization, the surface resistivity of the ITO layer can be reduced. At the same time, the adhesion strength can be improved and the storage elastic modulus can be increased.

  The transparent conductive layer has a thickness of 10 to 200 nm, a refractive index of 1.90 to 3.00, and a surface resistivity of 300Ω / □ or less, preferably 150Ω / □ or less. When the thickness, refractive index, and surface resistivity are within the above ranges, when used as a touch panel, high light transmittance, low power consumption, and high-speed response can be ensured even when the area is increased.

The transparent conductive layer is used by forming a predetermined pattern by patterning. The shape of the pattern is not particularly limited as long as it is a shape and arrangement that can provide a predetermined position detection function and minimize the degradation of visibility when used as a touch panel, for example.
The pattern pitch of the transparent conductive layer is preferably 5 mm or less, more preferably 2 mm or less. When the pitch of the pattern is within this range, it is possible to cope with high definition of display pixels and high touch detection accuracy, and the storage elastic modulus Ec (N / m ² ) of the substrate at 130 ° C. and the thickness d of the substrate. By making Et (N / m) obtained by multiplying (m) within the scope of the present invention, even if heat treatment is applied to the patterned transparent conductive layer after crystallization, generation of washboard ripples will occur. Absent.

  In FIG. 2, an example of the pattern of the transparent conductive layer used for this invention is shown. The pattern layer 100 includes a plurality of X electrode portions 111 to 116 electrically connected in the horizontal direction and a number of Y electrode portions 211 to 214 electrically connected in the vertical direction. Are arranged so as to cross each other through an insulating layer. For example, (i) forming an X electrode portion on one surface of a transparent substrate and a Y electrode portion on the other surface, (ii) an X electrode portion and another transparent substrate on a transparent substrate By forming the Y electrode portion on the material and pasting both base materials together, the X electrode portion and the Y electrode portion are crossed through the insulator.

  As a pattern used for a projected capacitive touch panel, usually a plurality of linear electrodes X and a plurality of linear electrodes Y made of a transparent conductive layer are insulating layers (transparent substrate, hard coat layer, etc.) It arrange | positions so that it may mutually orthogonally cross. As a specific example of the pattern of the electrode X and the electrode Y, a linear lattice pattern having a mesh shape and straight lines (both electrodes X and Y are arranged in parallel at a predetermined pitch) and substantially perpendicular to each other, conductivity between intersections Examples thereof include a wavy lattice pattern in which the portion has at least one curve, a diamond-like pattern (a pattern similar to FIG. 2), and the like.

As for the laminated body of this invention, the following (A) and (B) are mentioned, for example. As the transparent layer, a hard coat layer is preferable. The optical adjustment layer preferably has a two-layer structure of a high refractive index layer and a low refractive index layer.
(A) Transparent layer / transparent substrate / transparent layer / optical adjustment layer / patterned transparent conductive layer (B) patterned transparent conductive layer / optical adjustment layer / transparent layer / transparent substrate / transparent layer / optical adjustment layer / Patterned transparent conductive layer

The laminated body of this invention can be used conveniently as a structural member of a touch panel. Examples of the touch panel include a resistance film type touch panel and a capacitive touch panel, and can be suitably used particularly as a constituent member of the capacitive touch panel.
When incorporating a laminated body in a touch panel, it is preferable that a laminated body has the structure of said (A) and (B).

As a more specific configuration of the touch panel, two laminates of the above (A) are used, and the hard coat layer side is overlapped with the adhesive, or the hard coat layer side and the transparent conductive layer side are used as the adhesive. The structure (GFF structure) which laminated | stacked protective plates, such as a cover glass, with respect to the structure piled up through PSA is mentioned.
Moreover, the structure (G1F structure) which laminated | stacked the transparent conductive layer side of the glass substrate which has a transparent conductive layer, and the transparent conductive layer side of the laminated body of said (A) through an adhesive is mentioned.
Furthermore, the structure (GF2 structure) which uses the said laminated body of (B) independently is mentioned.

[Manufacturing method of laminate]
The method for producing a laminate of the present invention is a method for producing a laminate having a patterned transparent conductive layer on a substrate having a transparent layer on one or both sides of a transparent substrate, Et (N / m) obtained by multiplying the storage elastic modulus Ec (N / m ² ) at 130 ° C. by the thickness d (m) of the substrate is 4.0 × 10 ⁴ ≦ Et ≦ 10.5 × 10 ^4. A substrate forming step of forming the transparent layer on the transparent substrate, a transparent conductive layer forming step of forming a transparent conductive layer on the substrate, a pattern forming step of patterning the transparent conductive layer, transparent It is a manufacturing method of a laminated body including the crystallization process of heating and crystallizing a conductive layer.

