CN104658641A - Low-resistance transparent conductive laminate, low-resistance patterned transparent conductive laminate, and touch panel - Google Patents
Low-resistance transparent conductive laminate, low-resistance patterned transparent conductive laminate, and touch panel Download PDFInfo
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- CN104658641A CN104658641A CN201310716908.8A CN201310716908A CN104658641A CN 104658641 A CN104658641 A CN 104658641A CN 201310716908 A CN201310716908 A CN 201310716908A CN 104658641 A CN104658641 A CN 104658641A
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- transparent conductive
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- 230000003287 optical effect Effects 0.000 claims abstract description 68
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- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 26
- 239000010410 layer Substances 0.000 claims description 163
- 238000000059 patterning Methods 0.000 claims description 54
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 239000002346 layers by function Substances 0.000 claims description 11
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 6
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- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
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Landscapes
- Laminated Bodies (AREA)
- Non-Insulated Conductors (AREA)
Abstract
A low-resistance transparent conductive laminate comprises a transparent substrate, a transparent optical adjustment layer, a silicon oxide layer and a transparent conductive layer, wherein the silicon oxide is made of SiOx(x is more than 1.6 and less than 2.0). The transparent optical adjustment layer has a thickness in the range of 50nm to 4,000nm and a refractive index in the range of 1.58 to 1.70. The transparent conductive layer has a thickness ranging from 20nm to 25nm and a surface resistance value ranging less than 200 Ω/sq. The absolute value range of the difference between the refractive index of the transparent substrate and the refractive index of the transparent optical adjustment layer is 0.05 or less. The low-resistance transparent conductive lamination body has no interference fringes, and the low-resistance patterned transparent conductive lamination body formed by the low-resistance transparent conductive lamination body can be used for users to observe when applied to a touch panelThe patterned trace of the transparent conductive layer is not easy to see when the touch panel is seen, so that the touch panel has better display quality.
Description
Technical field
The present invention relates to a kind of low resistance transparent Electroconductive lamination body of contact panel, particularly relate to a kind of low resistance transparent Electroconductive lamination body comprising transparency carrier, transparent optical adjustment layer, silicon oxide layer and transparency conducting layer.
Background technology
In recent years market is proposed many commodity of wisdom easily, such as, intelligent mobile phone, touch control screen, touch-control flat board, e-book etc.Along with the release of these height application touch control technology, drive the use of whole contact panel.And this contact panel is such as but not limited to electric resistance touch-control panel or capacitance type touch-control panel.Described contact panel is one comprise transparent organic polymer base material and be arranged at the transparent conductive lamination body of the nesa coating on this transparent organic polymer base material.
Nesa coating can be carried out patterned process depending on demand by above-mentioned transparent conductive lamination body further, form the transparent conductive lamination body of a patterning, wherein, this patterned process is for remove partially transparent conducting film, to form non-conducting areas, remaining partially transparent conducting film then forms conductive region.But, light enter this patterning transparent conductive lamination body and by reflex time, because transparent organic polymer base material is not identical for light reflectance with nesa coating, make the light by conductive region large with the light reflectance difference by non-conducting areas, be applied on contact panel, when user uses, easily and see significantly and pick out conductive region and non-conducting areas, the display quality of contact panel is then affected.
TaiWan, China patent publication 201213136 discloses a kind of transparent and electrically conductive film.This transparent and electrically conductive film comprises transparent base, the first hard conating, the first transparent dielectric layer and the first transparent conductor layer.The film thickness range of this transparent base is 2 μm to 250 μm.The film thickness range of the first hard conating is 0.5 μm to 6 μm, and ranges of indices of refraction is 1.40 to 1.90.The film thickness range of the first transparent dielectric layer is 10nm to 50nm, and ranges of indices of refraction is 1.30 to 1.50.This first transparent conductor layer has carried out patterning and film thickness range is 10nm to 2 μm.From the announcement of table 1 in the specification of this TaiWan, China case, the sheet resistance value of the first transparent conductor layer after crystallization is when 270 Ω/more than sq, by the regulation and control of described Parameter Conditions, the reflectivity of the light of conductive region and the difference by the reflectivity of the light of non-conducting areas can be decreased through, when user is used, not easily see conductive region and non-conducting areas, to reach the effect of pattern-free.But, because current contact panel size has increasing trend, if the sheet resistance value of the first transparent conductor layer is too high, when being applied to large touch panel, easily produce noise.But for avoiding the generation of noise, sheet resistance value is reduced by the thickness increasing by the first transparent conductor layer, the reflectivity by the light of conductive region then can be made to become greatly with the difference of the reflectivity of the light by non-conducting areas, cause user easily see when watching contact panel and pick out conductive region and non-conducting areas.
Because above-mentioned, improve transparent and electrically conductive film thus be reduced by the reflectivity of the light of conductive region and the difference by the reflectivity of the light of non-conducting areas, to solve user easily sees the vestige of pattern for transparent conductive layer problem when watching contact panel, then improve the display quality of contact panel, be still the problem that this technical field person skilled can break through again.
