CN101066011A - Electroconductive laminate, and electromagnetic wave shielding film and protective plate for plasma display - Google Patents
Electroconductive laminate, and electromagnetic wave shielding film and protective plate for plasma display Download PDFInfo
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- CN101066011A CN101066011A CN 200580040719 CN200580040719A CN101066011A CN 101066011 A CN101066011 A CN 101066011A CN 200580040719 CN200580040719 CN 200580040719 CN 200580040719 A CN200580040719 A CN 200580040719A CN 101066011 A CN101066011 A CN 101066011A
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Abstract
The invention provides an electroconductive laminate (10) exhibiting broad ransmission and reflection bands and is excellent in electromagnetic wave shielding property, visible light transmissivity and near-infrared ray shielding property. The electroconductive laminate (10) which has a substrate (11) and an electroconductive film (12) formed on the substrate (11), wherein the electroconductive film (12) is a multi-layer structure where oxide layers (12a) and metal layers (12b) are alternately laminated from the substrate (11) side in a total layer number of (2n + 1) (wherein n is an integer of 1 or more) and wherein the oxide layer (12a) contains zinc oxide and a metal oxide having a high refractive index of 2.3 or more as a main component and the metal layer (12b) contains silver or a silver alloy as a main component.
Description
Technical field
The present invention relates to electroconductive laminate, be arranged at the plasma display of electromagnetic wave shielding ability of observer's side of PDP in order to protect plasma display panel (hereinafter to be referred as PDP) body with electromagnetic shielding film and plasma display baffle with electromagnetic noise that shielding produces by PDP.
Background technology
Electroconductive laminate with transparency is used as the transparency electrode of liquid crystal display cells etc., windshield, heat mirror, electromagnetic wave shielding glass pane etc.For example, patent documentation 1 has disclosed the electroconductive laminate in the coating of total (2n+1) layer (n is the integer more than 1) of be provided with cross laminate on the transparency carrier transparent oxide layer that formed by zinc oxide and silver layer.This electroconductive laminate is considered to have sufficient conductivity (electromagnetic wave shielding performance) and visible light transmission.But, increase lamination for the conductivity (electromagnetic wave shielding performance) that makes electroconductive laminate further improves and count under the situation of quantity of n and silver layer, the problem that exists visible light transmission to descend.
In addition, electroconductive laminate also is used as the plasma display electromagnetic shielding film.Therefore electromagnetic wave is emitted by the front from PDP, in order to shield this electromagnetic wave, is configured in the electromagnetic shielding film that has formed conducting film on the matrix such as plastic film in observer's side of PDP.
For example, put down in writing the plasma display baffle of the laminate of the oxide skin(coating) that had cross laminate and metal level in the patent documentation 2 as conducting film.
For electromagnetic shielding film, require in whole visible region transmissivity height and reflectivity low, promptly the Transflective bandwidth also requires shielding height near infrared region.For the Transflective band is broadened, the lamination number that can increase oxide skin(coating) and metal level gets final product.But if increase the lamination number, then the internal stress in the electromagnetic shielding film increases, and produces that this film curls or conducting film breaks and problems such as resistance value rising.In addition, if increase the lamination number, then visible light transmission may descend.Therefore, there was the limit in the lamination number of oxide skin(coating) in the conducting film and metal level in the past, did not count Transflective band also wide and conductivity (electromagnetic wave shielding performance) and the good electromagnetic shielding film of visible light transmission even also found to reduce lamination.
Patent documentation 1: the special fair 8-32436 communique of Japan Patent
Patent documentation 2: the international text that discloses No. 98/13850
The announcement of invention
Reduce lamination and count Transflective band also wide and conductivity (electromagnetic wave shielding performance), visible light transmission and near-infrared shielding good electrical conductivity laminate, plasma display with electromagnetic shielding film and plasma display baffle even the object of the present invention is to provide.
