TWI527063B - Conductive transparent laminates, patterned conductive transparent laminates and touch panels - Google Patents

Description

Conductive transparent laminate, patterned conductive transparent laminate and touch panel

The invention relates to a conductive transparent laminate for a touch panel, in particular to a conductive transparent laminate comprising an optical adjustment layer.

In recent years, touch-type 3C products, such as smart phones, touch-type notebook computers, and tablet computers, have become more and more popular, driving the booming of the touch panel industry.

The touch panel comprises a conductive transparent laminate, wherein the conductive transparent laminate comprises a transparent substrate and a transparent conductive layer deposited on the transparent substrate. When the total light transmittance of the conductive transparent laminate is low, the brightness of the screen of the touch panel is lowered, which is difficult for the user to view. In addition, when the material of the transparent conductive layer is Indium Tin Oxide (ITO), the ITO itself will be slightly yellow, which will make the transparent color of the conductive transparent laminate appear yellow, which will cause the touch panel to be Display color deviation. Therefore, a manufacturer proposes to provide a plurality of optical adjustment layers between a transparent substrate and a transparent conductive layer, adjust the refractive index and thickness of the optical adjustment layers, adjust the penetration color of the conductive transparent laminate, and improve the conductive transparent laminate. Full light penetration.

In addition, the "projected capacitive touch panel" researched and developed by various touch panel manufacturers will further pattern the transparent conductive layer on the conductive transparent laminate to produce a patterned conductive transparent. Laminated body. 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 transparent. In the pattern portion and the non-pattern portion of the laminate, the difference between the reflected color and the reflectance of the reflected light emitted from the pattern portion and the reflected color and the reflectance of the reflected light emitted from the non-pattern portion is large, and the user is likely to view the touch panel. Traces of the patterning of the transparent conductive layer are clearly visible.

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 setting is disclosed in Japanese Laid-Open Patent Publication No. TW201133515 An indium oxide layer 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 transparent conductive film of the patent has a penetrating chromaticity b ₁ * ranging from -0.6 to 0.5, and the total light transmittance is in the range of 88.2 to 91.4 (TT%), but the inventor of the present invention according to the content of the patent A transparent conductive film was prepared, and an indium oxide ruthenium (ITO) layer was patterned and tested, and the reflected color and reflectance of the reflected light emitted from the pattern portion of the transparent conductive film of the patent and the reflection from the non-pattern portion were found. The difference between the reflected color and the reflectance of the light is still too large. Therefore, the transparent conductive film of the Taiwan patent case obviously does not meet the demand for the user's desire to see the trace of the transparent conductive layer pattern when the user touches the touch panel. .

In summary, the problem of improving the display quality of the touch panel is greatly improved by improving the conductive transparent laminate to solve the problem that the user can easily see the trace of the transparent conductive layer during viewing.

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

Accordingly, a first object of the present invention is to provide a conductive transparent laminate. Patterning the transparent conductive layer of the conductive transparent laminate to obtain a patterned conductive transparent laminate, and reflecting color and reflectance of the reflected light emitted from the pattern portion of the patterned conductive transparent laminate and the non-pattern The difference between the reflected color and the reflectance of the reflected light emitted by the portion is small, and when applied to the touch panel, the user can hardly see the trace of the patterning of the transparent conductive layer when viewing.

The conductive transparent laminate of the present invention comprises a transparent substrate, a first optical adjustment layer disposed on the transparent substrate, a second optical adjustment layer disposed on the first optical adjustment layer, and a first optical adjustment layer disposed on the first optical adjustment layer A transparent conductive layer on the second optical adjustment layer. The first optical adjustment layer has a refractive index ranging from 1.65 to 1.83 and a physical thickness ranging from 25 nm to 35 nm; the second optical adjustment layer has a refractive index ranging from 1.33 to 1.52 and a physical thickness ranging from 20 nm to 40 nm.

