JP6642863B2 - Manufacturing method of laminate - Google Patents

Description

The present invention relates to a method for manufacturing a product layer thereof.

  BACKGROUND ART A transparent conductive layer having a light-transmitting property while having conductivity, for example, a transparent conductive layer made of indium tin oxide (hereinafter, ITO) is used for a transparent electrode in a liquid crystal display device or an organic EL display device, or for a detection in a touch panel sensor. Is used as a transparent conductive pattern.

  In order to enhance the characteristics of the transparent electrode and the transparent conductive pattern, it is expected to lower the sheet resistance of the transparent conductive layer. It is known that the sheet resistance of a transparent conductive layer made of ITO is lower when ITO is crystallized than when it is in an amorphous state. In consideration of such characteristics, Patent Literature 1 proposes performing an annealing treatment on an ITO layer formed on a base material to thereby promote crystallization of the ITO layer.

JP 2003-16858 A

  By the way, the sheet resistance of the ITO layer can be decreased as the thickness of the ITO layer is increased. However, when the thickness of the ITO layer is increased, the light transmittance of the ITO layer is deteriorated, and the ITO layer is colored. Therefore, the thickness of the ITO layer is generally about several tens nm. In order to reduce the sheet resistance of such a thin-film ITO layer, it is not enough to simply promote the crystallization of the ITO layer, and it is considered that further improvement to the ITO layer is necessary.

  An object of the present invention is to provide a laminate and a conductive pattern base material for a touch panel, which can effectively solve such a problem.

The present invention relates to a laminate comprising a support and a transparent conductive layer made of ITO formed on one surface of the support, wherein an X-ray is applied to one surface of the laminate. The height of the diffraction peak based on the (222) plane of the ITO crystal of the transparent conductive layer when the measurement of the diffraction peak generated by making the incident light is performed by the In-Plane measurement is defined as P _{ITO (222).} Assuming that the height of the diffraction peak based on the (400) plane of the ITO crystal of the transparent conductive layer is P _{ITO (400)} , the laminate having P _{ITO (222)} / P _{ITO (400)} of 3.6 or more is used. is there.

For example, in the laminate of the present invention, the weight ratio of tin oxide to indium tin oxide in the transparent conductive layer is 7:93 .

  For example, in the laminate of the present invention, the support includes one or more layers, and a layer of the support that is in contact with the transparent conductive layer includes polysiloxane.

  The present invention is a conductive pattern base material for a touch panel, obtained by processing the above-described laminate.

According to the present invention, the (222) plane of the ITO crystal of the transparent conductive layer when the diffraction peak generated when X-rays are incident on one surface of the laminate is measured by In-Plane measurement. When the height of the diffraction peak based on the _ITO is P _{ITO (222)} and the height of the diffraction peak based on the (400) plane of the ITO crystal of the transparent conductive layer is P _{ITO (400)} , P _{ITO (222)} / P _{ITO (400)} is 3.6 or more. Thereby, a transparent conductive layer having a low sheet resistance can be realized.

FIG. 1 is a sectional view showing a laminated body according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view showing a support used to produce the laminate of FIG. FIG. 3 is a sectional view showing a modification of the laminate of FIG. 1. FIG. 4 is a cross-sectional view showing a support used to produce the laminate of FIG. FIG. 5A is a diagram for explaining a method of manufacturing the support shown in FIG. 2. FIG. 5B is a diagram for explaining a method of manufacturing the support shown in FIG. 2. FIG. 6 is a plan view showing a conductive pattern base material for a touch panel obtained by processing the laminate shown in FIG. 3. FIG. 7 is a cross-sectional view of the conductive pattern base material of FIG. 6 along line VII-VII. FIG. 8 is a view showing a crystal structure of ITO. FIG. 9 is a diagram showing diffraction peaks obtained from the laminate of Sample 5. FIG. 10 is a view showing the relationship between P _{ITO (222)} / P _{ITO (400)} in the laminate of each sample and the sheet resistance of the transparent conductive layer. FIG. 11 is a view showing the relationship between P _{ITO (222)} / P _{ITO (400)} in the laminate of each sample and the surface free energy of the support of each sample.

