TW201616294A - Conductive transparent laminate, patterned conductive transparent laminate and touch panel - Google Patents

Abstract

A conductive transparent laminate comprises: a transparent substrate, an optical modification layer in contact with the transparent substrate and having a refractivity between 1.33 and 1.52 under 400 nm wavelength and a physical thickness between 10 and 30 nm, and a transparent conductive layer in contact with the optical modification layer and having a carrier concentration ranging from 10*10<SP>21</SP>/cm3 to 20*10<SP>21</SP>/cm3 and a physical thickness between 10 and 30 nm. After patterning the transparent conductive layer of the conductive transparent laminate, a patterned conductive transparent laminate is made, which has a pattern part having a refractivity close to that of a non-pattern part. When applied to a touch panel, traces of the patterned transparent conductive layer are substantially invisible to users.

Description

Conductive transparent laminate, patterned conductive transparent laminate and touch panel

The invention relates to a conductive transparent laminate applied to a touch panel, in particular to a conductive layer comprising an optical adjustment layer contacting a transparent substrate and having a refractive index ranging from 1.33 to 1.52 and a physical thickness ranging from 10 nm to 30 nm. Transparent laminate.

In order to improve the quality of the touch panel, the conductive transparent laminate currently used in the touch panel comprises a transparent substrate, a transparent conductive layer, and optical adjustment of a plurality of layers disposed between the transparent substrate and the transparent conductive layer. The layer adjusts the refractive index and thickness of the optical adjustment layer to adjust the total light transmittance and the penetration color of the conductive transparent laminate, thereby improving the brightness of the touch panel and improving the display color deviation of the touch panel. . In addition to the above-mentioned lifting methods, various touch panel manufacturers have also researched and developed "projected capacitive touch panels". The main technique is to further pattern a transparent conductive layer of a conductive transparent laminate to form a patterned conductive transparent laminate. . However, when light enters the projected capacitive touch panel from the outside and contacts the layers in the patterned conductive transparent laminate, the light is partially reflected. When reflected, the reflected light passes through the patterned conductive respectively. Pattern portion and non-pattern portion of transparent laminate, pattern The difference between the reflectance of the reflected light emitted from the portion and the reflectance of the reflected light emitted from the non-pattern portion is large, and the trace of the patterning of the transparent conductive layer can be clearly seen when the user views the touch panel.

A transparent conductive film comprising a polyester film, a high refractive index layer disposed on the polyester film, a low refractive index layer disposed on the high refractive index layer, and a transparent conductive film disclosed in the Korean Patent Publication No. TW201133515 An indium tin oxide layer disposed on the low refractive index layer. The high refractive index layer has a refractive index ranging from 1.63 to 1.86 at a wavelength of 400 nm and a thickness ranging from 40 nm to 90 nm. The low refractive index layer has a refractive index ranging from 1.33 to 1.53 at a wavelength of 400 nm and a thickness ranging from 10 nm to 50 nm.

The transparency of the transparent conductive film of this patent has a b ₁ * range of -0.6 to 0.5, and a total light transmittance of 88.2 to 91.4 (TT%). The main purpose of the patent is to reduce the b ₁ * of the transparent chromaticity of the transparent conductive film, so as to achieve the effect that the transparent conductive film does not exhibit yellow color, but the inventors of the present invention prepare a transparent conductive film according to the contents of the patent. The indium tin oxide (ITO) layer was patterned and tested, and the reflectance of the reflected light emitted from the pattern portion of the transparent conductive film of the patent was compared with that of the reflected light emitted from the non-pattern portion. The difference is still too large. Therefore, the transparent conductive film of the patent is obviously not suitable for the user's desire to see the trace of the transparent conductive layer pattern when the user touches the touch panel.

In view of the above, it is still necessary to solve the problem that the user can easily see the trace of the patterning of the transparent conductive layer during the viewing by improving the conductive transparent laminate to improve the display quality of the touch panel.

Herein, (meth)acrylate means acrylate and/or methacrylate.

Accordingly, a first object of the present invention is to provide a conductive transparent laminate. When the transparent conductive layer of the conductive transparent laminate is patterned to obtain a patterned conductive transparent laminate and applied to the touch panel, the user can hardly see the trace of the transparent conductive layer during viewing.

The conductive transparent laminate of the present invention comprises: a transparent substrate; an optical adjustment layer contacting the transparent substrate, the optical adjustment layer having a refractive index ranging from 1.33 to 1.52 at a wavelength of 400 nm, and a physical thickness ranging from 10 nm to 30 nm; A transparent conductive layer is in contact with the optical adjustment layer, and the transparent conductive layer has a carrier concentration ranging from 10×10 ²¹ /cm ³ to 20×10 ²¹ /cm ³ and a physical thickness ranging from 10 nm to 30 nm.

Accordingly, a second object of the present invention is to provide a patterned conductive transparent laminate in which the patterning marks are not conspicuous.

The patterned conductive transparent laminate of the present invention comprises: a transparent substrate; an optical adjustment layer contacting the transparent substrate, the optical adjustment layer having a refractive index ranging from 1.33 to 1.52 at a wavelength of 400 nm and a physical thickness ranging from 10 nm. Up to 30 nm; a patterned transparent conductive layer contacting the optical adjustment layer, the patterned transparent conductive layer having a carrier concentration ranging from 10×10 ²¹ /cm ³ to 20×10 ²¹ /cm ³ , physical The thickness ranges from 10 nm to 30 nm.