Electroconductive laminate of the present invention is the electroconductive laminate that has matrix and be formed at the conducting film on the matrix, it is characterized in that, conducting film is the multilayer structure making of amounted to cross laminate from the matrix side (2n+1) layer [n is the integer more than 1] oxide skin(coating) and metal level, oxide skin(coating) contain zinc oxide and refractive index at the high refractive index metal oxide more than 2.3 as main component, metal level contains silver or silver alloy as main component.
High refractive index metal oxide better is titanium oxide and/or niobium oxide.
Metal level better is to be provided with 2～8 layers.
Metal level better is fine silver or contains gold and/or the silver alloy of bismuth.
Plasma display of the present invention is characterised in that with electromagnetic shielding film, is made of electroconductive laminate of the present invention.
Plasma display of the present invention is characterised in that with baffle, has support base, is arranged at the electrode that the plasma display of the present invention on this support base is electrically connected with the conducting film of electromagnetic shielding film with electromagnetic shielding film, with this plasma display.
Plasma display of the present invention can also have the conductive grid film with baffle.
Even electroconductive laminate of the present invention reduces the lamination number, the Transflective band is also wide, and conductivity (electromagnetic wave shielding performance), visible light transmission and near-infrared shielding are good.
Even plasma display of the present invention reduces the lamination number with electromagnetic shielding film, the Transflective band is also wide, and conductivity (electromagnetic wave shielding performance), visible light transmission and near-infrared shielding are good.
Plasma display of the present invention is good with the electromagnetic wave shielding ability of baffle, the Transflective bandwidth, and the transmission of visible light height, near-infrared shielding is good.
The simple declaration of accompanying drawing
Fig. 1 is the sectional view of a kind of execution mode of expression electroconductive laminate of the present invention.
Fig. 2 is the sectional view of the another kind of execution mode of expression electroconductive laminate of the present invention.
Fig. 3 is the sectional view of the 1st execution mode of expression baffle of the present invention.
Fig. 4 is the sectional view of the 2nd execution mode of expression baffle of the present invention.
Fig. 5 is the sectional view of the 3rd execution mode of expression baffle of the present invention.
Fig. 6 is the figure of the reflection collection of illustrative plates of the baffle of expression embodiment 1,2 and comparative example 1,2.
Fig. 7 is the figure of the transmission collection of illustrative plates of the baffle of expression embodiment 1,2 and comparative example 1,2.
The explanation of symbol
1,2,3: baffle, 10: electroconductive laminate, 11: matrix; 12: conducting film, 12a: oxide skin(coating), 12b: metal level; 12c: barrier layer, 12d: diaphragm, 20: support base; 30: the colored ceramic layer; 40: the anti-film that disperses, 70: bond layer, 50: electrode; 80: conductive grid film, 90: electrode.
The best mode that carries out an invention
" electroconductive laminate "
A kind of execution mode (hereinafter referred to as execution mode) to electroconductive laminate of the present invention describes.
The electroconductive laminate 10 of expression present embodiment among Fig. 1.This electroconductive laminate 10 has matrix 11 and conducting film 12.
＜matrix 〉
As the material of matrix 11, can exemplify glass plate (comprising tempered glasses such as air-quench toughened glass, chemically reinforced glass) and polyethylene terephthalate (PET), tri acetyl cellulose (TAC), Merlon (PC), polymethyl methacrylate transparent plastic materials such as (PMMA) etc.
＜conducting film 〉
Conducting film 12 is the multilayer structure making of amounted to cross laminate from matrix 11 sides (2n+1) layer [n is the integer more than 1] oxide skin(coating) 12a and metal level 12b.
In the conducting film 12, metal level better is to be provided with 2～8 layers, is more preferably and is provided with 2～6 layers.If metal level more than 2 layers, can fully reduce resistance value, if below 8 layers, the internal stress that can further suppress electroconductive laminate 10 increases.
In the conducting film 12, in order fully to guarantee the electromagnetic wave shielding ability, resistance value better is 0.4～3.5 Ω, is more preferably 0.5～2.5 Ω, and good especially is 0.5～1.5 Ω.