Summary of the invention
The first object of the present invention is to provide a kind of light to be reflected the rear low resistance transparent Electroconductive lamination body without interfering line to produce.
Low resistance transparent Electroconductive lamination body of the present invention, comprises:
One transparency carrier;
One transparent optical adjustment layer, is arranged on this transparency carrier, and thickness range is 50nm to 4,000nm, and ranges of indices of refraction is 1.58 to 1.70;
One silica layer, be arranged in this transparent optical adjustment layer, and thickness range is 23nm to 27nm; And
One transparency conducting layer, is arranged on this silicon oxide layer, and thickness range is 20nm to 25nm, and sheet resistance value scope is for being less than 200 Ω/sq;
Wherein, the absolute value range of the difference of the refractive index of the refractive index of this transparency carrier and this transparent optical adjustment layer is less than 0.05, and this silica is by shown in formula (I);
SiO
x(I)
In formula (I), x is for being greater than 1.6 to being less than 2.0.
Without interfering line to produce after the second object of the present invention is to provide a kind of light reflection, and user not easily sees the transparent conductive lamination body of the low resistance patterning of the vestige of pattern for transparent conductive layer when watching.
The transparent conductive lamination body of low resistance patterning of the present invention, comprises:
One transparency carrier;
One transparent optical adjustment layer, is arranged on this transparency carrier, and thickness range is 50nm to 4,000nm, and ranges of indices of refraction is 1.58 to 1.70;
One silica layer, be arranged in this transparent optical adjustment layer, and thickness range is 23nm to 27nm; And
The transparency conducting layer of one patterning, is arranged on this silicon oxide layer, and thickness range is 20nm to 25nm, and sheet resistance value scope is for being less than 200 Ω/sq;
Wherein, the absolute value range of the difference of the refractive index of the refractive index of this transparency carrier and this transparent optical adjustment layer is less than 0.05, and silica is by shown in formula (I);
SiO
x(I)
In formula (I), x is for being greater than 1.6 to being less than 2.0.
The third object of the present invention is to provide a kind of contact panel with better display quality.
Contact panel of the present invention comprises the transparent conductive lamination body of above-mentioned low resistance transparent Electroconductive lamination body or above-mentioned low resistance patterning.
Beneficial effect of the present invention is: by the regulation and control of described Parameter Conditions, low resistance transparent Electroconductive lamination body of the present invention produces without interference line, and, when the transparent conductive lamination body of the low resistance patterning formed by this low resistance transparent Electroconductive lamination body is applied to contact panel, user not easily sees the vestige of pattern for transparent conductive layer when watching, then make contact panel have preferably display quality.
Embodiment
Below will be described in detail with regard to content of the present invention:
Low resistance transparent Electroconductive lamination body of the present invention, comprises:
One transparency carrier;
One transparent optical adjustment layer, is arranged on this transparency carrier, and thickness range is 50nm to 4,000nm, and ranges of indices of refraction is 1.58 to 1.70;
One silica layer, be arranged in this transparent optical adjustment layer, and thickness range is 23nm to 27nm; And
One transparency conducting layer, is arranged on this silicon oxide layer, and thickness range is 20nm to 25nm, and sheet resistance value scope is for being less than 200 Ω/sq;
Wherein, the absolute value range of the difference of the refractive index of the refractive index of this transparency carrier and this transparent optical adjustment layer is less than 0.05, and silica is by shown in formula (I);
SiO
x(I)
In formula (I), x is for being greater than 1.6 to being less than 2.0.
The present invention is less than 0.05 by the absolute value range of the difference adjusting the refractive index of this transparency carrier and the refractive index of this transparent optical adjustment layer, makes the interface of this transparency carrier and this transparent optical adjustment layer not cause reflection, to reduce the generation interfering line.Meanwhile, by the regulation and control of described Parameter Conditions, when making the transparent conductive lamination body of low resistance patterning be applied to contact panel, user not easily sees the vestige of pattern for transparent conductive layer when watching, then make contact panel have preferably display quality.
Preferably, in low resistance transparent Electroconductive lamination body of the present invention, also comprise one to be arranged on this transparency carrier and with the functional layer of transparent optical adjustment layer opposition side.
The preparation method of low resistance transparent Electroconductive lamination body of the present invention, can adopt the existing method preparing the low resistance transparent Electroconductive lamination body of contact panel.For example, the preparation method of low resistance transparent Electroconductive lamination body of the present invention comprises following steps: provide a transparency carrier; On this transparency carrier, form a transparent optical adjustment layer, obtain one first laminate; In the transparent optical adjustment layer of this first laminate, form one silica layer, obtain one second laminate; On the silicon oxide layer of this second laminate, form a transparency conducting layer, low resistance transparent Electroconductive lamination body of the present invention can be obtained.