Therefore, a third object of the present invention is to provide a touch panel.

Therefore, the touch panel of the present invention comprises the above-mentioned conductive transparent laminate or the above-mentioned patterned conductive transparent laminate.

The effect of the present invention is that the conductive transparent laminate has an optical adjustment layer having a refractive index ranging from 1.33 to 1.52 and a physical thickness ranging from 10 nm to 30 nm at a wavelength of 400 nm contacting the transparent substrate, and matching the contact The optical adjustment layer and the carrier concentration range is from 10×10 ²¹ /cm ³ to 20×10 ²¹ /cm ³ of the transparent conductive layer, and in the subsequently obtained patterned conductive transparent laminate, the pattern is made There is a small difference between the reflectance of the reflected light emitted by the portion and the reflectance of the reflected light emitted from the non-pattern portion, and the trace of the transparent conductive layer is not obvious when viewed by the user, and then the display of the touch panel is improved. quality.

Hereinafter, the content of the present invention will be described in detail. The method for preparing the conductive transparent laminate of the present invention may be a method for preparing a transparent conductive laminate for a touch panel. More specifically, the method for preparing the conductive transparent laminate of the present invention comprises the steps of: providing a transparent substrate on which an optical adjustment layer having a refractive index ranging from 1.33 to 1.52 at a wavelength of 400 nm is formed, to obtain a first One layer fit. A metal oxide layer is formed on the optical adjustment layer to obtain a second laminate. Then, the metal oxide layer of the second laminate is subjected to crystallization annealing treatment to obtain a transparent conductive layer (the carrier concentration ranges from 10×10 ²¹ /cm ³ to 20×10 ²¹ /cm ³ ), that is, The conductive transparent laminate of the present invention.

The method of forming the optical adjustment layer on the transparent substrate is not particularly limited, and a conventional method may be employed. For example, a dry coating method or a wet coating method may be employed. In terms of production efficiency and manufacturing cost, a wet coating method is preferred. Among them, the specific embodiment of the wet coating method is a roll coating method, a spin coating method, a dip coating method, or the like, and the roll coating method is preferable because the optical adjustment layer can be continuously formed.

The material of the metal oxide layer is selected from the group consisting of indium oxide, tin oxide, titanium oxide, aluminum oxide, zinc oxide, gallium oxide or a combination thereof. The method for forming the metal oxide layer on the optical adjustment layer is not particularly limited, and may be a conventional method such as vapor deposition, sputtering, ion plating, chemical vapor deposition (CVD) or electroplating. Law and so on. In the above method, from the viewpoint of controlling the thickness of the transparent conductive layer, a vapor deposition method and a sputtering method are preferable.

The transparent conductive layer is formed after the metal oxide layer is subjected to crystallization annealing treatment. The crystallization annealing treatment has a temperature in the range of 100 to 200 ° C and a treatment time ranging from 0.5 hour to 2 hours.

The method for preparing a patterned conductive transparent laminate of the present invention comprises the steps of: providing a conductive transparent laminate as described above, and patterning the transparent conductive layer in the conductive transparent laminate to partially remove the transparent conductive layer Thereby, a "pattern portion" and a "non-pattern portion" of the patterned conductive transparent laminate are formed. The manner in which the transparent conductive layer is patterned is not particularly limited, and a conventional method may be employed. For example, laser etching, plasma etching, photolithography etching, or screen printing etching may be employed.

As used herein, the "pattern portion" of the patterned conductive transparent laminate refers to the region of the optical adjustment layer having a transparent conductive layer, and "non- The pattern portion refers to a region on the optical adjustment layer that does not have the transparent conductive layer.

Herein, the reflectance of the pattern portion of the patterned conductive transparent laminate refers to light entering from the pattern portion of the patterned conductive transparent laminate, and when contacting the layers in the patterned conductive transparent laminate. The light is partially reflected, and the reflected light is added by the light emitted from the pattern portion after reflection. The reflectance of the non-pattern portion of the patterned conductive transparent laminate refers to light entering from the non-pattern portion of the patterned conductive transparent laminate, and when contacting the layers in the patterned conductive transparent laminate, the light It will be partially reflected, and the reflected light will be added by the light emitted from the non-pattern portion after reflection.

The transparent substrate, the optical adjustment layer, and the transparent conductive layer will be described in detail below:

[Transparent substrate]

Preferably, the transparent substrate has a refractive index ranging from 1.40 to 1.80 at a wavelength of 400 nm.