Accordingly, a second object of the present invention is to provide a conductive transparent laminate that improves and reduces the patterning of patterned traces.

The patterned conductive transparent laminate of the present invention comprises a transparent substrate, a first optical adjustment layer disposed on the transparent substrate, a second optical adjustment layer disposed on the first optical adjustment layer, and a setting a patterned transparent conductive layer on the second optical adjustment layer. The first optical adjustment layer has a refractive index ranging from 1.65 to 1.83 and a physical thickness ranging from 25 nm to 35 nm; the second optical adjustment layer has a refractive index ranging from 1.33 to 1.52 and a physical thickness ranging from 20 nm to 40 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 adjusts the refractive index and thickness of the first optical adjustment layer and the second optical adjustment layer to form a subsequently patterned conductive transparent laminate, because of the pattern portion thereof. The difference between the reflected color and the reflectance of the reflected light emitted from the reflected light and the reflected light emitted from the non-pattern portion is small, so that the trace of the transparent conductive layer is not obvious, and 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, forming a first optical adjustment layer on the transparent substrate, and then forming a second optical on the first optical adjustment layer; Adjusting the layer to obtain a first laminate, and forming a transparent conductive layer on the second optical adjustment layer The layer is the conductive transparent laminate of the present invention.

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. 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 where the transparent conductive layer of the patterned conductive transparent laminate is not removed, and the "non-pattern of the patterned conductive transparent laminate" "Part" refers to the area of the patterned conductive transparent laminate after the transparent conductive layer has been removed.

Herein, the reflection color and reflectance of the pattern portion of the patterned conductive transparent laminate means that light enters from the pattern portion of the patterned conductive transparent laminate and contacts the patterned conductive transparent laminate. The light is partially reflected at each layer, and the reflected light and reflectance obtained by the light emitted from the pattern portion after reflection are added. The reflection color and reflectance of the non-pattern portion of the patterned conductive transparent laminate means that light enters from the non-pattern portion of the patterned conductive transparent laminate and contacts the layers in the patterned conductive transparent laminate. The light is partially reflected, and the reflected light and reflectance are added by the light emitted from the non-pattern portion after the reflection.

The transparent substrate, the first optical adjustment layer, the second 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.

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 polyvinylidene chloride (PVDC), etc.; (4). Cellulose esters: triacetate (triacetyl cellulose (TAC) or acetate cellulose, etc.; (5). Polycarbonate: polycarbonate (PC), etc.; (6). Polyvinyl acetate ( Polyvinyl acetate) and its derivatives: polyvinyl alcohol (PVA), etc.; (7). (meth) acrylate polymer: methacrylate homopolymer [eg polymethyl methacrylate (polymethylmethacrylate, PMMA)]; (8). Cycloolefin polymer (cyclo olefin polymer) Polymer, COP): a cyclic olefin copolymer (COC), etc.; (9). Polyimides.

Preferably, the transparent substrate has a physical thickness ranging from 2 μm to 300 μm, more preferably 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 bent or even broken due to the inability to withstand the tension in the subsequent process, thereby making the subsequent layer process difficult. If it is transparent When the physical thickness of the substrate exceeds 300 μm, the total light transmittance of the conductive transparent laminate is lowered, and the manufacturing cost is increased, and the current technical product is not required to be thinned.

[First optical adjustment layer]

The first optical adjustment layer is formed by photohardening a composition for a first optical adjustment layer comprising a photocurable binder, a plurality of metal oxide particles, a photoinitiator, and a solvent.

The photocurable adhesive is not particularly limited, and examples thereof include, but are not limited to, a photocurable acrylic resin, a polyfunctional monomer having a (meth)acryl group, 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.

Preferably, the metal oxide particles are selected from the group consisting of titanium oxide, zirconium oxide or a combination thereof. Preferably, the metal oxide particles have a refractive index ranging from 2.0 to 3.0. Preferably, the metal oxide particles have an average particle diameter ranging from 5 nm to 20 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, benzyl group knot a compound, a compound having a benzoin structure (for example, benzoin methyl ether), an ester having an α-methoxy group, a thioxanthone or anthraquinone, etc. The agents can be used singly or in combination.