The method that this transparent optical adjustment layer is formed is not particularly limited.This formation method is such as but not limited to rolling method, spin-coating method, or dip coating etc.Based on can quantity-produced viewpoint, preferably, this formation method be rolling method.
The formation method of this silicon oxide layer is not particularly limited.This formation method is such as but not limited to dry coating method, or wet coating method etc.This dry coating method is such as but not limited to vapour deposition method, sputtering method, ion plating method (ion Plating), chemical vapour deposition technique or galvanoplastic etc.Based on can quantity-produced viewpoint, preferably, this dry coating method be sputtering method.This wet coating method is such as but not limited to rolling method, spin-coating method or dip coating etc.Based on can quantity-produced viewpoint, preferably, this wet coating method be rolling method.
The formation method of this transparency conducting layer is not particularly limited.This formation method is such as but not limited to vapour deposition method, sputtering method, ion plating method, chemical vapour deposition technique, or galvanoplastic.Effectively to control the viewpoint of electrically conducting transparent layer thickness, preferably, this formation method is vapour deposition method or sputtering method.
The preparation method of this low resistance transparent Electroconductive lamination body of the present invention also comprises a pair this transparency conducting layer and bestows annealing process step, and to make transparency conducting layer crystallization and to adjust its resistance value, wherein, the operating temperature range of this annealing in process is 100 DEG C to 200 DEG C.
The preparation method of this low resistance transparent Electroconductive lamination body of the present invention also comprises one and to be formed on this transparency carrier and the step of functional layer with this transparent optical adjustment layer opposition side.The formation method of this functional layer is not particularly limited.This formation method such as but do not limit rolling method, spin-coating method, dip coating, stick coating method, or gravure coating process etc.
The transparent conductive lamination body preparation method of low resistance patterning of the present invention comprises the preparation method of above-mentioned low resistance transparent Electroconductive lamination body, and a patterned process is bestowed to the transparency conducting layer of this low resistance transparent Electroconductive lamination body, form the transparency conducting layer of a patterning, the transparent conductive lamination body of low resistance patterning of the present invention can be obtained, wherein, annealing process step can carry out after forming transparency conducting layer or after the transparency conducting layer of patterning again.
This patterned process is for remove partially transparent conductive layer, and to form nonconductive regions, remaining partially transparent conductive layer then forms conduction region.This patterned process is such as but not limited to dry ecthing method or wet etch method.
Below will be described in detail to this transparency carrier, transparent optical adjustment layer, silicon oxide layer, transparency conducting layer and functional layer one by one.
<< transparency carrier >>
In the present invention, the material of this transparency carrier is not particularly limited, such as but not limited to polyester resin (polyester-based resin), or polycarbonate resin (polycar-bonate-based resin) etc.This polyester resin is such as but not limited to polyethylene terephthalate (polyethylene terephthalate is called for short PET) etc.This polycarbonate resin is such as but not limited to Merlon (polycarbonate is called for short PC) etc.Preferably, the material of this transparency carrier is polyethylene terephthalate.
Preferably, in the present invention, the ranges of indices of refraction of this transparency carrier is 1.58 to 1.80.When the refractive index of this transparency carrier is for being less than 1.58, after transparency conducting layer carries out patterned process, the reflectivity passing through the light of formed conduction region is larger with the difference in reflectivity of the light passing through formed nonconductive regions, when being applied to contact panel, user easily sees the vestige of pattern for transparent conductive layer when watching.
In the present invention, the thickness of this transparency carrier is not particularly limited, and preferably, the thickness range of this transparency carrier is 2 μm to 300 μm; More preferably, be 10 μm to 250 μm.When the thickness of this transparency carrier is less than 2 μm, have the problem of mechanical strength deficiency, successive process is operated not easily.When the thickness of this transparency carrier is greater than 300 μm, then cost of manufacture can increase, and total light penetration rate of the transparent conductive lamination body of low resistance transparent Electroconductive lamination body or low resistance patterning can be caused to decline, and meanwhile, cannot meet the demand of sci-tech product slimming.
<< transparent optical adjustment layer >>
Transparent optical adjustment layer is arranged on this transparency carrier, and thickness range is 50nm to 4,000nm, and ranges of indices of refraction is 1.58 to 1.70.When the thickness of this transparent optical adjustment layer is less than 50nm, thickness evenness is wayward.When the thickness of this transparent optical adjustment layer is greater than 4,000nm, then cost of manufacture can increase.Preferably, the thickness range of this transparent optical adjustment layer is that 50nm is to being less than 500nm.
When the refractive index of this transparent optical adjustment layer is greater than 1.70, then not easily the absolute value range of the refractive index difference of itself and transparency carrier is controlled below 0.05, then easily cause the generation interfering line.When the refractive index of this transparent optical adjustment layer is less than 1.58, then cannot promote the refractive index of the first laminate, therefore, after transparency conducting layer carries out patterned process, the reflectivity passing through the light of formed conduction region is large with the difference in reflectivity of the light passing through formed nonconductive regions, when being applied to contact panel, user easily sees the vestige of pattern for transparent conductive layer when watching.Preferably, the ranges of indices of refraction of this transparent optical adjustment layer is 1.63 to 1.68.