  Hereinafter, an embodiment of the present invention will be described with reference to FIGS. As shown in FIG. 1, the laminate 10 includes a support 11 and a first transparent conductive layer 16 a provided on a surface 11 a on one side of the support 11. First, the support 11 will be described, and then the first transparent conductive layer 16a will be described.

(Support)
As shown in FIGS. 1 and 2, the support 11 includes a substrate 12, a first hard coat layer 13 a and a first index matching layer 14 a sequentially provided on one surface 12 a of the substrate 12. , Including. Hereinafter, the substrate 12, the first hard coat layer 13a, and the first index matching layer 14a will be described.

(Base material)
As the substrate 12, a film or glass having sufficient translucency is used. Examples of a material constituting the film used for the base material 12 include polyethylene terephthalate (PET), cycloolefin polymer (COP), cyclic olefin copolymer (COC), polycarbonate (PC), triacetyl cellulose (TAC), and polyacetylene. Methyl methacrylate (PMMA) and the like. The thickness of the substrate 12 is, for example, in the range of 25 to 200 μm.

(Hard coat layer)
The first hard coat layer 13a is a layer provided for the purpose of preventing scratches and the purpose of preventing a low-molecular polymer (oligomer) from depositing at the interface between the layers and appearing cloudy white. As the first hard coat layer 13a, for example, an acrylic resin or the like is used. As shown in FIGS. 1 and 2, a second hard coat layer 13b made of the same material as the first hard coat layer 13a may be further provided on the other surface 12b of the base material 12. The thickness of the hard coat layers 13a and 13b is, for example, in the range of 0.1 to 10 μm.

(Index matching layer)
The first index matching layer 14a is a layer provided between the base material 12 and the first transparent conductive layer 16a for the purpose of adjusting the light transmittance and the reflectance of the laminated body 10. In the present embodiment, the first index matching layer 14a includes a first high-refractive-index layer made of a material having a higher refractive index than the material forming the base material 12. Further, the first index matching layer 14a of the present embodiment is formed of a material having a lower refractive index than the material forming the base material 12, between the first high refractive index layer and the first transparent conductive layer 16a. A first low-refractive-index layer.

  As a material for forming the first low refractive index layer, for example, silicon oxide or magnesium fluoride is used. As a material constituting the first high refractive index layer, for example, niobium oxide or zirconium is used. The thicknesses of the first high-refractive index layer and the first low-refractive index layer are appropriately set according to the materials used so that desired transmittance and reflectance are achieved.

  In the present embodiment, an example in which the above-described first index matching layer 14a is included in the stacked body 10 will be described. However, the first index matching layer 14a may not necessarily be provided. Similarly, the hard coat layers 13a and 13b are also provided as needed. Therefore, the first transparent conductive layer 16a may be provided so as to directly contact the surface 12a on one side of the base material 12 or the surface on one side of the first hard coat layer 13a. Further, when the base material 12, the hard coat layers 13a and 13b, and the first index matching layer 14a are made of a material that generates a so-called outgas including oxygen and the like, the outgassing of the ITO of the first transparent conductive layer 16a is performed. In order to prevent crystallization from being hindered, a barrier layer that blocks outgas may be provided on one surface of the base material 12, the hard coat layers 13a and 13b, or the first index matching layer 14a. As a material forming the barrier layer, for example, silica is used.

(Transparent conductive layer)
As a material forming the first transparent conductive layer 16a, a material having a light-transmitting property while having conductivity is used. In the present embodiment, indium tin oxide (ITO) is used. Here, ITO means a metal oxide containing 89 to 99% by weight of indium, 1 to 11% by weight of tin, and 0.5% by weight or less of other additive elements or unavoidable impurities. I have. The thickness of the first transparent conductive layer 16a is, for example, in the range of 18 to 50 nm.