(1) Substrate formation step This is a step of forming a substrate by forming a transparent layer on one or both sides of a transparent substrate. In this step, Et (N / m) obtained by multiplying the storage elastic modulus Ec (N / m ² ) of the substrate at 130 ° C. by the thickness d (m) of the substrate is 4.0 × 10 ⁴ ≦ Et ≦ 10.5 × 10 ⁴ . In FIG. 1A, a transparent layer 3 a and a transparent layer 3 b are formed on a transparent substrate 2.

When the above-described hard coat layer is used as the transparent layer, it is formed by applying an ionizing radiation curable resin composition on a transparent substrate to form a coating film, drying it, and then curing the coating film. be able to.
Examples of the method for applying the ionizing radiation curable resin composition for forming the hard coat layer include application methods such as a roll coating method, a bar coating method, and a gravure coating method.
Although the drying conditions after application | coating are not specifically limited, Usually, it is good to carry out for 20 to 120 second at 40-200 degreeC. The method for curing the coating film is not particularly limited and may be a known method.
It is also possible to improve the uniformity of the molecules and control the storage modulus by changing the cross-linking form and cross-linking density of the hard coat layer by changing the irradiation intensity while keeping the total irradiation amount constant. It is. Further, the storage elastic modulus can be controlled not only by the material composition but also by the curing conditions. For example, in order to increase the storage elastic modulus, it is preferable to increase the irradiation light density by using a fusion ultraviolet lamp, which will be described later, and increase the crosslinking density by rapidly generating a large amount of radicals. Further, by lowering the irradiation light amount density and increasing the irradiation time, it is possible to suppress a rapid increase in radical density and suppress the crosslinking density, thereby suppressing the storage elastic modulus and enhancing the flexibility.

As a method of irradiating with ionizing radiation, ultraviolet rays in a wavelength region of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, a fusion lamp or the like are irradiated. Among these lamps, a fusion lamp is preferable. The amount of irradiation is usually 100 to 500 mJ / cm ² by integration. Moreover, it can carry out by irradiating the electron beam of a wavelength range below 100 nm emitted from a scanning type or a curtain type electron beam accelerator. As an electron beam, what has the energy of 50-1000 eV is preferable, More preferably, it is 100-300 eV.
In addition, you may perform surface treatments, such as a corona discharge process and an oxidation process, previously in order to improve adhesiveness to a transparent base material.

(1 ′) Optical Adjustment Layer Formation Step A step of further forming an optical adjustment layer may be performed on the transparent layer formed in the substrate formation step. In addition, you may form an optical adjustment layer etc. directly on a transparent base material as needed. In FIG. 1A, the optical adjustment layer 4 is formed on the transparent layer 3a.
The optical adjustment layer is formed by applying a resin composition containing an ionizing radiation curable resin or a thermosetting resin used as the binder described above to form a coating film, drying the coating, and then curing the coating film. can do. Examples of the coating method include a micro gravure coating method, a roll coating method, a curtain coating method, a spray coating method, a die coating method, a knife coating method, and a spin coating method. In addition, as a formation method in the case of using a metal oxide or a metal fluoride, a sputtering method, a vacuum evaporation method, an ion plating method, or the like is used when the physical vapor deposition method is used. In the case of chemical vapor deposition, plasma CVD or the like that can be processed at a relatively low temperature is used. In addition, when the optical adjustment layer has a plurality of layers, each layer may be formed by a different method.

(2) Transparent conductive layer formation process A transparent conductive layer formation process is a process of forming the transparent conductive layer which consists of a metal oxide etc. on a base | substrate. In FIG. 1A, a transparent conductive layer 5 is formed on the optical adjustment layer 4.
There are various methods for forming a transparent conductive layer, such as a physical vapor deposition method such as sputtering, vacuum vapor deposition, ion plating, or chemical vapor deposition, other printing methods, coating methods, etc. From the viewpoint of characteristics, physical vapor deposition and chemical vapor deposition are preferable, and physical vapor deposition that can be processed at a lower temperature is particularly preferable as compared with chemical vapor deposition.