Preferably, this transparent optical adjustment layer formed by a transparent optical adjustment layer constituent that formed comprising metal oxide microparticle and a function component, and wherein, this function component comprises photohardenable adhesive and light initiator.This metal oxide microparticle is such as but not limited to titanium oxide or zirconia etc.Preferably, the ranges of indices of refraction of this metal oxide microparticle is 2.0 to 3.0.Preferably, the average particle size range of this metal oxide microparticle is 5nm to 20nm.Preferably, be 100 parts by weight with the total amount of this function component, the content range of this metal oxide microparticle is 2 weight portion to 50 weight portions.This photohardenable adhesive such as but not limited to having the polyfunctional monomer of (methyl) acrylic, having the oligomer of (methyl) acrylic, or has the polymer etc. of (methyl) acrylic.This light initiator can make this photohardenable adhesive carry out photocuring reaction person all can, and this light initiator can be used alone or as a mixture, such as but not limited to vinyl benzene ketone, benzophenone derivates, michler's ketone, benzyne, benzyl derivative, benzoin derivatives, benzoin methylether class, alpha-acyloxy ester, thioxanthene ketone and Anthraquinones.Preferably, in the total amount of this function component for 100wt%, the content range of this light initiator is 0.1wt% to 10wt%.
<< silicon oxide layer >>
This silicon oxide layer is arranged in transparent optical adjustment layer, and thickness range is 23nm to 27nm.The thickness of this silicon oxide layer for being greater than 27nm, then the b penetrated in look of silicon oxide layer
*value becomes large, can be with yellow hue.The thickness of this silicon oxide layer is for being less than 23nm, then total light penetration rate of the transparent conductive lamination body of low resistance transparent Electroconductive lamination body or low resistance patterning declines.The oxygen content of this silicon oxide layer can adjust by the amount of oxygen passed into when controlling preparation.When the x in formula (I) is less than 1.6, not exclusively cause the silicon oxide layer transparency not good because being oxidized, then total light penetration rate of the transparent conductive lamination body of low resistance transparent Electroconductive lamination body or low resistance patterning is caused to decline, and, make the reflectivity by the light of conduction region large with the reflection differences mutation of the light by nonconductive regions, when being applied to contact panel, user easily sees the vestige of pattern for transparent conductive layer when watching.Due to occurring in nature, SiO
xthe maximum of middle x is 2.0, increases amount of oxygen and makes on the contrary to make sputtering rate reduce, cause production capacity to reduce if continue again.
<< transparency conducting layer >>
The material of this transparency conducting layer can be used alone or as a mixture, and the material of this transparency conducting layer is such as but not limited to indium oxide, tin oxide, titanium oxide, aluminium oxide, zinc oxide, gallium oxide, or tin indium oxide (tin ash and indium sesquioxide formed, Indium tin oxide, is called for short ITO).Preferably, the material of this transparency conducting layer is tin indium oxide.
When the material of this transparency conducting layer is tin indium oxide, after crystallization (as carrying out annealing in process), tin (Sn
4+) instead of indium (In
3+) position in lattice, and release an electronics, then make sheet resistance value be declined.Preferably, in the total amount of this tin indium oxide for 100wt%, the content range of this tin ash is 3wt% to 10wt%.When the content of this tin ash is greater than 10wt%, transparency conducting layer is crystallization not easily.More preferably, the content range of this tin ash is 5wt% to 7wt%.
Theoretical according to Solid–state Optics, when this transparency conducting layer is after crystallization, the electron concentration of increase, this transparency conducting layer refractive index can be made to decline, and therefore, the refractive index before non-crystallization is high compared with the refractive index after crystallization.Preferably, the ranges of indices of refraction of this transparency conducting layer is 1.85 to 2.15.The refractive index of this transparency conducting layer lower than 1.85 or higher than 2.15 time, this transparency conducting layer can with color, and penetrance can reduce, simultaneously, when the transparent conductive lamination body of this low resistance patterning is applied to contact panel, user easily sees the vestige of pattern for transparent conductive layer when watching.More preferably, the ranges of indices of refraction of this transparency conducting layer is 1.90 to 2.05.
The thickness range of this transparency conducting layer is 20nm to 25nm.When the thickness of this transparency conducting layer is lower than 20nm, sheet resistance value is too high.When the thickness of this transparency conducting layer is higher than 25nm, the b penetrated in look of low resistance transparent Electroconductive lamination body can be made
1 *value becomes large, and inclined yellow hue.