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

The preparation method of the composition for the first 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. Alternatively, after the photocurable binder, the photoinitiator, and the solvent are uniformly mixed to form a first mixed solution, a plurality of metal oxide particles are uniformly mixed with the first mixed solution. The photocurable adhesive is used in an amount ranging from 3 to 80% by weight based on the total amount of the first mixed solution of 100% by weight, and the photoinitiator is used in an amount ranging from 0.1 to 10% by weight, the amount of the solvent used. The range is from 10 to 95% by weight. The metal oxide particles are used in a total amount ranging from 10 to 90 parts by weight based on 100 parts by weight of the total of the first mixed solution.

The formation method of the first optical adjustment layer 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, and in terms of productivity and manufacturing cost, Wet coating Cloth is better. 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 first optical adjustment layer can be continuously formed.

The refractive index of the first optical adjustment layer ranges from 1.65 to 1.83, preferably from 1.68 to 1.78. If the refractive index of the first optical adjustment layer is less than 1.65, the penetration color of the conductive transparent laminate is yellowish, and the patterning trace of the subsequently obtained patterned conductive transparent laminate is more remarkable. If the refractive index is greater than 1.83, the content of the metal oxide particles in the first optical adjustment layer is large, so that the dispersibility of the metal oxide particles is not good, and further, the patterned conductive transparent obtained later is made transparent. The patterning traces of the laminate are more pronounced.

The first adjustment layer has a physical thickness ranging from 25 nm to 35 nm. When the physical thickness of the first optical adjustment layer is less than 25 nm, the reflectance of the first laminate cannot be effectively improved, so that the subsequently formed patterned conductive transparent laminate is light that is emitted by the pattern portion and is emitted therefrom. The reflectance difference between the reflectance and the light emitted by the non-pattern portion thereof is increased, resulting in a more pronounced patterning trace. When the physical thickness is greater than 35 nm, the reflected color difference between the reflected color of the reflected light emitted from the pattern portion of the patterned conductive transparent laminate and the reflected light emitted from the non-pattern portion is significantly increased, and then the patterned Conductive transparent laminate patterning marks are more pronounced.

[Second optical adjustment layer]

The second optical adjustment layer is composed of a second optical adjustment layer composition comprising a second mixed solution and a plurality of inorganic particles. Formed by the chemical composition, wherein the second mixed solution comprises a photocurable binder, a photoinitiator, and a solvent.

The photocurable binder, photoinitiator, and solvent are as described above, and therefore will not be described again.

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 1.30 to 1.50. Preferably, the inorganic particles have an average particle diameter ranging from 10 nm to 100 nm.

The second mixed solution further includes a fluorine-containing compound for adjusting the refractive index of the second optical adjustment layer to meet the demand. 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 preparation method of the composition for the second 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 second mixed solution, and the photoinitiator is used in an amount ranging from 0.1 to 10% by weight, and the use of the solvent The amount ranges from 10 to 95% by weight. 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 second mixed solution.

The second optical adjustment layer is formed in the same manner as the first optical The formation of the adjustment layer is not described here.

The second optical adjustment layer has a refractive index ranging from 1.33 to 1.52. When the refractive index of the second optical adjustment layer is less than 1.33, the content of the inorganic particles in the second optical adjustment layer is large, so that the dispersibility of the inorganic particles in the second optical adjustment layer is not good, and the inorganic particles cannot be satisfactorily The second optical adjustment layer is formed into a film. If the refractive index of the second optical adjustment layer is greater than 1.52, not only the total light transmittance of the conductive transparent laminate is reduced, but also the patterned conductive transparent laminate obtained later is reflected by the pattern portion. The reflected color difference between the reflected color of the light and the reflected light emitted from the non-patterned portion becomes large, resulting in a more pronounced patterning trace.