The material of the transparent substrate is not particularly limited herein, such as but not limited to: (1) polyester: polyethylene terephthalate (PET) or polyethylene naphthalate. (polyethylene naphthalate, PEN), etc.; (2). Polyolefin: polypropylene (PP), high-density polyethylene (HDPE) or low-density polyethylene (low-density polyethylene, LDPE), etc.; (3). Polyvinyl chloride: polyvinyl chloride (PVC) or polydichloroethylene (polyvinylidene chloride, PVDC), etc.; (4). Cellulose esters: triacetyl cellulose (TAC) or acetate cellulose, etc.; (5). Polycarbonate ( Polycarbonate (polycarbonate, PC), etc.; (6). Polyvinyl acetate and its derivatives: polyvinyl alcohol (PVA), etc.; (7). (Methyl) Acrylate-based polymer: methacrylate-based homopolymer [for example, polymethylmethacrylate (PMMA)]; (8). Cycloolefin polymer (COP): cycloolefin copolymerization (cyclic olefin copolymer, COC), etc.; (9). Polyimides.

Preferably, the transparent substrate has a physical thickness ranging from 2 μm to 300 μm. More preferably, the transparent substrate has a physical thickness ranging from 10 μm to 250 μm. When the physical thickness of the transparent substrate is less than 2 μm, the tensile strength of the transparent substrate is insufficient, and the transparent substrate may be tortuous or even broken due to the inability to withstand the tension in the subsequent process, thereby making the subsequent layer process difficult. If the physical thickness of the transparent substrate exceeds 300 μm, the total light transmittance of the conductive transparent laminate is lowered, the manufacturing cost is increased, and the demand for thinning of the current technology products is not met.

[Optical adjustment layer]

The optical adjustment layer is formed by ultraviolet curing of a composition for an optical adjustment layer comprising a mixed solution, wherein the mixed solution comprises a photocurable binder, a photoinitiator, and a solvent.

The photocurable adhesive is not particularly limited herein, and is not limited to, for example, a photocurable acrylic resin or a poly(meth)acrylic group. A monomer or a polymer having a (meth)acryl group. Specific examples of the (meth)acryl group-containing polyfunctional monomer are (meth)acrylic acid, butyl (meth)acrylate or 2-hydroxyethyl acrylate. The (meth)acryl group-containing polymer is obtained by polymerization of one or more polyfunctional monomers having a (meth)acryl group. Preferably, the photocurable adhesive has a refractive index ranging from 1.4 to 1.7 at a wavelength of 400 nm.

The photoinitiator may be such that the photocurable adhesive can be photohardened when exposed to light, such as, but not limited to, a compound having a benzophenone structure (for example, a vinyl benzophenone). , Michler's ketone, phenylene, a compound having a benzyl group structure, a compound having a benzoin structure (for example, benzoin methyl ether), an ester having an α-methoxy group , ttioxanthone or anthraquinone, etc., the above photoinitiators can be used singly or in combination.

The solvent may be such that the components of the optical conditioning layer composition are uniformly mixed, such as, but not limited to, methyl isobutyl ketone, acetone, cyclohexanone, cyclopentanone, 2-hexanone, propylene glycol methyl ether, Methanol, ethanol, 1,2-propanediol, ethyl acetate, methyl acetate, butyl acetate, diethyl acetate, dimethyl carbonate, dichloromethane, chloroform, toluene, tetrahydrofuran, acetonitrile, chlorophenol, cyclohexane And N,N-dimethylacetamide, etc., the above solvents can be used singly or in combination.

The mixed solution also optionally includes a fluorine-containing compound for adjusting the refractive index of the optical adjustment layer to meet the demand. The fluorine-containing compound The refractive index at a wavelength of 400 nm ranges from 1.20 to 1.40. The fluorine-containing compound is, for example but not limited to, a fluororesin (commercially available as F-8261 manufactured by Degussa Co., Ltd.), a fluorine-based monomer (commercially available as FSO manufactured by DuPont Co., Ltd.), or the like.

The composition for an optical adjustment layer also optionally includes a plurality of inorganic particles for adjusting the refractive index of the optical adjustment layer to meet the demand. The inorganic particles are, for example but not limited to, cerium oxide particles. Specific examples of the cerium oxide-based particles are colloidal cerium oxide particles or hollow cerium oxide fine particles. Preferably, the inorganic particles have a refractive index lower than a refractive index of the photocurable bonding agent. Preferably, the inorganic particles have a refractive index ranging from 1.10 to 1.50 at a wavelength of 400 nm. Preferably, the inorganic particles have an average particle diameter ranging from 5 nm to 10 nm.

The preparation method of the composition for an optical adjustment layer is not particularly limited, and a conventional method may be employed. For example, the above components may be placed in a stirrer and stirred uniformly. The photocurable adhesive is used in an amount ranging from 3 to 80% by weight based on the total amount of the mixed solution, and the photoinitiator is used in an amount ranging from 0.1 to 10% by weight, and the solvent is used in an amount ranging from 100 to 80% by weight. It is 10 to 95% by weight. When the mixed solution further contains a fluorine-containing compound, the photocurable adhesive is used in an amount ranging from 3 to 80% by weight based on 100% by weight of the total of the mixed solution, and the photoinitiator is used in an amount ranging from 0.1 to 0.1% by weight. Up to 10% by weight, and the solvent is used in an amount ranging from 10 to 95% by weight, and the fluorine-containing compound is used in an amount ranging from 0.1 to 10% by weight. Preferably, the fluorine-containing compound is used in an amount ranging from 0.5 to 5 wt%. The total amount of the inorganic particles used is in the range of 1 to 90 parts by weight based on 100 parts by weight of the total of the mixed solution.