<< functional layer >>
This functional layer is such as but not limited to hard conating, Bewildering resistance layer, anti-finger print layer, or self repair layer.Preferably, in low resistance transparent Electroconductive lamination body of the present invention, the thickness range of this functional layer is 1 μm to 10 μm.This hard conating can strengthen the hardness of transparency carrier.When the thickness of this functional layer is less than 1.0 μm, the standard that pencil hardness is more than H cannot be met.When the thickness of this functional layer is greater than 10 μm, in the process of draft machine ergosphere, film can be caused to contract because of sclerosis, and then cause this transparency carrier that curling phenomenon occurs, and cost of manufacture can increase.
The present invention will be described further with regard to following examples, but it is to be understood that described embodiment is only and illustrates use, and should not be interpreted as restriction of the invention process.
<< synthesis example 1>> forms transparent optical adjustment layer constituent
By the acrylic acid series uv-hardening resin of 40wt%, the propylene glycol monomethyl ether of 20wt%, and the methylisobutylketone of 35wt% mixes, and then, adds the light initiator (label: Ciba system of 5wt%; Model: IRGACURE184) to form a function component, finally, by the zirconia (label: Sakai Chemical Industry Co., Ltd.'s system of 20 weight portions; Model: SZR-K) be scattered in this function component, can obtain and form transparent optical adjustment layer constituent, hereinafter referred to as H-1.
<< synthesis example 2>>
By the acrylic acid series uv-hardening resin of 40wt%, the propylene glycol monomethyl ether of 20wt%, and the methylisobutylketone of 35wt% mixes, and then, adds the light initiator (label: Ciba system of 5wt%; Model: IRGACURE184) to form a function component, finally, by the zirconia (label: Sakai Chemical Industry Co., Ltd.'s system of 28 weight portions; Model: SZR-K) be scattered in this function component, can obtain and form transparent optical adjustment layer constituent, hereinafter referred to as H-2.
<< synthesis example 3>>
The acrylic acid series uv-hardening resin of 44wt% and the methylisobutylketone of 55wt% are mixed, then, adds the light initiator (label: Ciba system of 1wt%; Model: IRGACURE184) to form a function component, finally, by the silicon dioxide (label: Nissan Chemical system of 25 weight portions; Model: MIBK-ST) be scattered in this function component, can obtain and form transparent optical adjustment layer constituent, hereinafter referred to as H-3.
<< synthesis example 4>>
By the acrylic acid series uv-hardening resin of 40wt%, the propylene glycol monomethyl ether of 20wt%, and the methylisobutylketone of 35wt% mixes, and then, adds the light initiator (label: Ciba system of 5wt%; Model: IRGACURE184) to form a function component, finally, by the zirconia (label: Sakai Chemical Industry Co., Ltd.'s system of 36 weight portions; Model: SZR-K) be scattered in this function component, can obtain and form transparent optical adjustment layer constituent, hereinafter referred to as H-4.
<< synthesis example 5>>
The acrylic acid series uv-hardening resin of 40wt% and the methylisobutylketone of 59wt% are mixed, then, adds the light initiator (label: Ciba system of 1wt%; Model: IRGACURE184) to form a function component, finally, by the silicon dioxide (label: Nissan Chemical system of 33 weight portions; Model: MIBK-ST) be scattered in this function component, can obtain and form transparent optical adjustment layer constituent, hereinafter referred to as H-5.
<< embodiment 1>>
Polyethylene terephthalate (TOYOBO system, trade name: A4300 are called for short PET) is used to produce the polyethylene terephthalate transparency carrier that a thickness is 125 μm.Coat with coiling rod (wire-bar) mixed solution that comprises the acryl resin of 32.5wt% and the 2-butanone (methyl ehtyl ketone) of 67.5wt% on the surface of polyethylene terephthalate transparency carrier.Then, carrying out the drying process of 2 minutes with 80 DEG C, then, take exposure as 200mJ/cm
2ultraviolet light irradiate, to form the hard conating that thickness is 4 μm on this polyethylene terephthalate transparency carrier.
Being coated on the polyethylene terephthalate transparency carrier with hard conating opposition side with coiling rod by the H-1 of synthesis example 1, then, take exposure as 600mJ/cm
2ultraviolet light irradiate, to form the transparent optical adjustment layer that thickness is 0.05 μm on this polyethylene terephthalate transparency carrier, obtain one first laminate.Then, this first laminate is placed in magnetic control sputtering plating cavity, take silicon as target, and chamber vacuum degree is reduced to 3 × 10
-6after torr, pass into argon gas and oxygen in cavity, wherein, the flow-rate ratio of oxygen and argon gas is 0.23, and makes the vacuum degree control of cavity 5 × 10
-3under torr.Use the power of 4KW, and the temperature adjusting of this first laminate is in room temperature, in the transparent optical adjustment layer of this first laminate, form the silicon oxide layer that a thickness is 25nm, obtains one second laminate.Then, using tin indium oxide as target, wherein, the content of tin is 5wt%, then, passes into argon gas and oxygen in cavity, and wherein, the flow-rate ratio of oxygen and argon gas is 0.02, and makes the vacuum degree control of cavity 5 × 10
-4under torr.Use the power of 4KW, and the temperature adjusting of this second laminate is in room temperature, on the silicon oxide layer of this second laminate, form a thickness is the transparency conducting layer of 25nm, can obtain low resistance transparent Electroconductive lamination body of the present invention.Then, this low resistance transparent Electroconductive lamination body is cut into the size of 6cm × 6cm, and be vertically soaked in the hydrochloric acid solution of 5wt%, and soak 3 minutes, to be removed by partially transparent conductive layer, form conduction region and nonconductive regions, then, be placed in the baking oven of 150 DEG C, the annealing in process that the transparency conducting layer of patterning is carried out 1 hour, the transparent conductive lamination body of low resistance patterning of the present invention can be obtained.