  In general, it is expected that a transparent conductive layer made of ITO is formed so that its sheet resistance is reduced without increasing its thickness. In this regard, the present inventors have conducted intensive studies and found that the sheet resistance of the transparent conductive layer differs depending on the film forming conditions of the transparent conductive layer, the configuration of the support on which the transparent conductive layer is formed, and the like. Was. As a result of examining the crystal structure of the first transparent conductive layer 16a made of ITO in order to investigate the cause, as shown in an example described later, the ratio of the predetermined crystal plane of the ITO crystal of the first transparent conductive layer 16a was sufficient. Higher, the sheet resistance of the first transparent conductive layer 16a is sufficiently low.

  Specifically, the crystal structure of ITO is a Bixbyte structure as shown in FIG. 8, and the measurement of a diffraction peak generated by making X-rays incident on one surface of the laminate 10 is performed. When the measurement is performed by the in-plane measurement, diffraction peaks based on the (222) plane, the (400) plane, the (440) plane, and the like of the ITO crystal of the first transparent conductive layer 16a appear. Here, the In-Plane measurement means that X-rays are incident on a very small surface of the first transparent conductive layer 16a of the laminate 10 and the diffraction of the X-rays generated at this time is observed, whereby the first transparent conductive layer 16a is measured. This method measures the crystal plane of the ITO crystal. In this method, the orientation of the crystal plane extending parallel to the normal direction of the first transparent conductive layer 16a is measured. According to the In-Plane measurement, signals caused by the base material 12, the first hard coat layer 13a, and the first index matching layer 14a can be suppressed as compared with the θ / 2θ measurement generally used in the related art. The crystal information on the surface of the first transparent conductive layer 16a can be measured with high sensitivity.

According to the results of the research by the present inventors, the height of the diffraction peak based on the (222) plane of the ITO crystal of the first transparent conductive layer 16a obtained by performing the above-described In-Plane measurement is determined. When P _{ITO (222)} and the height of the diffraction peak based on the (400) plane of the ITO crystal of the first transparent conductive layer 16a is P _{ITO (400)} , P _{ITO (222)} / P _{ITO (400)} becomes If it is sufficiently high, the sheet resistance of the first transparent conductive layer 16a will be sufficiently low.
When P _{ITO (222)} / P _{ITO (400)} is 3.6 or more, the sheet resistance of the first transparent conductive layer 16a is sufficiently low for practical use as a conductive pattern base material for a touch panel. Specifically, it was found that the resistance was 140Ω / □ or less.

The method for controlling the orientation of the ITO crystal such that the height P _{ITO (222) of the} diffraction peak based on the (222) plane of the ITO crystal of the first transparent conductive layer 16a is not particularly limited, As a result of repeated trial and error by the present inventors, it has been found that the following method can be adopted. That is, as is supported by the embodiment described later, the surface free energy on the surface 11a on one side of the support 11 is sufficiently increased, so that the ITO crystal of the first transparent conductive layer 16a formed on the surface 11a is formed. Can be controlled so that P _{ITO (222)} / P _{ITO (400)} becomes sufficiently high. Specifically, by setting the surface free energy on the surface 11a to 60 mJ / m ² or more, P _{ITO (222)} / P _{ITO (400)} becomes 3.6 or more, more preferably 3.8 or more, and still more preferably. Can control the orientation of the ITO crystal so that is not less than 4.4.

  The method for increasing the surface free energy on the surface of the support 11 is not particularly limited. For example, the surface of the support 11 is subjected to plasma treatment, or the outermost layer of the support 11 is made of a material containing polysiloxane. May be adopted. Here, the reason why the surface free energy on the surface of the support 11 can be increased by subjecting the surface of the support 11 to plasma treatment or forming the outermost layer of the support 11 from a material containing polysiloxane is particularly limited. However, for example, the following reasons can be considered. That is, by performing the plasma treatment on the surface of the support 11, the OH groups in the support 11 are exposed on the surface of the support 11. Further, since the outermost layer of the support 11 is made of a material containing polysiloxane, OH groups exist on the surface of the support 11. Then, the presence of OH groups on the surface of the support 11 contributes to increasing the surface free energy on the surface.

  In addition, the surface free energy on the surface of the support 11 can be checked using a water contact angle, a diiodomethane contact angle, an ethylene glycol contact angle, and the like on the surface of the support 11.