The optical adjustment layer has a refractive index ranging from 1.33 to 1.52 at a wavelength of 400 nm. If the refractive index of the optical adjustment layer is less than 1.33, the content of the inorganic particles or the fluorine-containing compound in the optical adjustment layer is large, so that the dispersion of the inorganic particles or the fluorine-containing compound in the optical adjustment layer is poor, and the influence is affected. The adhesion between the optical adjustment layer and the transparent substrate does not allow the optical adjustment layer to be formed well. If the refractive index of the optical adjustment layer is greater than 1.52, not only the total light transmittance of the conductive transparent laminate is lowered, but also the patterned conductive transparent laminate obtained later is reflected by the pattern portion. The difference between the reflectance and the reflectance of the reflected light emitted from the non-pattern portion becomes large (ΔR>1), so that the user can see a significant trace of the pattern of the transparent conductive layer.

The optical adjustment layer has a physical thickness ranging from 10 nm to 30 nm. When the physical thickness of the optical adjustment layer is less than 10 nm, the optical adjustment layer cannot be favorably formed into a film, so that the total light transmittance of the conductive transparent laminate is insufficient. If the physical thickness of the optical adjustment layer is greater than 30 nm, the penetration color of the conductive transparent laminate may be yellow. Preferably, the optical adjustment layer has a physical thickness ranging from 15 nm to 25 nm.

[Transparent Conductive Layer]

The material of the transparent conductive layer is selected from the group consisting of indium oxide, tin oxide, titanium oxide, aluminum oxide, zinc oxide, gallium oxide or a combination thereof. Preferably, the transparent conductive layer is made of Indium Tin Oxide (ITO), which is a mixture of indium oxide and tin oxide.

The transparent conductive layer of the conductive transparent laminate has a carrier concentration of 10 × 10 ²¹ /cm ³ to 20 × 10 ²¹ /cm ³ . When the carrier concentration of the transparent conductive layer of the conductive transparent laminate is less than 10 × 10 ²¹ /cm ³ , the reflectance of the reflected light emitted from the patterned portion of the patterned conductive transparent laminate obtained in the subsequent manner is The reflectance of the reflected light emitted from the non-pattern portion has a large difference, and when the user views it, the trace of the transparent conductive layer is marked. When the carrier concentration of the transparent conductive layer of the conductive transparent laminate is greater than 20×10 ²¹ /cm ³ , the transparent conductive layer of the conductive transparent laminate exhibits metal characteristics, thereby allowing the transparent conductive layer of the conductive transparent laminate to pass through. Poor permeability. Preferably, the transparent conductive body of the conductive transparent laminate has a carrier concentration of 15 × 10 ²¹ /cm ³ to 20 × 10 ²¹ /cm ³ .

The transparent conductive layer of the conductive transparent laminate has a physical thickness ranging from 10 nm to 30 nm, preferably from 15 nm to 30 nm. When the thickness of the transparent conductive layer of the conductive transparent laminate is less than 10 nm, it is difficult to uniformly form the transparent conductive layer into a film and there is a problem of uneven film thickness, which leads to uneven conductivity and a stable surface cannot be obtained. The value of the resistance, or the surface resistance value is too high. When the thickness of the transparent conductive layer is greater than 30 nm, the total light transmittance of the conductive transparent laminate is decreased, and the transparent conductive layer of the conductive transparent laminate is prone to brittle cracking in the subsequent process of the touch panel, and is not conducive to technology. The need for thinner products. Moreover, when the transparent conductive layer of the conductive transparent laminate is made of indium tin oxide and has a thickness of more than 30 nm, the transparent color of the transparent conductive layer is yellow.

Preferably, the conductive transparent laminate further comprises a functional layer disposed on the transparent substrate and opposite to the optical adjustment layer.

Preferably, the functional layer is selected from the group consisting of a hard coat layer, an anti-glare layer, an anti-fingerprint layer, a self-healing layer, an anti-reflective layer or a combination thereof. E.g When the functional layer is a combination of a hard coat layer and an anti-glare layer, the position of the hard coat layer and the anti-glare layer is not particularly limited, for example, the hard coat layer is disposed on the transparent substrate and the optical adjustment layer On the opposite side, the anti-glare layer is disposed on the hard coat layer.

The hard coat layer can enhance the mechanical strength of the transparent substrate.

The preparation method of the hard coat layer is not particularly limited, and a conventional method such as a roll coating method, a spin coating method, a dip coating method, a bar coating method, and a gravure method may be employed. A coating method or the like is applied on the transparent substrate, and the mixed solution for forming a hard coat layer is hardened and dried, that is, the hard coat layer is formed on the transparent substrate.

The kind of the mixed solution for forming the hard coat layer is not particularly limited herein, and is not limited thereto, for example, but not limited to a mixture for forming a hard coat layer comprising polymethyl methacrylate, 2-butanone, and a photoinitiator. Solution.