[oxide skin(coating)]
Oxide skin(coating) 12a in the conducting film 12 contains refractive index at the high refractive index metal oxide more than 2.3 and the zinc oxide layer as main component.Oxide skin(coating) 12a amounts to contain the above refractive index of 90 quality % at high refractive index metal oxide more than 2.3 and zinc oxide, is more preferably and contains more than the 95 quality %, and good especially is to contain more than the 99 quality %.
Refractive index because the zone of reflections is further broadened, better is titanium oxide (refractive index 2.5) and/or niobium oxide (refractive index 2.4) in the high refractive index metal oxide more than 2.3.Among the present invention, " refractive index " is meant the refractive index at wavelength 550nm place.
By the existence of high refractive index metal oxide, can improve the refractive index of oxide skin(coating) 12a, the Transflective band of conducting film 12 is broadened.Among the oxide skin(coating) 12a, the metal of high refractive index metal oxide better is 1～50 atom % with respect to the ratio of the summation of this metal and zinc, and good especially is 5～20 atom %.By making it in this scope, not only can keep Transflective band broad, and can obtain moisture-proof favorable conductive film.Its reason is also unclear, but thinks by making it in this scope, can alleviate the stress of oxide skin(coating) 12a and metal level 12b under the good rerum natura state that keeps zinc oxide.
Oxide skin(coating) 12a can contain metal oxide except that zinc oxide, titanium oxide and niobium oxide in the scope of not damaging rerum natura.For example, in order to give conductivity, can the mixed oxidization gallium, indium oxide, aluminium oxide, magnesium oxide, tin oxide etc.
The geometry thickness (hereinafter to be referred as thickness) of oxide skin(coating) 12a it is desirable to, be that (good especially is 30～50nm) to 20～60nm, and oxide skin(coating) in addition is that (good especially is 40～100nm) to 40～120nm near the oxide skin(coating) of matrix with from matrix oxide skin(coating) farthest.
[metal level]
From the angle of the resistance value that reduces conducting film 12, metal level 12b better be by fine silver forms layer." fine silver " among the present invention is meant and contains the above silver of 99.9 quality % among the metal level 12b (100 quality %).
Improve the angle of moisture-proof from suppressing silver-colored diffusion, metal level 12b better is the layer that is formed by the silver alloy that contains gold and/or bismuth.In order to make resistivity below 4.5 μ Ω cm, the summation of gold and bismuth better is 0.2～1.5 quality % in metal level 12b (100 quality %).
The total film thickness of metal level 12b better is that (good especially is 25～50nm) to 25～60nm, and being made as under the situation of 0.9 Ω in the target with resistance value better is that (good especially is 35～70nm) to 35～80nm under the situation that for example target of the resistance value of the electroconductive laminate 10 that obtains is made as 1.5 Ω.The thickness of each metal level is obtained by the metal number of plies by aforementioned total film thickness suitable the distribution.In addition, if the quantity of metal level increases, the resistivity of each metal level rises, so in order to reduce resistance, the tendency that exists total film thickness to increase.
[the formation method of conducting film]
The formation method of the conducting film 12 on matrix 11 (oxide skin(coating) 12a, metal level 12b) is unqualified, can use for example sputtering method, vacuum vapour deposition, ion plating method, chemical vapour deposition technique etc.Wherein, because having good stability of quality, characteristic better is sputtering method.As sputtering method, can exemplify pulse sputtering method, AC sputtering method etc.
Adopt the formation of the conducting film 12 of sputtering method for example can followingly to carry out.At first, use the target (hereinafter referred to as ZnO mixing target) that constitutes by zinc oxide and high refractive index metal oxide, import the argon gas that has mixed oxygen, carry out the pulse sputter, form oxide skin(coating) 12a on matrix 11 surfaces.
Then, use the target of silver-colored target or silver alloy, import argon gas, carry out the pulse sputter, form metal level 12b.By repeating this operation,, thereby form the conducting film 12 of multilayer structure making at last forming oxide skin(coating) 12a with aforementioned same method.