  In addition, it is considered that the material used for forming the first transparent conductive layer 16a also affects the orientation of the ITO crystal of the first transparent conductive layer 16a.

  Next, the operation and effect of the present embodiment having such a configuration will be described. Here, first, a method of manufacturing the above-described support 11 and a method of manufacturing the laminated body 10 using the support 11 will be described. Next, a method for manufacturing a conductive pattern base material for a touch panel obtained by processing the laminate 10 will be described.

Method of Manufacturing Support First, as shown in FIG. 5A, a base material 12 is prepared. Next, as shown in FIG. 5B, a coating solution containing an acrylic resin is applied to both sides of the base material 12 using a coater. Thereby, the hard coat layers 13a and 13b are formed on both sides of the base material 12. Next, a coating liquid containing particles of an organic resin and a high refractive index material dispersed in the organic resin, for example, particles of zirconium, is applied onto the first hard coat layer 13a using a coater. Thereby, a first high refractive index layer is formed on the first hard coat layer 13a. Thereafter, a coating solution containing particles of an organic resin and a low refractive index material dispersed in the organic resin, for example, particles of silicon oxide, is applied onto the first high refractive index layer using a coater. Thereby, the first low refractive index layer is formed on the first high refractive index layer. Thus, the first index matching layer 14a is formed on the first hard coat layer 13a, and the support 11 shown in FIG. 2 can be obtained.

Method for producing a laminate Next, in this embodiment, to increase the surface free energy of the one surface 11a of the support 11 the first transparent conductive layer 16a is formed, plasma treatment on the first index matching layer 14a Is applied. Subsequently, the first transparent conductive layer 16a is formed on the first index matching layer 14a by using a vacuum film forming method such as a sputtering method. In this embodiment mode, sputtering is performed using a target with a weight ratio of tin oxide to indium tin oxide of 7:93 (within a range of 7.5: 92.5 to 6.5: 93.5 ). The first transparent conductive layer 16a is formed. Thereafter, in order to further promote the crystallization of ITO in the first transparent conductive layer 16a, the first transparent conductive layer 16a may be subjected to an annealing treatment. Thus, the laminate 10 shown in FIG. 1 can be obtained.

Method for Manufacturing Conductive Pattern Substrate for Touch Panel Next, as an example of the use of the laminate 10, a conductive pattern substrate for a touch panel obtained by processing the laminate 10 will be described. The conductive pattern base material 60 for a touch panel is provided on a viewer side of a display panel such as a liquid crystal display panel or an organic EL display panel, and includes a transparent conductive pattern and the like for detecting a contact position of a detection target such as a human body. It is a sensor. As the conductive pattern base material 60 for the touch panel, a touch panel sensor of a resistive film type that detects a touch location based on pressure from a detection target, or a touch location is detected based on static electricity from a detection target such as a human body. Various types such as a capacitive touch panel sensor are known, but here, a conductive pattern base material 60 for a touch panel as a capacitive touch panel sensor is formed by patterning the laminate 10. An example will be described with reference to FIGS. 6 is a plan view showing the conductive pattern base material 60 for a touch panel, and FIG. 7 is a cross-sectional view of the conductive pattern base material 60 for a touch panel shown in FIG. 6 along line VII-VII. 6 and 7 show the laminate 10 manufactured using the support 11 including the index matching layers 14a and 14b arranged on one side and the other side of the base material 12 shown in FIG. As shown in FIG. 3, the touch panel sensor 60 is manufactured by using the laminate 10 including the transparent conductive layers 16a and 16b disposed on one side and the other side of the support 11.

  As shown in FIG. 6, the conductive pattern base material for a touch panel 60 includes transparent conductive patterns 62a and 62b for detecting a change in capacitance caused by the approach of an external conductor such as a finger. The transparent conductive patterns 62a and 62b are arranged on one side of the base material 12, and are arranged on the other side of the base material 12 with the first transparent conductive pattern 62a extending in the horizontal direction of FIG. And a second transparent conductive pattern 62b extending to In FIG. 6, the second transparent conductive pattern 62b provided on the lower side is represented by a dotted line. As shown in FIG. 7, the transparent conductive patterns 62a and 62b are obtained by patterning the transparent conductive layers 16a and 16b of the laminate 10. As a method of patterning the transparent conductive layers 16a and 16b, for example, a photolithography method is used.