Preferably, the mixed solution for forming a hard coat layer is coated on the transparent substrate to a thickness ranging from 1.0 μm to 10 μm. When the thickness of the mixed solution for forming a hard coat layer coated on the transparent substrate is less than 1.0 μm, the hard coat layer formed by subsequent hardening cannot effectively enhance the mechanical strength of the transparent substrate (ie, the pencil hardness of the transparent substrate is not H). When the thickness of the mixed solution for forming a hard coat layer on the transparent substrate is greater than 10 μm, the hard coat layer formed by the subsequent hardening shrinks to a large extent, thereby causing the transparent substrate to be easily curled, and Will reduce production efficiency and follow-up operations.

The material of the antiglare layer is not particularly limited, and is not limited thereto, for example, polyacrylic acid, polyurethane, or polyester.

The material of the anti-fingerprint layer is not particularly limited, and is not limited thereto, for example, polyacrylic acid, polyurethane, or polyester.

The self-repairing layer can improve the recovery of the transparent conductive layer or the patterned transparent conductive layer when squeezed. The material of the self-healing layer is not particularly limited herein, and is not limited to, for example, polyacrylic acid, polyurethane, or polyester.

The material of the antireflection layer is not particularly limited, and examples thereof include, but are not limited to, polyacrylic acid, polyurethane, or polyester.

1‧‧‧ Conductive transparent laminate

11‧‧‧Transparent substrate

12‧‧‧Optical adjustment layer

13‧‧‧Transparent conductive layer

15‧‧‧ patterned conductive transparent layer

151‧‧‧The Department of Patterns

152‧‧‧Non-pattern department

14‧‧‧ functional layer

2‧‧‧ patterned conductive transparent laminate

5‧‧‧Light

6‧‧‧Light emitted by the pattern

7‧‧‧Light emitted by the non-patterned part

Other features and effects of the present invention will be apparent from the following description of the drawings. FIG. 1 is a schematic view showing the structure of the conductive transparent laminate of the present invention; FIG. 2 is a schematic view showing the conductive of the present invention. FIG. 3 is a schematic view showing the structure of the patterned conductive transparent laminate of the present invention; and FIG. 4 is a schematic view showing how to measure the pattern portion and the non-pattern of the patterned conductive transparent laminate. The reflectivity of the part.

The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting. Before the present invention is described in detail, it should be noted that in the following description, similar elements are denoted by the same reference numerals.

Referring to FIG. 1, the conductive transparent laminate 1 of the present invention comprises: The transparent substrate 11 , an optical adjustment layer 12 contacting the transparent substrate 11 , and a transparent conductive layer 13 contacting the optical adjustment layer 12 . The transparent substrate 11, the optical adjustment layer 12, and the transparent conductive layer 13 are as described above, and thus will not be described again.

Referring to FIG. 2, the conductive transparent laminate 1 of the present invention comprises: a transparent substrate 11, an optical adjustment layer 12 contacting the transparent substrate 11, a transparent conductive layer 13 contacting the optical adjustment layer 12, and a transparent layer The functional layer 14 on the transparent substrate 11 opposite to the optical adjustment layer 12. The functional layer 14 is as described above and will not be described again.

Referring to FIG. 3 , the patterned conductive transparent laminate 2 of the present invention comprises: a transparent substrate 11 , an optical adjustment layer 12 contacting the transparent substrate 11 , and a patterned transparent conductive contact with the optical adjustment layer 12 . Layer 15. The transparent substrate 11, the optical adjustment layer 12, and the patterned transparent conductive layer 15 are as described above, and thus will not be described again.

Referring to Fig. 3, the patterned transparent conductive layer 15 of the patterned conductive transparent laminate of the present invention has a "pattern portion 151" and a "non-pattern portion 152". The "pattern portion 151" refers to a region having the transparent conductive layer 15 on the optical adjustment layer 12, and the "non-pattern portion 152" refers to a region on the optical adjustment layer 12 that does not have the transparent conductive layer 15.

<Example> [Preparation Example 1] Composition for optical adjustment layer

4 wt% of ultraviolet curable acrylic resin (model: 7150, manufactured by DIC, refractive index: 1.52), 93 wt% of methyl isobutyl ketone, 1 wt% of fluororesin (model: F-8261, manufactured by Degussa), 1 wt% Fluorine single The body (model: FSO, manufactured by DuPont), and 1 wt% of a photoinitiator (model: IRGACURE 184, manufactured by Ciba) were uniformly mixed to form a mixed solution. Then, 3 parts by weight of cerium oxide particles (Model: MIBK-ST, manufactured by Nissan Chemical Co., Ltd., average particle diameter: 20 nm) was added in an amount of 100 parts by weight based on the total amount of the mixed solution, and the optical of Preparation Example 1 was obtained. Adjust the layer composition.

[Preparation Examples 2 to 5] Compositions for Optical Adjustment Layer

According to the raw material type and the amount of use in the following Table 1, the same procedure as in Preparation Example 1 was carried out, and the optical conditioning layer compositions of Preparation Examples 2 to 5 were respectively obtained. Among the preparation examples 4 and 5, cerium oxide particles were replaced with zirconia (model: SZR-K, manufactured by Seiko Chemical Co., Ltd., refractive index: 2.2, average particle diameter range: 5 to 20 nm).

No use.