The second adjustment layer has a physical thickness ranging from 20 nm to 40 nm, preferably from 25 nm to 35 nm. When the physical thickness of the second optical adjustment layer is less than 20 nm, the total light transmittance of the conductive transparent laminate is insufficient. If the physical thickness of the second optical adjustment layer is greater than 40 nm, the penetration color of the conductive transparent laminate may be yellow.

[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.

Preferably, the transparent conductive layer has a refractive index ranging from 1.85 to 2.35, more preferably from 1.90 to 2.30.

Preferably, the transparent conductive layer has a thickness ranging from 5 nm to 100 nm, more preferably from 10 nm to 50 nm. When the thickness of the transparent conductive layer is small When the thickness is 5 nm, it is difficult to form the transparent conductive layer uniformly, and there is a problem that the film thickness is uneven, which further causes a phenomenon of uneven conductivity, and a stable surface resistance value cannot be obtained, or the surface resistance value is too high. When the thickness of the transparent conductive layer is greater than 100 nm, the manufacturing cost increases, the total light transmittance of the conductive transparent laminate decreases, the transparent conductive layer is brittle during subsequent processing, and the demand for thinning of the technology product is disadvantaged. When the material of the transparent conductive layer is indium tin oxide and the thickness is greater than 100 nm, the transparent color of the transparent conductive layer is yellow.

The method for preparing the transparent conductive layer is not particularly limited, and may be a conventional method such as a vapor deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method (CVD), or a plating method. 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.

In addition, the transparent conductive layer or the patterned transparent conductive layer may be subjected to a crystal annealing treatment to crystallize it as needed. Preferably, 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.

Preferably, the conductive transparent laminate further comprises a first functional layer disposed between the first optical adjustment layer and the transparent substrate.

Preferably, the first functional layer has a physical thickness ranging from 1 μm to 10 μm.

Preferably, the first functional layer is a hard coat layer, an anti-glare layer or a combination thereof. When the first 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 An anti-glare layer is disposed on the hard coat On the floor.

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

The method for preparing 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, or a gravure coating method may be employed. The method is applied to the transparent substrate, and the hard coat layer is hardened and dried with a mixed solution, that is, the hard coat layer is formed on the transparent substrate.

The type of the mixed solution for hard coat layer is not particularly limited herein. In a specific example of the present invention, the mixed solution for hard coat layer contains 32.5 wt% of polymethyl methacrylate and 66.5 wt% of 2-butene. Ketone and 1% by weight of photoinitiator.

Preferably, the hard coat layer is coated on the transparent substrate with a mixed solution having a thickness ranging from 1.0 μm to 10 μm. When the thickness of the hard coat layer coated on the transparent substrate is less than 1.0 μm, the hard coating layer formed by subsequent hardening cannot effectively strengthen the mechanical strength of the transparent substrate (ie, the pencil hardness of the transparent substrate is less than H) . When the thickness of the hard coat layer coated on the transparent substrate by the mixed solution 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 the production is lowered. Sex and workability.

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

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

Preferably, the second functional layer is selected from a hard coat layer and an anti-glare Layer, anti-fingerprint layer, self-healing layer, anti-reflective layer or a combination of the above.

The hard coat layer and the antiglare layer are as described above, and therefore will not be described again.

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.

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.

<Example>

[Preparation Example 1] Composition for First Optical Adjustment Layer

40 wt% of an ultraviolet curable acrylic resin (Model: 7150, manufactured by DIC, refractive index: 1.52), 20 wt% of propylene glycol methyl ether, and 35 wt% of methyl isobutyl ketone, and 5 wt% of a photoinitiator was added. (Model: IRGACURE 184, manufactured by Ciba) A first mixed solution was formed. Next, taking 36 parts by weight based on 100 parts by weight of the total amount of the first mixed solution The zirconia (model: SZR-K, manufactured by Seiko Chemical Co., Ltd., refractive index: 2.2, average particle size range: 5 to 20 nm) is mixed with the mixed solution to prepare the first optical adjustment layer of Preparation Example 1. Composition (abbreviated as H-1).