<< embodiment 2 to 8 and comparative example 1 to 9>>
Embodiment 2 to 8 and comparative example 1 to 9 are that different places is as shown in table 1 and table 2 with the step identical with embodiment 1 to prepare the transparent conductive lamination body of low resistance transparent Electroconductive lamination body and low resistance patterning.
<< embodiment 9>>
Embodiment 9 is to prepare the transparent conductive lamination body of low resistance transparent Electroconductive lamination body and low resistance patterning with the step identical with embodiment 1, when different places is to prepare transparency conducting layer, using tin indium oxide as target, wherein, the content of tin is 5wt%, then, argon gas and oxygen is passed in cavity, wherein, the flow-rate ratio of oxygen and argon gas is 0.01, and makes the vacuum degree control of cavity 5 × 10
-4under torr.Use the power of 4KW, and the temperature adjusting of this second laminate is in room temperature, on the silicon oxide layer of this second laminate, form a thickness is the transparency conducting layer of 25nm.
<< comparative example 10>>
Comparative example 10 is with the step identical with embodiment 1 to prepare the transparent conductive lamination body of low resistance transparent Electroconductive lamination body and low resistance patterning, and different places is that transparency conducting layer does not carry out annealing in process.
<< assessment item >>
1. refractive index and thickness measuring:
The refractive index of < transparent optical adjustment layer and thickness G reatT.GreaT.GT
(1) with trade name " A4300 ", TOYOBO system] PET is base material, utilize coiling rod (wire-bar) that the formation transparent optical adjustment layer constituent of synthesis example 1 to 5 is coated above-mentioned substrate surface, respectively sequentially with 80 DEG C of dryings 2 minutes, and with 200mJ/cm
2uV energy carry out dry through after, form transparent optical adjustment layer.
(2) manufacture Abbe refractometer with Atago company and measure refractive index.
(3) transmission electron microscope (model: JEM-2100F) that the thickness of described transparent optical adjustment layer manufactures with JEOL company carries out cross-section and measures.
The refractive index of < transparency conducting layer and thickness G reatT.GreaT.GT
Use Si wafer to be substrate, after ITO sputter completes, had on surface the Si wafer of ITO to put into hot-air oven, with 150 DEG C of baking 60min, carry out crystallization process, then, the elliptical polarizer (Ellipsomete manufactured with Sopra company; Model; GES5) detecting refractive index is carried out.The transmission electron microscope (model: JEM-2100F) that the thickness of this transparency conducting layer manufactures with JEOL company carries out cross-section and measures.
2. the silicon in silicon oxide layer and oxygen ratio measuring method: use Energy distribution formula spectrometer (Energy Dispersive Spectrometer; Oxford company manufactures; Model: Inca Energy), the silicon in measurement silicon oxide layer and the atomicity ratio of oxygen, x=(oxygen atom quantity/silicon atom quantity).
3. penetrate colo(u)r specification to survey: the transparent conductive lamination body of the low resistance patterning of embodiment 1 to 9 and comparative example 1 to 10 is used sub-ray spectrometer (label: Hitachi with JISZ8722 standard determination method respectively; Model: U4100) measure, with the L defined in JIS
*a
*b
*the blue yellow chromaticity sense index b of color specification system
*for benchmark.
4. total light penetration rate (unit: TT%) measures: by the transparent conductive lamination body of the low resistance patterning of embodiment 1 to 9 and comparative example 1 to 10 respectively with JISK7105 standard determination method and the measuring instrument (model NDH-2000) using Japanese electric look industry (stock) to manufacture measure.
5. sheet resistance value (unit: Ω/sq) measures: by the transparent conductive lamination body of the low resistance patterning of embodiment 1 to 9 and comparative example 1 to 10 respectively with JISK7194 standard determination method and the four terminal measurement instruments (model: Loretest AMCP-T400MCP-T610) using Mitsubishi's oiling (stock) to manufacture measure.