[Example 1] Conductive transparent laminate and patterned conductive transparent laminate

The composition for an optical adjustment layer of Preparation Example 1 was coated on a surface of a transparent substrate (material: PET, A4300 manufactured by TOYOBO; physical thickness: 125 μm) using a wire-bar at 80 ° C. After drying for 2 minutes, followed by hardening and drying with ultraviolet light of 900 mJ/cm ² , an optical adjustment layer (physical thickness: 10 nm, refractive index: 1.33) was formed on one surface of the transparent substrate to obtain a first layer. Fit.

The first laminate is placed in a magnetron sputtering chamber, the target is Sn/(In+Sn)=5wt% ITO target, and the cavity vacuum is pumped to 3×10 ^-6 torr, After the sputtering gas Ar and O ₂ are introduced into the cavity (O ₂ /Ar flow ratio = 0.02), the optical adjustment layer 1 of the first laminate is sputtered (working pressure: 5 × 10 ^-4 torr, power) : 4 KW, first laminate temperature: 25 to 30 ° C), that is, a metal oxide layer is formed on the optical adjustment layer of the first laminate (material: ITO, thickness: 25 nm, carrier concentration: 8.27×10) ²¹ / cm ³ ), a second laminate was obtained.

Next, the second laminate was placed in an oven, and a crystal annealing treatment of the metal oxide layer was performed at 150 ° C for 1 hour to obtain a transparent conductive layer (material: ITO, thickness: 25 nm, carrier concentration: 17.5×). 10 ²¹ /cm ³ ), that is, the conductive transparent laminate of Example 1 was obtained.

After the conductive transparent laminate of Example 1 was cut into 6 cm×6 cm, it was partially immersed in a 5 wt% hydrogen chloride (HCl) solution for 3 minutes to remove part of the transparent conductive layer to make the transparent guide. The electric layer was patterned to obtain the patterned conductive transparent laminate of Example 1.

[Examples 2 to 4 and Comparative Examples 1 to 2] Conductive transparent laminate and patterned conductive transparent laminate

The composition for the optical adjustment layer was selected according to the preparation example numbers shown in Table 2, and the physical thickness of the coating was controlled, and the preparation was carried out in the same manner as in Example 1 to prepare Examples 2 to 4 and Comparative Examples 1 to 2. Conductive transparent laminate and patterned conductive transparent laminate.

[Example 5 and Comparative Example 3] Conductive transparent laminate and patterned conductive transparent laminate

The composition for the optical adjustment layer was selected according to the preparation example numbers shown in Table 2, the physical thickness of the coating was controlled, and the carrier concentration and physical thickness of the transparent conductive layer were prepared according to the same procedure as in Example 1. The conductive transparent laminate of Example 5 and Comparative Example 3 and the patterned conductive transparent laminate were obtained. Wherein, the condition parameters of the transparent conductive layer of Example 5 were prepared, except that the first laminate temperature during the sputtering process was 100 ° C, and the other conditions were the same as in Example 1. The condition parameters of the transparent conductive layer of Comparative Example 3 were prepared, except that the target was an ITO target of Sn/(In+Sn)=10% by weight, and the other conditions were the same as in Example 1.

[Comparative Example 4] Conductive transparent laminate and patterned conductive transparent laminate

The optical adjustment layer composition of Preparation Example 5 was coated on a surface of a transparent substrate (material: PET, A4300 manufactured by TOYOBO; physical thickness: 125 μm) using a wire bar, and dried at 80 ° C for 2 minutes. Then, after hardening and drying with ultraviolet light of 1200 mJ/cm ² , a first optical adjustment layer (physical thickness: 60 nm, refractive index: 1.74) was formed on one surface of the transparent substrate. Further, the composition for optical adjustment layer of Preparation Example 2 was applied onto the first optical adjustment layer by using a wire bar, and dried at 80 ° C for 2 minutes, and then hardened and dried by ultraviolet light of 900 mJ/cm ² to form a film. The second optical adjustment layer (physical thickness: 25 nm, refractive index: 1.40) gave a first laminate.

The first laminate is placed in a magnetron sputtering chamber, the target is Sn/(In+Sn)=5wt% ITO target, and the cavity vacuum is pumped to 3×10 ^-6 torr, After the sputtering gas Ar and O ₂ were passed through the chamber (O ₂ /Ar flow ratio = 0.02), sputtering was performed (working pressure: 5 × 10 ^-4 torr, power: 4 KW, first laminate temperature: 25) Up to 30 ° C), that is, a metal oxide layer (material: ITO, thickness: 25 nm, carrier concentration: 8.27 × 10 ²¹ /cm ³ ) was formed on the second optical adjustment layer of the first laminate. The second laminate.

Next, the second laminate was placed in an oven, and a crystal annealing treatment of the metal oxide layer was performed at 150 ° C for 1 hour to obtain a transparent conductive layer (material: ITO, thickness: 25 nm, carrier concentration: 17.5×). 10 ²¹ /cm ³ ), that is, the conductive transparent laminate of Comparative Example 4 was obtained.

After the conductive transparent laminate of Comparative Example 4 was cut into 6 cm×6 cm, it was partially immersed in a 5 wt% hydrogen chloride (HCl) solution for 3 minutes to remove a part of the transparent conductive layer to make the transparent conductive layer pattern. The patterned conductive transparent laminate of Comparative Example 4 was obtained.