[Preparation Examples 2 to 5] Composition for First Optical Adjustment Layer

The compositions for the first optical adjustment layer of Preparation Examples 2 to 5 were prepared in the same manner as in Preparation Example 1, and the kinds of the respective raw materials were also the same as those used in Preparation Example 1, except that the change was made according to Table 1. The amount of zirconia used.

[Preparation Example 6] Composition for second 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% The fluorine-based monomer (model: FSO, manufactured by DuPont), and 1 wt% of a photoinitiator (model: IRGACURE 184, manufactured by Ciba) were uniformly mixed to form a second 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) were added in an amount of 100 parts by weight based on the total amount of the second mixed solution, thereby preparing Preparation Example 6 The composition for the second optical adjustment layer (abbreviated as L-1).

[Preparation Example 7] Composition for second optical adjustment layer

Preparation Example 7 The composition for the second optical adjustment layer (abbreviated as L-2, refractive index = 1.40) was obtained by the same procedure as in Preparation Example 6, and the kind of each raw material was also the same as that used in Preparation Example 6. The difference is that according to Table 2, the amount of each raw material used is changed.

[Preparation Example 8] Composition for second optical adjustment layer

44 wt% of an ultraviolet curable acrylic resin (Model: 7150, manufactured by DIC, refractive index: 1.52) and 55 wt% of methyl isobutyl ketone were mixed, and 1 wt% of a photoinitiator (Model: IRGACURE 184, manufactured by Ciba) was added. ), that is, a second mixed solution is formed. Next, 25 parts by weight of cerium oxide (Model: MIBK-ST, manufactured by Nissan Chemical Co., Ltd., average particle diameter: 20 nm) was added and mixed uniformly in a total amount of 100 parts by weight of the second mixed solution, thereby preparing a preparation example. 8 second optical adjustment layer composition (abbreviated as L-3).

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

A hard coating mixed solution was applied to each of two opposite surfaces of a transparent substrate (material: PET, A4300 manufactured by TOYOBO; thickness: 125 μm) using a wire-bar [including: 32.5 wt% polymethyl Methyl acrylate, 66.5 wt% 2-butanone and 1 wt% photoinitiator]. After drying at 80 ° C for 2 minutes, and then hardening and drying with ultraviolet light of 200 mJ / cm ² , a first hard coat layer (thickness: 4 μm) and a second hard film are respectively formed on the opposite surfaces of the transparent substrate. Coating (thickness: 4 μm).

Next, the first optical adjustment layer composition (H-1) of Preparation Example 1 was applied onto the first hard coat layer using a wire bar, and then hardened and dried by ultraviolet light of 1000 mJ/cm ² to form a First optical adjustment layer [physical thickness: 35 nm, refractive index: 1.74].

Further, the second optical adjustment layer composition (L-1) of Preparation Example 6 was coated on the first optical adjustment layer using a wire bar, and dried at 80 ° C for 2 minutes, and then passed through 900 mJ/cm ² of ultraviolet light. After hardening and drying, a second optical adjustment layer [physical thickness: 30 nm, refractive index: 1.33] was formed, that is, a first laminate was obtained.

The first laminate is placed in a magnetron sputtering chamber, the target is Sn/(In+Sn)=10wt% ITO target, and the cavity vacuum is pumped to 3×10 ^-6 torr, After the sputtering gas Ar and O ₂ (O ₂ /Ar flow ratio = 0.02) were introduced into the cavity, sputtering was performed [Working pressure: 5 × 10 ^-4 torr, power: ⁴ kW, laminate temperature: 25 to 30 ° C That is, a transparent conductive layer [material: ITO, thickness: 30 nm, refractive index: 2.0] was formed on the second optical adjustment layer of the first laminate, that is, the conductive transparent laminate of Example 1.