(3) Crystallization step This is a step of crystallizing the transparent conductive layer by temperature heating. This crystallization step may be performed after the transparent conductive layer forming step, after the transparent conductive layer pattern forming step described later, or at the same time as the extraction electrode forming step described later. It selects suitably from viewpoints, such as the ease of the etching of the metal oxide to be used, and production efficiency.
Although heating temperature changes with metal oxides to be used, it is 100-200 degreeC normally, Preferably it is 120-160 degreeC. The heating time is usually 5 minutes to 24 hours, and may be appropriately adjusted in consideration of production efficiency and crystallinity (which affects mechanical properties, surface resistivity values, etc.). The heating method is not particularly limited and can be performed by a known method. However, when ITO is used as the metal oxide, it is preferably performed in the air using a heating furnace, an infrared lamp heater, or the like.

(4) Pattern formation step The pattern formation step is a step of patterning the transparent conductive layer into a predetermined pattern. For example, a step of forming a stripe pattern in which patterns as shown in FIG. It is. Patterning can be performed by a known method, and is usually performed by a photolithography method. Specifically, a photoresist is applied on the transparent conductive layer, exposed through a photomask having a predetermined pattern, developed using a developer such as an alkaline solution, and a resist pattern is formed. After the unnecessary transparent conductive layer is etched by the dry etching method, the resist is peeled off to form a predetermined transparent conductive layer pattern.
As described above, the laminate of the present invention can be produced. Further, it is preferable to further perform the following extraction electrode forming step.

(5) Extraction Electrode Formation Step The extraction electrode formation step is a step of forming an extraction electrode having a predetermined pattern on the transparent conductive layer having the pattern obtained in the pattern formation step. For example, FIG. , A predetermined extraction electrode pattern (before firing) 7 is formed from the transparent conductive layer pattern film 6 ′.
In this step, a conductive material such as silver paste is formed, and an electrode pattern related to the wiring is formed. There is no restriction | limiting in particular in the formation method of an electrode pattern, It can carry out by a well-known method and is normally performed by the screen printing method. The obtained electrode pattern is fired at high temperature (sintered by heat treatment) in order to improve the conductivity of the electrode pattern, including drying of the solvent used (in FIG. 1 (d), it is taken out). Electrode pattern (after firing) 7 ′). The heat treatment conditions are 125 to 150 ° C. and 10 to 60 minutes. When the heat treatment condition is within this range, the conductivity of the electrode pattern is improved, and according to the present invention, no washboard ripple occurs in the transparent conductive layer pattern. The heating method is not particularly limited and can be performed by a known method. Usually, a heating furnace, a vacuum heating furnace, an infrared lamp heater or the like is used.

  According to the manufacturing method of the present invention, even when the patterned transparent conductive layer is further subjected to heat treatment, no washboard ripple is generated, for example, when bubbles are bonded to a cover glass or the like constituting the touch panel. A laminate having excellent appearance properties and visibility without entanglement is obtained.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example. In the text, “part” or “%” is based on mass unless otherwise specified.

  The measurement of the storage elastic modulus of the substrates obtained in Examples and Comparative Examples, and the evaluation of the surface irregularities (washboard ripple) and the flexibility of the laminate having the patterned transparent conductive layer were performed by the following methods. .

(1) Storage elastic modulus A substrate composed of a transparent substrate / transparent layer is cut into a size of 5 mm × 20 mm as a test piece, and storage elastic modulus (Ec) at 130 ° C. and 150 ° C. (MD direction of the transparent substrate). Was measured under the following conditions using a dynamic viscoelasticity measuring apparatus (manufactured by UBM, apparatus name: Rheogel-E4000).
(Measurement condition)
Frequency: 10 Hz, measurement jig: tension, load: 50 g, vibration state: continuous vibration distortion control: 10 μm, measurement temperature range: 25 ° C. to 200 ° C., temperature increase rate: 2 ° C./min.

(2) Laminate surface irregularities (washboard ripple)
The unevenness of the patterned transparent conductive layer on the surface of the laminate was evaluated by visually observing the reflected state of the reflected image of the fluorescent lamp using the light of the fluorescent lamp. The evaluation criteria were as follows.
Level where no irregularities are visible: ◎
Level where unevenness is only slightly visible: ○
Level where irregularities can be easily seen: ×

(3) Flexibility The laminated body obtained in the example and the comparative example is wound around a cylindrical rod (mandrel rod) having a diameter of 6 mm, and irradiated with video light. Evaluation was performed by visual observation according to the evaluation criteria shown.
Cracks do not occur: ○ Cracks occur: ×