[Evaluation measurement]

1. The refractive index of the optical adjustment layer

To facilitate the description of the measurement process, the optical adjustment of Preparation Example 1 The layers are described by the composition, and the remaining preparations are measured in the same manner.

The optical conditioning layer composition of Preparation Example 1 was coated on the surface of a transparent substrate (material: PET, A4300 manufactured by TOYOBO; thickness: 125 μm) using a wire bar, followed by drying at 80 ° C for 2 minutes, and then at 900 mJ. After the UV light of /cm ² is hardened and dried, an optical adjustment layer is formed. Next, the refractive index of the optical adjustment layer at a wavelength of 400 nm was measured with an Abbe refractometer (manufactured by Atago Corporation).

2. Carrier concentration of transparent conductive layer

To facilitate the description of the measurement process, the description is made in the first embodiment, and the remaining embodiments and comparative examples are measured in the same manner.

The carrier concentration of the metal oxide layer of the second laminate of Example 1 and the carrier concentration of the transparent conductive layer of the conductive transparent laminate were measured by a Hall effect analyzer (manufactured by Ecopia, Model: HMS-3000) .

3. Optical adjustment layer and physical thickness of transparent conductive layer

The physical thickness measurement of the optical adjustment layer and the transparent conductive layer of each of the examples and the comparative examples was measured using a transmission electron microscope (manufactured by JEOL Co., Ltd., model: JEM-2100F).

The following is a description of the total light transmittance, the penetration color, the penetration color difference, the reflectance difference, and the appearance evaluation measurement process, and the conductive transparent laminate of Embodiment 1 and the patterned conductive transparent laminate are described. The remaining examples and comparative examples were measured in the same manner. The evaluation measurement results are shown in Table 2.

4. Full light transmittance (TT%)

The total light transmittance of the conductive transparent laminate of Example 1 was measured in accordance with the method of JIS K 7105 using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

5. Penetration color (b ₁ *) and penetration color difference (△b*)

The conductive transparent laminate patterned in Example 1 was measured by a JIS Z 8722 standard measurement method using a spectroscopic spectrometer manufactured by Hitachi, Ltd., and the blue-yellow color of the L*a*b* color system defined in JIS. The index b* is the benchmark. The light of the spectroscopic spectrometer enters from the transparent substrate of the patterned conductive transparent laminate, and the penetration color (b ₁ *) of the light emitted from the pattern portion is measured. The light of the spectroscopic spectrometer is entered from the transparent substrate of the patterned conductive transparent laminate, and the penetration color (b ₂ *) of the light emitted from the non-pattern portion is measured, and b ₁ * is subtracted from b ₂ * The color difference is Δb*.

6. Reflectance difference (△R)

The black tape (manufactured by Toyo Electric Co., Ltd.) was attached to the transparent substrate of the conductive transparent laminate patterned in Example 1 using a roller, and placed in a spectroscopic spectrometer (label: Hitachi; model: U4100) with an initial amount of 380 nm. The wavelength was measured and irradiated, and measured to 780 nm, and the reflection intensity of each wavelength was recorded to obtain a reflectance spectrum. Referring to Fig. 4, light rays 5 of the spectroscopic spectrometer are entered from the pattern portion 151 of the patterned conductive transparent laminate 2, and are in contact with each layer, and are reflected, and the reflectance spectrum of the reflected light 6 emitted from the pattern portion 151 is measured (A) _k ). The light 5 of the spectroscopic spectrometer is entered from the non-pattern portion 152 of the patterned conductive transparent laminate 2, and is in contact with each layer and then reflected, and the reflectance spectrum (B _k ) of the reflected light 7 emitted from the non-pattern portion 152 is measured. . The reflectance difference (ΔR) is obtained by the following formula. When the ΔR range is 1 or less, when the patterned conductive transparent laminate is applied to the touch panel, the user can not easily see the transparency when viewing. Traces of the patterned conductive layer.

n: number of samples measured

7. Appearance evaluation

After the black tape (manufactured by Toyo Electric Co., Ltd.) was bonded to the transparent substrate of the conductive transparent laminate patterned in Example 1, the pattern portion and the non-pattern portion of the patterned transparent conductive layer were visually observed. If the pattern portion and the non-pattern portion cannot be discriminated at any visual angle, the evaluation result is denoted by ○. When the visual angle is 60 degrees (0 degrees as the normal of the test plane), the pattern portion and the non-pattern portion can be slightly discriminated, and the evaluation result is recorded as Δ. If the pattern portion and the non-pattern portion can be clearly distinguished at any visual angle, the evaluation result is recorded as ×.

From the experimental data of Examples 1 to 5 of Table 2, it can be confirmed that the present invention is combined with an optical adjustment layer which is in contact with a transparent substrate and has a refractive index ranging from 1.33 to 1.52 at a wavelength of 400 nm and a physical thickness ranging from 10 nm to 30 nm. a transparent conductive layer in contact with the optical adjustment layer and having a carrier concentration ranging from 10 × 10 ²¹ /cm ³ to 20 × 10 ²¹ /cm ³ enables the pattern portion of the patterned conductive transparent laminate to enter The difference between the reflectance of the light emitted therefrom and the reflectance of the light emitted from the non-pattern portion and emitted therefrom is 0.57 to 0.92, and the user cannot discern the patterned transparent conductive by visual observation. The pattern portion and the non-pattern portion of the layer.