Then, the conductive transparent laminate was cut into 6 cm×6 cm, partially immersed in a 5 wt% hydrogen chloride (HCl) solution for 3 minutes to remove part of the transparent conductive layer, and the transparent conductive layer was patterned. The patterned conductive transparent laminate of Example 1 was prepared by performing an crystallization annealing treatment (processing conditions: 150 ° C, 1 hour) in an oven.

[Examples 2 to 9 and Comparative Examples 1 to 8]

The conductive transparent laminates of Examples 2 to 9 and Comparative Examples 1 to 8 and the patterned conductive transparent laminate were produced in the same manner as in Example 1, except that the changes were made according to Tables 3 and 4. The type and thickness of the first optical adjustment layer, the second optical adjustment layer, and the transparent conductive layer.

[Evaluation measurement]

1. Refractive index and thickness

Measurement Methods of First Optical Adjustment Layer and Second Optical Adjustment Layer: In order to facilitate the description of the measurement process, the composition for the first optical adjustment layer of Preparation Example 1 is described, and the remaining preparation examples are measured in the same manner.

First, the composition for the first optical adjustment layer (H-1) 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 80 ° C. After drying for 2 minutes and hardening and drying with ultraviolet light of 900 mJ/cm ² , a first optical adjustment layer was formed. Next, the refractive index of the first optical adjustment layer was measured with an Abbe refractometer (manufactured by Atago Corporation).

The method for measuring the refractive index of the transparent conductive layer is as follows: after the Si wafer is used as the substrate and a transparent conductive layer is sputtered on the surface of the Si wafer, the sputtering condition is the same as that of the first embodiment. Next, it was placed in a hot air oven, baked at 150 ° C for 1 hour, and subjected to crystallization treatment, and then the refractive index of the transparent conductive layer was measured by an ellipsometer (ellipettete, model: GES 5 manufactured by Sopra Co., Ltd.).

Thickness measurement of the first optical adjustment layer, the second optical adjustment layer, and the transparent conductive layer: measured using a transmission electron microscope (manufactured by JEOL Co., model: JEM-2100F).

The following is a convenient description of the total light transmittance, the penetration color difference value, the reflection color difference value, the reflectance difference value, the surface resistance value, and the appearance evaluation measurement process, and the conductive transparent laminate of Embodiment 1 and the patterned conductive transparent The laminates are described, and the remaining examples and comparative examples are measured in the same manner. The evaluation measurement results are shown in Tables 3 and 4.

2. 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.).

3. Penetration color difference value (Δb*): 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 defined as L in JIS. *a*b* The color blueness index b* of the color system 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*.

4. Reflected color difference (Δb*): A black tape (manufactured by Toyo Electric Co., Ltd.) was attached to the second hard coat layer of the conductive transparent laminate patterned in Example 1 using a roller, and the measurement method was JIS Z 8722. The measurement was carried out using a spectroscopic spectrometer manufactured by Hitachi, based on the blue-yellow sensation index b* of the L*a*b* color system defined in JIS. The light of the spectroscopic spectrometer enters from the pattern portion of the patterned conductive transparent laminate, and is in contact with each layer, and is reflected, and the reflected color (b ₃ *) of the reflected light emitted from the pattern portion is measured. The light of the spectroscopic spectrometer enters from the non-pattern portion of the patterned conductive transparent laminate, and is in contact with each layer, and is reflected, and the reflected color (b ₄ *) of the reflected light emitted from the non-pattern portion is measured. Subtracting b ₃ * from b ₄ * is the reflection color difference Δb*, and when Δb* is in the range of 1.5 to -1.5, it means that the patterned conductive transparent laminate can be used when applied to a touch panel. It is not easy to see the trace of the patterning of the transparent conductive layer when viewing.