6. reflectivity (unit: %) difference measures: the transparent conductive lamination body of the low resistance patterning of embodiment 1 to 9 and comparative example 1 to 10 is placed in sub-ray spectrometer (label: Hitachi respectively; Model: U4100) light is aimed at conduction region measure, irradiate using 380nm as initial measurement wavelength, and to measure to 780nm, and record the reflected intensity of each wavelength, to obtain a reflectance spectrum (A
k).Then, light is aimed at nonconductive regions, then, measure according to said method, to obtain a reflectance spectrum (B
k).Reflectivity difference Δ R is obtained by following formula:
N: measure total number; A
kand B
k: reflectance spectrum.
7. interfere line evaluation: be placed on visual examination table by the low resistance transparent Electroconductive lamination body of embodiment 1 to 9 and comparative example 1 to 10, opening fluorescent lamp makes center illumination at more than 2000LUX, by human eye observation, visual angle is 45 ° to 60 °, and detecting distance is 50cm to 100cm.Evaluation method is as follows: zero is without rainbow phenomena; X is for there being rainbow phenomena.
8. patterning evaluation: 16 black belts are affixed on respectively on the hard conating of the transparent conductive lamination body of the low resistance patterning of embodiment 1 to 9 and comparative example 1 to 10, then, by the transparency conducting layer of human eye visual observation patterning, and be confirmed whether to pick out conduction region and nonconductive regions.Evaluation method is as follows: ◎ is for cannot pick out conduction region and nonconductive regions; Zero for slightly picking out conduction region and nonconductive regions; X is for can pick out conduction region and nonconductive regions.
Table 1
PC: Merlon (label: Longhua Longhua; Model: PC-811);
TAC: cellulose triacetate (label: reach brightness TacBright; Model: N980).
Table 2
PC: Merlon (label: Longhua Longhua; Model: PC-811);
TAC: cellulose triacetate (label: reach brightness TacBright; Model: N980).
From the data result of table 1, by the regulation and control of described Parameter Conditions, low resistance transparent Electroconductive lamination body of the present invention is produced without interference line, and, the transparent conductive lamination body of the low resistance patterning formed by this low resistance transparent Electroconductive lamination body is under human eye observation, not easily pick out conduction region and the nonconductive regions of the transparency conducting layer of patterning, effective improvement also alleviates the obvious problem of pattern for transparent conductive layer vestige of existing existence, and contact panel then can be made to have preferably display quality.
From the data result of table 2, comparative example 1 to 3 and 5 the refractive index of transparent optical adjustment layer, and the absolute value of the difference of the refractive index of the refractive index of this transparency carrier and this transparent optical adjustment layer is not in the scope of design of this case, the low resistance transparent Electroconductive lamination body obtained has the generation interfering line, and, the transparent conductive lamination body of the low resistance patterning formed by it, under human eye observation, has significant patterning vestige.
Although the absolute value of the difference of the refractive index of the refractive index of this transparency carrier of comparative example 4 and this transparent optical adjustment layer is in the scope of design of this case, but the refractive index of transparent optical adjustment layer is not in the scope of design of this case, though obtained low resistance transparent Electroconductive lamination body can be made to produce without interference line, but the transparent conductive lamination body of the low resistance patterning formed by it is under human eye observation, there is significant patterning vestige.
The refractive index of the transparent optical adjustment layer of comparative example 6 and 7, though and the difference of the refractive index of the refractive index of this transparency carrier and this transparent optical adjustment layer is in the scope of design of this case, but the thickness of silicon oxide layer is not in the scope of design of this case, though obtained low resistance transparent Electroconductive lamination body can be made without the generation interfering line, but the transparent conductive lamination body of the low resistance patterning formed by it is under human eye observation, there is significant patterning vestige.
The refractive index of the transparent optical adjustment layer of comparative example 8, though and the difference of the refractive index of the refractive index of this transparency carrier and this transparent optical adjustment layer is in the scope of design of this case, but the oxygen ratio in silicon oxide layer is not in the scope of the design of this case, though obtained low resistance transparent Electroconductive lamination body can be made without the generation interfering line, but the transparent conductive lamination body of the low resistance patterning formed by it is under human eye observation, there is significant patterning vestige.
The refractive index of the transparent optical adjustment layer of comparative example 9, though and the difference of the refractive index of the refractive index of this transparency carrier and this transparent optical adjustment layer is in the scope of design of this case, but the thickness of transparency conducting layer is not in the scope of the design of this case, though obtained low resistance transparent Electroconductive lamination body can be made without the generation interfering line, but the transparent conductive lamination body of the low resistance patterning formed by it is under human eye observation, there is significant patterning vestige.
The refractive index of the transparent optical adjustment layer of comparative example 10, though and the difference of the refractive index of the refractive index of this transparency carrier and this transparent optical adjustment layer is in the scope of design of this case, but the sheet resistance value of transparency conducting layer and thickness is not in the scope of the design of this case, though obtained low resistance transparent Electroconductive lamination body can be made without the generation interfering line, but the transparent conductive lamination body of the low resistance patterning formed by it is under human eye observation, there is significant patterning vestige.