In Comparative Example 1, the physical thickness of the optical adjustment layer was 35 nm. The difference between the reflectance of the light emitted from the pattern portion of the patterned conductive transparent laminate and the reflectance of the light emitted from the non-pattern portion is large (ΔR is 1.16), and the user can clearly see by visual observation. The pattern portion and the non-pattern portion of the patterned transparent conductive layer are discriminated.

In Comparative Example 2, the refractive index of the optical adjustment layer at a wavelength of 400 nm was 1.60, so that the difference between the reflectance of the light emitted from the pattern portion of the patterned conductive transparent laminate and the reflectance of the light emitted from the non-pattern portion was Large (ΔR is 1.57), and the user can slightly discern the pattern portion and the non-pattern portion of the patterned transparent conductive layer by visual observation.

In Comparative Example 3, since the carrier concentration of the transparent conductive layer was 7.54 × 10 ²¹ /cm ³ , the reflectance of the light emitted from the pattern portion of the patterned conductive transparent laminate and the reflection of the light emitted from the non-pattern portion were caused. The difference in the rate is large (ΔR is 2.69), and the user can clearly distinguish the pattern portion and the non-pattern portion of the patterned transparent conductive layer by visual observation.

The patterned conductive transparent laminate of Comparative Example 4 is similar to the structure of the Republic of China Patent Publication No. TW201133515 described in the prior art paragraph, and has a refractive index ranging from 1.33 to 1.52 at a wavelength of 400 nm and a physical thickness ranging from 10 nm to When the 30 nm optical adjustment layer is in contact with the transparent substrate, the difference between the reflectance of the light emitted from the pattern portion of the patterned conductive transparent laminate and the reflectance of the light emitted from the non-pattern portion is large (ΔR is 2.29). And the user can clearly distinguish the pattern portion and the non-pattern portion of the patterned transparent conductive layer by visual observation.

In summary, the conductive transparent laminate of the present invention contacts the transparent substrate by an optical adjustment layer having a refractive index ranging from 1.33 to 1.52 at a wavelength of 400 nm and a thickness ranging from 10 nm to 30 nm at a wavelength of 400 nm, and is matched so that the carrier concentration range is a transparent conductive layer of 10 × 10 ²¹ /cm ³ to 20 × 10 ²¹ /cm ^{3 is} in contact with the optical adjustment layer such that the reflectance of the reflected light emitted from the pattern portion of the patterned conductive transparent laminate is Since the reflectance of the reflected light emitted from the non-pattern portion has a small difference, when the touch panel is applied, the trace of the pattern of the transparent conductive layer is not easily seen by the user during viewing, and the object of the present invention can be achieved.

The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.

1‧‧‧ Conductive transparent laminate

11‧‧‧Transparent substrate

12‧‧‧Optical adjustment layer

13‧‧‧Transparent conductive layer

Claims (9)

A conductive transparent laminate comprising: a transparent substrate; an optical adjustment layer contacting the transparent substrate, the optical adjustment layer having a refractive index ranging from 1.33 to 1.52 at a wavelength of 400 nm, and a physical thickness ranging from 10 nm to 30 nm; The conductive layer is in contact with the optical adjustment layer, and the transparent conductive layer has a carrier concentration ranging from 10×10 ²¹ /cm ³ to 20×10 ²¹ /cm ³ and a physical thickness ranging from 10 nm to 30 nm. The conductive transparent laminate according to claim 1, wherein the transparent substrate has a refractive index ranging from 1.40 to 1.80 at a wavelength of 400 nm. The conductive transparent laminate according to claim 1, wherein the transparent substrate has a physical thickness ranging from 2 μm to 300 μm. The conductive transparent laminate according to claim 1, wherein the transparent conductive body of the conductive transparent laminate has a carrier concentration of 15 × 10 ²¹ /cm ³ to 20 × 10 ²¹ /cm ³ . A patterned conductive transparent laminate comprising: a transparent substrate; an optical adjustment layer contacting the transparent substrate, the optical adjustment layer having a refractive index ranging from 1.33 to 1.52 at a wavelength of 400 nm and a physical thickness ranging from 10 nm to 30 nm a patterned transparent conductive layer contacting the optical adjustment layer, the patterned transparent conductive layer having a carrier concentration ranging from 10×10 ²¹ /cm ³ to 20×10 ²¹ /cm ³ , and a physical thickness range It is from 10 nm to 30 nm. The patterned conductive transparent laminate of claim 5, wherein the transparent substrate has a refractive index ranging from 1.40 to 1.80 at a wavelength of 400 nm. The patterned conductive transparent laminate of claim 5, wherein the transparent substrate has a physical thickness ranging from 2 μm to 300 μm. The patterned conductive transparent laminate according to claim 5, wherein the transparent conductive body of the conductive transparent laminate has a carrier concentration of 15 × 10 ²¹ /cm ³ to 20 × 10 ²¹ /cm ³ . A touch panel comprising the conductive transparent laminate of claim 1 or the patterned conductive transparent laminate of claim 5.