ZnO mixing target can use pressure sintering or HIP (high temperature insostatic pressing (HIP)) method to carry out sintering and make by mixing high-purity (common 99.9%) powder of each composition.Adopt under the situation of pressure sintering, specifically in vacuum or inert gas atmosphere, under the temperature of 1000～1200 ℃ of maximum temperatures, carry out hot pressing and make by the Zinc oxide powder that will contain high refractive index metal oxide.This ZnO mixing target better be the porosity below 5.0%, resistivity is less than 1 Ω cm.
[diaphragm]
In the conducting film 12 of present embodiment, the oxide skin(coating) 12a of the superiors is provided with diaphragm 12d.Diaphragm 12d protection oxide skin(coating) 12a and metal level 12b are not encroached on by moisture, bonding agent (the particularly alkaline bonding agent) infringement in the time of can protecting oxide skin(coating) 12a not to be subjected to bonding resin molding arbitrarily on the oxide skin(coating) 12a on surface (functional membranes such as the diaphragm used etc. of moisture barrier films, the anti-film that disperses, antireflection film, near-infrared shielding, near-infrared absorption film etc.).In addition, this diaphragm 12d is the inscape of choosing wantonly in the present invention, can omit.
As diaphragm 12d, specifically can exemplify the oxidation film of metals such as Sn, In, Ti, Si and nitride film etc., good especially is indium-tin-oxide (ITO) film.
The thickness of diaphragm 12d better is 2～30nm, is more preferably 3～20nm.
[barrier layer]
As shown in Figure 2, in the conducting film 12, oxide skin(coating) 12a and metal level 12b cross laminate are provided with barrier layer 12c between oxide skin(coating) 12a and metal level 12b.If barrier layer 12c is set on metal level 12b, as mentioned above, under oxygen atmosphere, form under the situation of oxide skin(coating) 12a, can prevent the oxidation of metal level 12b.As barrier layer 12c, can exemplify the layer that can under the condition that does not have oxygen, form, as material, can use for example Al-Doped ZnO, tin-doped indium oxide etc.
The transmission of visible light of electroconductive laminate of the present invention better is more than 55%, is more preferably more than 60%.In addition, the transmissivity at the wavelength 850nm place of electroconductive laminate of the present invention better is below 5%, and good especially is below 2%.
[purposes]
The conductivity of electroconductive laminate of the present invention (electromagnetic wave shielding performance), visible light transmission and near-infrared shielding are good, and lamination is under the situation of support bases such as glass, the Transflective band broadens, so can be used as the plasma display electromagnetic shielding film.
In addition, electroconductive laminate of the present invention can be as the transparency electrode of liquid crystal display cells etc.This transparency electrode is because sheet resistance is low, so responsiveness is good, and reflectivity is suppressed to the level of glass, so identification is good.
In addition, electroconductive laminate of the present invention can be used as windshield.This windshield can bring into play the function of antifog or ice-melt, and resistance is low by to the conducting film energising, so the required voltage of switching on is low, reflectivity is suppressed to the level of glass, therefore can not damage driver's identification.
In addition, the reflectivity in the infrared spectral range of electroconductive laminate of the present invention is very high, therefore can be as the heat mirror of the window that is arranged at building etc.
In addition, therefore the electromagnetic shielding effect of electroconductive laminate of the present invention is good, can drain to outdoor and the electromagnetic wave that prevents to influence electric/electronic device invades indoor electromagnetic wave shielding glass pane from outdoor from the electromagnetic wave of electric/electronic device radiation as preventing.
" plasma display baffle "
Below, to electroconductive laminate of the present invention is described as the example of plasma display with the electromagnetic shielding film of baffle (hereinafter referred to as baffle).