  As shown in FIG. 6, the conductive pattern base material for a touch panel 60 includes extraction patterns 64a and 64b connected to the transparent conductive patterns 62a and 62b, and extraction patterns 64a and 64b connected to the extraction patterns 64a and 64b. Terminal portions 65a and 65b for taking out signals from 62a and 62b to the outside may be further provided. The extraction patterns 64a and 64b and the terminal portions 65a and 65b are arranged in a region where the image light from the display panel does not pass through in the conductive pattern base material 60 for a touch panel, that is, a frame region. Therefore, it is not necessary that the material forming the extraction patterns 64a and 64b and the terminal portions 65a and 65b has transparency. Therefore, the extraction patterns 64a and 64b and the terminal portions 65a and 65b are generally made of a metal material having higher electric conductivity than the transparent conductive material forming the transparent conductive patterns 62a and 62b.

  The method for forming such extraction patterns 64a and 64b and the terminal portions 65a and 65b is not particularly limited, and a photolithography method or a printing method is appropriately used. For example, first, a metal material layer (not shown) is formed on the transparent conductive layer 16 of the laminated body 10, and then the metal material layer and the transparent conductive layers 16a and 16b are sequentially or simultaneously etched by using a photolithography method. Thus, the extraction patterns 64a and 64b, the terminal portions 65a and 65b, and the transparent conductive patterns 62a and 62b may be formed. In this case, as shown in FIG. 7, transparent conductive patterns 62a and 62b may be interposed between the extraction patterns 64a and 64b and the index matching layers 14a and 14b. Thereby, the electric resistance when extracting signals from the transparent conductive patterns 62a and 62b can be further reduced. In the etching for removing the metal material layer remaining on the transparent conductive patterns 62a and 62b in the area where the image light from the display panel passes, only the metal material layer is selectively dissolved as an etchant. An etchant is used.

According to the present embodiment, in the case where the conductive pattern base material 60 for a touch panel is subjected to In-Plane measurement of a diffraction peak generated when X-rays are incident on one surface of the laminate 10. The height of the diffraction peak based on the (222) plane of the ITO crystal of the transparent conductive layers 16a and 16b is defined as P _{ITO (222),} and the height of the diffraction peak based on the (400) plane of the ITO crystal of the transparent conductive layers 16a and 16b is When the height is set to P _{ITO (400)} , it is manufactured by processing the laminate 10 in which P _{ITO (222)} / P _{ITO (400)} is 3.6 or more. Thereby, it is possible to obtain the conductive pattern base material 60 for the touch panel having the transparent conductive patterns 62a and 62b having a sufficiently low sheet resistance, specifically, 140Ω / □ or less, more preferably 130Ω / □ or less. It is.

  Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the description of the following examples unless it exceeds the gist.

  Laminate samples 1 to 7 were produced under various production conditions. Hereinafter, first, samples 1 to 7 of the support prepared for manufacturing samples 1 to 7 of the laminate will be described, and then samples 1 to 7 of the laminate prepared using each support will be described. Will be described.

(Support)
Samples 1 to 11 of the support 11 including a base material 12 and a first hard coat layer 13a and a first index matching layer 14a provided in order on one side of the base material 12
Was prepared. The first index matching layer 14a includes a first high refractive index layer formed on the first hard coat layer 13a, and a first low refractive index layer formed on the first high refractive index layer. . The first low refractive index layer as the outermost layer of each support 11 was formed by applying a coating liquid containing the following materials on the first high refractive index layer. The application of the coating liquid was performed using a spin coater manufactured by Mikasa Corporation.
[Sample 1] Alkoxy metal-based material (Ceramica G-90 A, B, manufactured by Nippon Research Institute)
[Sample 2] Silicone material (Shin-Etsu Chemical Co., Ltd .: KS-3601 / CAT-PL-56)
[Sample 3] Silazane-based material (AZ-ELECTRONIC MATERIALS: NL-120A-20)
[Sample 4] Organic-inorganic hybrid material (Glaska HPC7506A, manufactured by JSR Corporation)
[Sample 5] Siloxane-based material (Colcoat N-103X, manufactured by Colcoat)
[Sample 6] Siloxane-based material (Colcoat PX: Colcoat PX)
[Sample 7] Siloxane-based material (Colcoat Co., Ltd .: Colcoat SS-C1)