Example 1
On one side of a transparent PET film (made by Teijin DuPont Films, trade name: KEL86W, with primer layer, thickness: 50 μm (biaxial stretching)), apply the following transparent layer coating solution (1) to the wire bar The coating is dried for 40 seconds in a heat oven at a temperature of 70 ° C., the solvent in the coating film is evaporated, and ultraviolet rays are irradiated using a fusion lamp so that the integrated light quantity becomes 160 mJ / cm ^2. Then, the coating film was cured. Similarly, the transparent layer coating solution is applied to one side of the PET film using a wire bar, and the coating film is cured to form a transparent layer having a thickness of 12 μm per side and a thickness of 24 μm on both sides. did.
In addition, the thickness of the transparent layer was measured with a Digimatic micrometer (Mitutoyo Corporation, model name: MDC-SB).

<Preparation of transparent layer coating solution>
4 parts by weight of a photopolymerization initiator (Lamberti, Esacure One) and 300 parts by weight of a diluting solvent (MIBK / cyclohexanone = 9/1) were added and stirred until there was no undissolved residue. Here, 100 parts by mass of a photocurable resin (manufactured by Nippon Kayaku Co., Ltd., DPHA) was added and stirred, and stirred until there was no undissolved residue. Finally, 0.25 parts by mass of a leveling agent (Seika Beam 10-28 (MB) manufactured by Dainichi Seika Kogyo Co., Ltd.) was added and stirred.

Next, on the one transparent layer, the following high refractive index layer coating solution is applied, dried, and irradiated with ultraviolet rays to form a high refractive index layer (thickness 50 nm, refractive index 1.66). A SiO ₂ film was formed on the top using a sputtering apparatus (thickness: 30 nm, refractive index 1.46) to obtain a substrate (transparent layer / transparent substrate / transparent layer / high refractive index layer / low refractive index layer). It was. The storage elastic modulus at 130 ° C. of the obtained substrate was measured. The results are shown in Table 1.

<High refractive index layer coating solution>
Pentaerythritol triacrylate 10 parts (Nippon Kayaku Co., Ltd., KAYARAD-PET-30)
-0.7 parts of photopolymerization initiator (BASF, Irgacure 127)
・ 0.3 parts of silicone leveling agent (Daiichi Seika Kogyo Co., Ltd., Seika Beam 10-28, solid content 10%)
・ High refractive index particles (zirconium oxide) 50 parts (manufactured by Sumitomo Osaka Cement Co., Ltd., MZ-230X, solid content 32.5%)
(Average primary particle size: 25 nm)
・ Methyl isobutyl ketone 500 parts ・ Cyclohexanone 250 parts ・ Methyl ethyl ketone 500 parts

  Next, a transparent conductive layer made of tin-doped indium oxide (ITO) is formed on the low refractive index layer of the obtained substrate using a sputtering apparatus (thickness: 23 nm), and is placed in an oven at a temperature of 150 ° C. for 30 minutes. The transparent conductive layer was crystallized by heat treatment.

Further, a striped pattern of photoresist was formed on the transparent conductive layer and immersed in hydrochloric acid for etching. After the etching treatment, the film was dried at 120 ° C. for 5 minutes to form a transparent conductive layer patterned in a stripe shape having a height of 23 nm, a width of 1.0 mm, and a pitch of 1.0 mm, thereby obtaining a laminate. Then, the laminated body which has the patterned transparent conductive layer was produced by performing heat processing (130 degreeC for 30 minutes) further.
Patterned surface irregularities (washboard ripple) and flexibility of the obtained laminate were evaluated. The results are shown in Table 1.

(Examples 2 to 6)
In Example 1, except that the thickness of the transparent layer was changed to 10, 8.5, 4, 2, 1 μm in order, a substrate composed of a transparent substrate and a transparent layer was obtained in the same manner as in Example 1, and further patterned. A laminate having a transparent conductive layer was prepared.
The storage elastic modulus at 130 ° C. and 150 ° C. of each of the obtained substrates was measured. Moreover, the surface unevenness | corrugation (washboard ripple) and the flexibility which were patterned of the laminated body were evaluated. The results are shown in Table 1.

(Comparative Examples 1-3)
A substrate comprising a transparent substrate and a transparent layer in the same manner as in Example 1 except that the thickness of the transparent layer was changed to 0.5, 0, and 15 μm in this order in Example 1 (to be exact, Comparative Example 2 is a transparent substrate) (Substrate made of only material) and a laminated body having a patterned transparent conductive layer.
The storage elastic modulus at 130 ° C. of the obtained substrate was measured. Moreover, the surface unevenness | corrugation (washboard ripple) and the flexibility which were patterned of the laminated body were evaluated. The results are shown in Table 1.