(the 1st execution mode)
The baffle of expression the 1st execution mode among Fig. 3.This baffle 1 has support base 20, be located at above-mentioned electroconductive laminate 10 on the support base 20, be located at electroconductive laminate 10 sides in the support base 20 face circumference colored ceramic layer 30, be bonded in the anti-film 40 that disperses of in the support base 20 and faces electroconductive laminate 10 side opposition sides, the electrode 50 that is electrically connected with the circumference of the conducting film 12 of electroconductive laminate 10 and be located at diaphragm 60 on the electroconductive laminate 10.
Between electroconductive laminate 10 and the support base 20, between electroconductive laminate 10 and the diaphragm 60, support base 20 and anti-dispersing be provided with bond layer 70 between the film 40.
In addition, in this baffle 1, electroconductive laminate 10 is located at the PDP side of support base 20.
＜support base 〉
As the material of support base 20, can exemplify and same material of the material of the matrix 11 of above-mentioned electroconductive laminate 10 etc.
＜colored ceramic layer 〉
Colored ceramic layer 30 is for being used for hidden electrode 50 can't directly be seen it from observer's side layer.Colored ceramic layer 30 can be by for example being printed on the support base 20 or pasting the painted formation that brings.
＜anti-the film that disperses 〉
The layer that disperses of anti-support base 20 fragments of film 40 when being used to prevent support base 20 damages that disperse.As the anti-film 40 that disperses, be not particularly limited, can use the material that generally is used for baffle.
The anti-film 40 that disperses can have anti-reflective function.The known various film that has anti-disperse function and anti-reflective function concurrently is so long as this kind film can use arbitrarily.For example, can exemplify the ARCTOP (trade name) of Asahi Glass corporate system.ARCTOP (trade name) implements the film that antireflection is handled for the anti-reflection layer that the one side at the polyurethanes soft resin film with self-regeneration and anti-dispersion characteristic forms the low-refraction that is made of noncrystalline fluoropolymer.In addition, can also exemplify on the film that forms by plastics such as PET the film etc. that has formed the anti-reflection layer of low-refraction with wet method or dry method.
＜electrode 〉
In order to ensure the electromagnetic shielding effect of conducting film 12, electrode 50 better is a whole circumference of being located at conducting film 12.
As the material of electrode 50, from the angle of electromagnetic wave shielding ability, the preferred low material of resistance.For example, the material of preferably using silver coating (Ag) thickener (thickener that contains Ag and frit) or copper (Cu) thickener (thickener that contains Cu and frit) and sintering to obtain.
＜diaphragm 〉
In addition, as diaphragm 60, can use the above-mentioned anti-film that disperses.
＜bond layer 〉
As the bonding agent of bond layer 70, can use commercially available bonding agent.As preferred object lesson, can the exemplified by acrylic ester copolymer, bonding agent such as polyvinyl chloride, epoxy resin, polyurethane, vinyl acetate copolymer, styrene-propene acid copolymer, polyester, polyamide, polyolefin, Styrene-Butadiene class rubber, butyl rubber, organic siliconresin.Because can obtain good moisture-proof, good especially is acrylic-based adhesives.
In addition, can mix the additive that ultra-violet absorber etc. has various functions in this bond layer 70.
(the 2nd execution mode)
The baffle of expression the 2nd execution mode among Fig. 4.This baffle 2 has support base 20, be located at the electroconductive laminate 10 of the one side of support base 20, be located at the anti-film 40 that disperses on the electroconductive laminate 10, with circumference be electrically connected on the conducting film 12 of electroconductive laminate 10 electrode 50, be located at the colored ceramic layer 30 of the circumference of in the support base 20 and faces electroconductive laminate 10 side opposition sides.In addition, the anti-film 40 that disperses is located at the inboard of electrode 50.
In addition, in the present embodiment, for the structure identical with the 1st execution mode, mark and the same symbol of Fig. 3 omit explanation.
In the baffle 2 of the 2nd execution mode, electroconductive laminate 10 is located at observer's side of support base 20.