[Evaluation 1 Surface Free Energy of Support]
Subsequently, a water contact angle, a diiodomethane contact angle, and an ethylene glycol contact angle on the surface 11a of the first low refractive index layer of each support 11 thus obtained were measured, and the surface free energy on the surface 11a was measured. Was measured. The measurement conditions for each contact angle and the conditions for measuring and analyzing the surface free energy are shown below.
<Measurement conditions of contact angle>
Measuring device: Contact angle meter manufactured by Kyowa Interface Science Co., Ltd. Drop amount of water, diiodomethane and ethylene glycol: 1.0 microliter <Measurement and analysis conditions of surface free energy>
Software used for measurement and analysis of surface free energy: KYOWA interFAce Measurement and Analysis System (FAMAS)
Surface free energy theory: Owens-Wendt

The surface free energy of the surface 11a of each support 11 measured as described above was as follows.
<Surface free energy>
[Sample 1] 62.1 mJ / m ²
[Sample 2] 25.3 mJ / m ²
[Sample 3] 19.3 mJ / m ²
[Sample 4] 26.2 mJ / m ²
[Sample 5] 63.2 mJ / m ²
[Sample 6] 62.0 mJ / m ²
[Sample 7] 66.0 mJ / m ²

(Laminate)
Subsequently, the first transparent conductive layer 16a was formed on the surface 11a of each support 11 by a sputtering method, and samples 1 to 7 of the laminate 10 were formed. The thickness of the first transparent conductive layer 16a of each laminate 10 was about 30 nm. The weight ratio of tin oxide to indium tin oxide in the target used for forming the first transparent conductive layer 16a of each laminate 10 was as follows.
<Weight ratio (tin oxide: indium tin oxide)>
[Sample 1] 5:95
[Sample 2] 7:93
[Sample 3] 10:90
[Sample 4] 7:93
[Sample 5] 7:93
[Sample 6] 7:93
[Sample 7] 7:93

[Evaluation 2 Sheet resistance of transparent conductive layer]
The sheet resistance of the first transparent conductive layer 16a of each of the laminates 10 thus obtained was measured. The conditions for measuring the sheet resistance are shown below.
<Measurement conditions>
Measuring device: Lorester manufactured by Mitsubishi Chemical Corporation Measuring method: 4-terminal method

The sheet resistance of the first transparent conductive layer 16a of each laminate 10 measured as described above was as follows.
<Measurement results>
[Sample 1] 159Ω / □
[Sample 2] 140Ω / □
[Sample 3] 169Ω / □
[Sample 4] 140Ω / □
[Sample 5] 125Ω / □
[Sample 6] 128Ω / □
[Sample 7] 129Ω / □

[Evaluation 3 Diffraction peak]
Thereafter, X-rays were incident on one surface of each of the laminates 10, and the diffraction peak of the ITO crystal contained in the first transparent conductive layer 16a was measured. The measurement was performed under the following conditions so that a diffraction peak of the ITO crystal could be obtained with high accuracy even for a transparent conductive layer having a thickness of about 30 nm.
Measuring device: Rigaku SmartLab
Measurement method: In-Plane measurement X-ray: tube voltage 45 kV, tube current 200 mA
Measurement range: 10 ° to 70 °
Scan axis: 2θχ / φ
Incident angle ω: 0.43 °
Fixed angle 2θ: 0.43 °

  FIG. 9 shows a diffraction peak obtained in the sample 5 of the laminate. In FIG. 9, the vertical axis represents the detected intensity of the diffracted X-ray (cps: count per sec.), And the horizontal axis represents the fixed angle 2θ.