From Table 1, the laminated body which has the patterned transparent conductive layer of Examples 1-6 of this invention does not generate | occur | produce a washboard ripple in the transparent conductive layer of the surface, and has the outstanding external appearance property and visibility. I understood it.
On the other hand, washboard ripples occurred in the transparent conductive layer on the surface of the laminates of Comparative Examples 1 and 2, and the laminate of Comparative Example 3 had no bending resistance and cracks.
In addition, when the laminated bodies of Examples 1 to 6 and Comparative Examples 1 to 3 were bonded to the glass substrate, the ones of Examples 1 to 6 and Comparative Example 3 were less likely to entrain air bubbles during bonding, whereas Examples 1 and 2 were easy to entrain bubbles.

  The laminate of the present invention can be suitably used as a constituent member of a touch panel, and can be particularly suitably used as a constituent member of a capacitive touch panel.

1: Laminate precursor (transparent conductive layer: no pattern; solid film)
2: Transparent base materials 3a, 3b: Transparent layer 4: Optical functional layer 5: Substrate 6: Transparent conductive layer solid film (no patterning)
6 ': Transparent conductive layer pattern film 7: Extraction electrode pattern (before firing)
7 ': Extraction electrode pattern (after firing)
8: Extraction electrode terminal (before firing)
8 ': Extraction electrode terminal part (after baking)
11: Transparent conductive film (transparent conductive layer: with pattern)
100: Pattern layer 110: Direction in which the stretch ratio of the biaxially stretched polyester film is large (MD; for X electrode portion)
111-116: X electrode part (transparent conductive layer pattern)
210: Direction in which the draw ratio of the biaxially stretched polyester film is large (MD; for Y electrode portion)
211-214: Y electrode part (transparent conductive layer pattern)

Claims (11)

A laminated body having a patterned transparent conductive layer on a substrate having a transparent layer on one or both sides of a transparent substrate, the storage elastic modulus Ec (N / m ² ) of the substrate at 130 ° C. A laminate in which Et (N / m) obtained by multiplying the thickness d (m) of the substrate is 4.0 × 10 ⁴ ≦ Et ≦ 10.5 × 10 ⁴ .   The laminate according to claim 1, wherein the storage elastic modulus of the transparent layer is larger than the storage elastic modulus of the transparent substrate. Wherein the thickness of the transparent substrate d _S (m), if the thickness of the transparent layer was d _L (m), satisfy the following relationship, the laminated body according to claim 1 or 2.
0.005 ≦ d _L / (d _S + d _L ) ≦ 0.7   The laminated body in any one of Claims 1-3 whose thickness of the said transparent base material is 15-125 micrometers, and the total thickness of the said transparent layer is 2.0-24 micrometers.   The laminated body in any one of Claims 1-4 in which the said base | substrate has an optical adjustment layer further.   The laminate according to claim 5, wherein the substrate has the transparent layer and the optical adjustment layer on the transparent substrate, and has the patterned transparent conductive layer on the optical adjustment layer.   The optical adjustment layer comprises a high refractive index layer and a low refractive index layer, the refractive index of the high refractive index layer is 1.55 to 1.75, and the refractive index of the low refractive index layer is 1.30. The laminate according to claim 5 or 6, which is 1.55.   The laminate according to any one of claims 1 to 7, wherein the transparent layer is a hard coat layer.   The touch panel which has the laminated body in any one of Claims 1-8 as a structural member.   The said laminated body has the said hard-coat layer and the said optical adjustment layer on the said transparent base material, The said patterned transparent conductive layer is formed on this optical adjustment layer of Claim 9. Touch panel. A method for producing a laminate comprising a patterned transparent conductive layer on a substrate having a transparent layer on one or both sides of a transparent substrate,
Et (N / m) obtained by multiplying the storage elastic modulus Ec (N / m ² ) of the substrate at 130 ° C. by the thickness d (m) of the substrate is 4.0 × 10 ⁴ ≦ Et ≦ 10.5. A substrate forming step for forming the transparent layer on the transparent substrate, a transparent conductive layer forming step for forming the transparent conductive layer on the substrate, and pattern formation for patterning the transparent conductive layer so as to be × 10 ⁴ The manufacturing method of a laminated body including the crystallization process of heating and crystallizing a process and a transparent conductive layer.