(the 3rd execution mode)
The baffle of expression the 3rd execution mode among Fig. 5.This baffle 3 has support base 20; be bonded in the electroconductive laminate 10 on support base 20 surfaces by bond layer 70; be bonded in the electroconductive laminate 10 lip-deep anti-films 40 that disperse by bond layer 70; be located at colored ceramic layer 30 with the circumference on support base 20 surfaces of electroconductive laminate 10 opposition sides; be bonded in the conductive grid film 80 on support base 20 surfaces by bond layer 70 with the circumference of conductive grid film 80 and colored ceramic layer 30 overlapping state; be located at the electrode 90 of the periphery of baffle 3 with the state of the conductivity mesh layer (diagram slightly) of the conducting film 12 that is electrically connected electroconductive laminate 10 and conductive grid film 80.Baffle 3 is observer's side that electroconductive laminate 10 is located at support base 20, and conductive grid film 80 is located at the example of the PDP side of support base 20.
In addition, in the 3rd execution mode, for the structure identical with the 1st execution mode, mark and the same symbol of Fig. 3 omit explanation.
The film that the conductivity mesh layer that conductive grid film 80 is made of copper for formation on hyaline membrane gets.Usually by behind bonding Copper Foil on the hyaline membrane, be processed into mesh-shape manufacturing.
Copper Foil can be in calendering copper, the cathode copper any, suitably use material known to get final product as required.Copper Foil can carry out various surface treatments.As surface treatment, can exemplify chromate processing, roughening treatment, pickling, zinc chromate processing etc.The thickness of Copper Foil better is 3～30 μ m, is more preferably 5～30 μ m, and good especially is 7～10 μ m.Thickness by making Copper Foil can shorten etching period below 30 μ m, by making them more than 3 μ m, electromagnetic wave shielding performance raises.
The aperture opening ratio of conductivity mesh layer better is 60～95%, is more preferably 65～90%, and good especially is 70～85%.
The peristome of conductivity mesh layer be shaped as equilateral triangle, square, regular hexagon, circle, rectangle, rhombus etc.Peristome better is the shape unanimity and is arranged in the face.
The size of peristome better is that 1 limit or diameter are 5～200 μ m, is more preferably 10～150 μ m.1 limit by making peristome or diameter are below 200 μ m, and electromagnetic wave shielding performance improves, and is by making them more than 5 μ m, few to the influence of PDP image.
The width of the metal part except that peristome better is 5～50 μ m.That is, the arrangement pitches of peristome better is 10～250 μ m.Width by making metal part is more than 5 μ m, and processing becomes easily, and is by making them below 50 μ m, few to the influence of PDP image.
If the face resistance of conductivity mesh layer is low excessively, then the film thickening becomes and can't fully guarantee peristome, to the generation harmful effects such as optical property of baffle 3.On the other hand, if the face too high in resistance of conductivity mesh layer, then becoming to obtain enough electromagnetic wave shielding performances.Therefore, the face resistance of conductivity mesh layer better is 0.01～10 Ω/, is more preferably 0.01～2 Ω/, and good especially is 0.05～1 Ω/.
1 limit of the face resistance use ratio open portion of conductivity mesh layer or the big electrode more than 5 times of diameter are measured by 4 terminal methods with the electrode gap more than 5 times of the arrangement pitch of peristome and are got final product.For example, peristome is the square of 1 limit, 100 μ m, under the situation that the width of the metal part of 20 μ m is arranged regularly, the electrode of diameter 1mm is spaced mensuration with 1mm gets final product.Perhaps, the conductive grid film can be processed into rectangle, electrode is located at the two ends of its long side direction, measure its resistance R, try to achieve according to following by the length a of long side direction, the length b of short side direction.
Face resistance=R * b/a
When being laminated in Copper Foil on the hyaline membrane, use transparent bonding agent.As bonding agent, can exemplified by acrylic class bonding agent, epoxies bonding agent, polyurethanes bonding agent, silicone based bonding agent, polyesters bonding agent etc.As the type of bonding agent, better be 2 liquid type or thermohardening types.In addition, as bonding agent, better be the good bonding agent of resistance to chemical reagents.