In sum, by the regulation and control of described Parameter Conditions, low resistance transparent Electroconductive lamination body of the present invention produces without interference line, and the transparent conductive lamination body of the low resistance patterning to be formed by this low resistance transparent Electroconductive lamination body is under human eye observation, not easily see the vestige of pattern for transparent conductive layer, when being applied to contact panel, contact panel can be made to have preferably display quality, so really object of the present invention can be reached.
Claims (13)
1. a low resistance transparent Electroconductive lamination body, is characterized in that comprising:
One transparency carrier;
One transparent optical adjustment layer, is arranged on this transparency carrier, and thickness range is 50nm to 4,000nm, and ranges of indices of refraction is 1.58 to 1.70;
One silica layer, be arranged in this transparent optical adjustment layer, and thickness range is 23nm to 27nm; And
One transparency conducting layer, is arranged on this silicon oxide layer, and thickness range is 20nm to 25nm, and sheet resistance value scope is for being less than 200 Ω/sq;
Wherein, the absolute value range of the difference of the refractive index of the refractive index of this transparency carrier and this transparent optical adjustment layer is less than 0.05, and this silica is by shown in formula (I);
SiO
x(I)
In formula (I), x is for being greater than 1.6 to being less than 2.0.
2. low resistance transparent Electroconductive lamination body according to claim 1, is characterized in that: the ranges of indices of refraction of this transparent optical adjustment layer is 1.63 to 1.68.
3. low resistance transparent Electroconductive lamination body according to claim 1, is characterized in that: the thickness range of this transparent optical adjustment layer is that 50nm is to being less than 500nm.
4. low resistance transparent Electroconductive lamination body according to claim 1, is characterized in that: the ranges of indices of refraction of this transparency carrier is 1.58 to 1.80.
5. low resistance transparent Electroconductive lamination body according to claim 1, is characterized in that: the ranges of indices of refraction of this transparency conducting layer is 1.85 to 2.15.
6. low resistance transparent Electroconductive lamination body according to claim 1, is characterized in that: described low resistance transparent Electroconductive lamination body also comprise one to be arranged on this transparency carrier and with the functional layer of transparent optical adjustment layer opposition side.
7. a transparent conductive lamination body for low resistance patterning, is characterized in that comprising:
One transparency carrier;
One transparent optical adjustment layer, is arranged on this transparency carrier, and thickness range is 50nm to 4,000nm, and ranges of indices of refraction is 1.58 to 1.70;
One silica layer, be arranged in this transparent optical adjustment layer, and thickness range is 23nm to 27nm; And
The transparency conducting layer of one patterning, is arranged on this silicon oxide layer, and thickness range is 20nm to 25nm, and sheet resistance value scope is for being less than 200 Ω/sq;
Wherein, the absolute value range of the difference of the refractive index of the refractive index of this transparency carrier and this transparent optical adjustment layer is less than 0.05, and this silica is by shown in formula (I);
SiO
x(I)
In formula (I), x is for being greater than 1.6 to being less than 2.0.
8. the transparent conductive lamination body of low resistance patterning according to claim 7, is characterized in that: the ranges of indices of refraction of this transparent optical adjustment layer is 1.63 to 1.68.
9. the transparent conductive lamination body of low resistance patterning according to claim 7, is characterized in that: the thickness range of this transparent optical adjustment layer is that 50nm is to being less than 500nm.
10. the transparent conductive lamination body of low resistance patterning according to claim 7, is characterized in that: the ranges of indices of refraction of this transparency carrier is 1.58 to 1.80.
The transparent conductive lamination body of 11. low resistance patternings according to claim 7, is characterized in that: the ranges of indices of refraction of this transparency conducting layer is 1.85 to 2.15.
The transparent conductive lamination body of 12. low resistance patternings according to claim 7, is characterized in that: the transparent conductive lamination body of described low resistance patterning also comprise one to be arranged on this transparency carrier and with the functional layer of transparent optical adjustment layer opposition side.
13. 1 kinds of contact panels, is characterized in that: described contact panel comprises the transparent conductive lamination body of low resistance transparent Electroconductive lamination body according to claim 1 or low resistance patterning according to claim 7.
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| TW102141693 | 2013-11-15 | ||
| TW102141693A TWI486258B (en) | 2013-11-15 | 2013-11-15 | Low resistance transparent transparent laminate, low resistance patterned transparent Conductive laminated body and touch panel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109491545A (en) * | 2018-12-19 | 2019-03-19 | 武汉华星光电半导体显示技术有限公司 | Touch panel unit and electronic equipment |
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| KR20110038517A (en) * | 2009-10-08 | 2011-04-14 | 엘지이노텍 주식회사 | Planer member for touch panel and method for manufacturing same |
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| CN104658641B (en) | 2017-04-12 |
| TWI486258B (en) | 2015-06-01 |
| TW201518111A (en) | 2015-05-16 |
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