5. Reflectance difference (ΔR): A black tape (manufactured by Toyo Electric Co., Ltd.) was attached to the second hard coat layer of the conductive transparent laminate patterned in Example 1 using a roller, and then placed on a spectroscopic spectrometer (label: In Hitachi; model: U4100), 380 nm was used as the initial measurement wavelength and irradiated, and measured to 780 nm, and the reflection intensity of each wavelength was recorded to obtain a reflection spectrum. The light of the spectroscopic spectrometer enters from the pattern portion of the patterned conductive transparent laminate, and is in contact with each layer, and is reflected, and the reflection spectrum (A _k ) of the reflected light emitted from the pattern portion is measured. The light of the spectroscopic spectrometer enters from the non-pattern portion of the patterned conductive transparent laminate, and is in contact with each layer, and is reflected, and the reflection spectrum (B _k ) of the reflected light emitted from the non-pattern portion is measured. The reflectance difference (ΔR) is obtained by the following formula. When the ΔR range is 2 or less, when the patterned conductive transparent laminate is applied to the touch panel, the user can not easily see the transparent view. Traces of the patterned conductive layer.

n : number of samples measured

6. Surface resistance value

The surface resistance value of the conductive transparent laminate of Example 1 was measured by a four-terminal method using a measuring instrument manufactured by Mitsubishi Chemical Corporation (Model: Loresta AMC P-T400 MCP-T61) in accordance with the method of JIS K 7194.

7. Appearance evaluation

After the black tape (manufactured by Toyo Electric Co., Ltd.) was attached to the second hard coat layer 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. When it is difficult to distinguish the pattern portion from the non-pattern portion, the evaluation result is denoted by ○, and if the pattern portion and the non-pattern portion can be clearly distinguished, the evaluation result is denoted by ×.

From the results of the experimental data of Examples 1 to 9 of Table 3, it is understood that the present invention is patterned by adjusting the physical thickness and refractive index of the first optical adjustment layer and the second optical adjustment layer of the patterned conductive transparent laminate. The difference value (Δb*) between the reflected color of the reflected light emitted from the pattern portion of the conductive transparent laminate and the reflected color of the reflected light emitted from the non-pattern portion is between -1.42 and 1.36, and the patterned conductive transparent The difference value (ΔR) between the reflectance of the light emitted from the pattern portion of the laminate and the light emitted from the non-pattern portion and the light emitted therefrom is between 0.69 and 1.8, indicating the pattern of the present invention. The conductive transparent laminate effectively improves and alleviates the problem of patterning traces existing in the past. When applied to the touch panel, the user can hardly see the trace of the transparent conductive layer during viewing.

From the results of the experimental data of Comparative Examples 1 to 3 of Table 4, it is understood that when the physical thickness of the first optical adjustment layer is 40 nm and 50 nm, the reflected color of the reflected light emitted from the pattern portion of the patterned conductive transparent laminate is The difference values (Δb*) of the reflected colors of the reflected light emitted from the non-pattern portions are -1.78, -2.68, and -3.03, respectively, indicating that the patterned conductive transparent laminate has significant patterning marks.

From the results of the experimental data of Comparative Example 6 of Table 4, it is understood that when the physical thickness of the first optical adjustment layer is 20 nm, the reflectance of the emitted light is entered by the pattern portion of the patterned conductive transparent laminate. The difference value (ΔR) of the reflectance of the light emitted from and after the non-pattern portion enters is 3.11, indicating that the patterned conductive transparent laminate has a significant patterning trace.

From the results of the experimental data of Comparative Examples 5 and 7 of Table 4, it is understood that the reflected color of the reflected light emitted from the pattern portion of the patterned conductive transparent laminate when the refractive indices of the first optical adjustment layer are 1.95 and 1.60, respectively. The difference value (Δb*) between the reflected colors of the reflected light emitted from the non-pattern portion is between -13.56 and 3.63, respectively, and the light that is emitted by the pattern portion of the patterned conductive transparent laminate enters and is emitted therefrom The difference between the reflectance and the reflectance of the light emitted from the non-pattern portion and emitted therefrom is (ΔR) of 4.39 and 3.65, respectively, indicating that the patterned conductive transparent laminate has significant patterning marks.