  In FIG. 9, the diffraction peak near 2θ = 30.5 ° is a diffraction peak based on the (222) plane of the ITO crystal. The diffraction peak near 2θ = 35 ° is a diffraction peak based on the (400) plane of the ITO crystal.

P _{ITO (222)} / P _{ITO (400)} of the first transparent conductive layer 16a of each laminate 10 measured as described above was as follows.
[Sample 1] 2.8
[Sample 2] 3.0
[Sample 3] 2.9
[Sample 4] 3.3
[Sample 5] 4.4
[Sample 6] 3.8
[Sample 7] 3.6

FIG. 10 shows the relationship between P _{ITO (222)} / P _{ITO (400)} in the first transparent conductive layer 16a of each laminate 10 and the sheet resistance. In FIG. 10, the vertical axis represents P _{ITO (222)} / P _{ITO (400)} , and the horizontal axis represents the sheet resistance (Ω / □) of the first transparent conductive layer 16a. As can be seen from FIG. 10, if P _{ITO (222)} / P _{ITO (400)} is sufficiently high, the sheet resistance of the transparent conductive layer is sufficiently low. When P _{ITO (222)} / P _{ITO (400)} was 3.6 or more, the sheet resistance of the transparent conductive layer formed on the surface was reduced to a practically sufficient level. That is, it was reduced to 140Ω / □ or less, more specifically, to 130Ω / □ or less. When P _{ITO (222)} / P _{ITO (400)} is higher, for example, 3.8 or more, more preferably 4.4 or more, the sheet resistance of the transparent conductive layer formed on the surface is further increased. Reduced.

FIG. 11 shows the surface free energy of the surface 11a of each of the samples 1 to 7 of the support 11, the P _{ITO (222)} / P _{ITO (400) of} the first transparent conductive layer 16a formed on the surface 11a, Shows the relationship. In FIG. 11, the vertical axis represents P _{ITO (222)} / P _{ITO (400)} , and the horizontal axis represents sheet resistance. As can be seen from FIG. 11, if the surface free energy on the surface of the support is sufficiently high, P _{ITO (222)} / P _{ITO (400) of the} transparent conductive layer formed on the surface is sufficiently high. .
When the surface free energy was 60 mJ / m ² or more, P _{ITO (222)} / P _{ITO (400)} became 3.6 or more.

DESCRIPTION OF SYMBOLS 10 Laminated body 11 Support body 12 Substrate 13 Hard coat layer 14 Index matching layer 16 Transparent conductive layer 60 Touch panel sensor 62 Transparent conductive pattern 64 Extraction pattern 65 Terminal part

Claims (4)

A laminate including a transparent conductive layer made of ITO, wherein the measurement of a diffraction peak generated by irradiating an X-ray to one surface of the laminate is performed by an In-Plane measurement. The height of the diffraction peak based on the (222) plane of the ITO crystal of the conductive layer is defined as P _{ITO (222),} and the height of the diffraction peak based on the (400) plane of the ITO crystal of the transparent conductive layer is defined as P _{ITO (400). Wherein} P _{ITO (222)} / P _{ITO (400)} is 3.6 or more,
Providing a support having a surface free energy on one side of 60 mJ / m ² or more;
Forming the transparent conductive layer on the one side surface of the support to make the P _{ITO (222)} / P _{ITO (400)} 3.6 or more ;
A method for producing a laminate, comprising: The lamination according to claim 1 , wherein in the step of forming the transparent conductive layer, the transparent conductive layer is formed by performing sputtering using a target having a weight ratio of tin oxide to indium tin oxide of 7:93. How to make the body. The support includes one or more layers,
The contact with the transparent conductive layer a layer of the support, contains a polysiloxane, method for producing a laminate according to claim 1 or 2. The step of preparing the support,
Wherein the surface of said one side of the support, the surface free energy of the surface of the one side has a step of performing a plasma treatment so that 60 mJ / m ² or more, according to claim 1 or 2 A method for manufacturing a laminate.