From the results of the experimental data of Comparative Example 4 of Table 4, it is understood that when the physical thickness of the second optical adjustment layer is 50 nm, the reflected color of the reflected light emitted from the pattern portion of the patterned conductive transparent laminate and the non-pattern portion are The difference value (Δb*) of the reflected color of the reflected light emitted was 6.2, indicating that the patterned conductive transparent laminate had significant patterning marks.

From the results of the experimental data of Comparative Example 8 of Table 4, it is understood that the reflected color of the reflected light emitted from the pattern portion of the patterned conductive transparent laminate and the non-pattern portion when the refractive index of the second optical adjustment layer is 1.60 The difference value (Δb*) of the reflected color of the reflected light emitted was -3.54, indicating that the patterned conductive transparent laminate had significant patterning marks.

In summary, the conductive transparent laminate of the present invention has a refractive index ranging from 1.65 to 1.83 and a physical thickness ranging from 25 nm to 35 nm, and the second optical adjustment layer has a refractive index ranging from 1.33 to 1. 1.52 and the physical thickness range is 20 nm to 40 nm, and the difference between the reflected color and the reflectance of the reflected light emitted from the pattern portion of the patterned conductive transparent laminate and the reflected color and reflectance of the reflected light emitted from the non-pattern portion is small. When applied to the touch panel, the user can hardly see the trace of the patterning of the transparent conductive layer when viewing, so 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.

Claims (11)

A conductive transparent laminate comprising: a transparent substrate; a first optical adjustment layer disposed on the transparent substrate, the first optical adjustment layer having a refractive index ranging from 1.65 to 1.83 and a physical thickness ranging from 25 nm to 35 nm; a second optical adjustment layer disposed on the first optical adjustment layer, the second optical adjustment layer having a refractive index ranging from 1.33 to 1.52 and a physical thickness ranging from 20 nm to 40 nm; and a transparent conductive layer disposed on the second optical Adjust the layer. The conductive transparent laminate according to claim 1, wherein the transparent conductive layer has a refractive index ranging from 1.85 to 2.35. The conductive transparent laminate according to claim 1, wherein the transparent conductive layer has a physical thickness ranging from 5 nm to 100 nm. The conductive transparent laminate according to claim 1, wherein the transparent substrate has a refractive index ranging from 1.40 to 1.80. The conductive transparent laminate according to claim 1, further comprising a first functional layer disposed between the first optical adjustment layer and the transparent substrate. The conductive transparent laminate according to claim 5, wherein the first functional layer is a hard coat layer, an antiglare layer, or a combination thereof. The conductive transparent laminate according to claim 5, wherein the first functional layer has a physical thickness ranging from 1 μm to 10 μm. The conductive transparent laminate according to claim 1, further comprising a second functional layer disposed on the transparent substrate and opposite to the first optical adjustment layer. The conductive transparent laminate according to claim 8, wherein the second functional layer is selected from the group consisting of a hard coat layer, an antiglare layer, an anti-fingerprint layer, a self-healing layer, or a combination thereof. A patterned conductive transparent laminate comprising: a transparent substrate; a first optical adjustment layer disposed on the transparent substrate, the first optical adjustment layer having a refractive index ranging from 1.63 to 1.83 and a physical thickness ranging from 25 nm to 35 nm; a second optical adjustment layer disposed on the first optical adjustment layer, the second optical adjustment layer has a refractive index ranging from 1.33 to 1.52, and a physical thickness ranging from 20 nm to 40 nm; a patterned transparent conductive layer, And disposed on the second optical adjustment layer. A touch panel comprising the conductive transparent laminate of claim 1 or the patterned conductive transparent laminate of claim 10.