As Copper Foil being processed into cancellous method, can exemplify photoetching process.In the print process, the figure that carries out peristome by silk screen printing forms.In the photoetching process, photo-induced corrosion resistant material is formed on the Copper Foil, forms the figure of peristome by exposure, development, etching by rolling method, spin-coating method, whole print process, transfer printing etc.As other method that forms the conductivity mesh layer, can exemplify the method that forms the figure of peristome by print processes such as silk screen printings.
More than the baffle 1～3 of Shuo Ming the 1st execution mode～the 3rd execution mode have support base 20, be located at electroconductive laminate 10 on the support base 20, with the electrode 50 or the electrode 90 of the conducting film 12 of electroconductive laminate 10.In addition, as mentioned above, the conducting film 12 of electroconductive laminate 10 is the multilayer structure making of amounted to cross laminate from matrix 11 sides (2n+1) layer [n is the integer more than 1] oxide skin(coating) 12a and metal level 12b, oxide skin(coating) 12a contain refractive index at the high refractive index metal oxide more than 2.3 and zinc oxide as main component, metal level 12b contains silver or silver alloy as main component.In such electroconductive laminate 10, because the oxide skin(coating) 12a of conducting film 12 contains high refractive index metal oxide, so the Transflective band is broadened.Therefore, even do not increase the lamination number, also can obtain the baffle of Transflective bandwidth.In addition, by not increasing the lamination number, can improve visible light transmission.And, because the contained zinc oxide of oxide skin(coating) 12a has crystallinity, therefore be formed at the also easy crystallization of metal among the metal level 12b on the oxide skin(coating) 12a, the difficult migration.Its result, the conductivity height of baffle, the electromagnetic wave shielding ability is strong.
In addition, baffle of the present invention is not limited to above-mentioned execution mode.For example, in the above-mentioned execution mode, bond layer 70 is set comes laminated film, but also can not use adhesive or bonding agent, adopt the bonding of heating.
In addition, in the baffle of the present invention, can have antireflection film as required or as the anti-reflection layer of low refractive index film.As antireflection film, be not particularly limited, can use the film that generally is used for baffle.If particularly use the film of fluorine resin class, antireflection is better.
Because the reflectivity step-down of the baffle that obtains obtains desirable reflected colour, so for this anti-reflection layer itself, it better is 500～600nm that the reflectivity in the visible region reaches minimum wavelength, good especially is 530～590nm.
In addition, can make baffle have the near-infrared shielding function.As making its method, can exemplify the method for using near infrared shielding film, the method for using the near-infrared absorbing matrix, when rete is long-pending, use the method for the bonding agent that has added near infrared ray absorption, in antireflection resin molding etc., add near infrared ray absorption and make its method that has the near-infrared absorbing function simultaneously, use have the method etc. of the conducting film of near infrared ray reflective function with near-infrared shielding function.
Embodiment
(embodiment 1)
With highly purified Zinc oxide powder and titanium dioxide powder with zinc oxide: the condition of titanium oxide=80: 20 (mass ratio) is mixed with ball mill, the modulation mixed-powder.This mixed-powder is filled in the hot pressing mould of carbon system,, obtains zinc oxide and titanium oxide mixing target in argon gas atmosphere, to implement hot pressing in 1100 ℃ of conditions that kept 1 hour.The pressure of hot pressing is 100kg/cm
2
Followingly make electroconductive laminate shown in Figure 2.
At first, following be used to clean as the dry method of the employing ion beam on the PET film surface of the thick 100 μ m of matrix 11 clean.In argon gas, mix about 30% oxygen earlier, apply the electric power of 100W.Argon ion that will obtain by the ion beam source ionization and irradiation of oxygen are in matrix surface.
Then, use zinc oxide and titanium oxide mixings target [zinc oxide: titanium oxide=80: 20 (mass ratio)], in argon gas, import behind the oxygen of mixing 10 volume %, carry out frequency 50kHz, electrical power density 4.5W/cm with the pressure of 0.73Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the oxide skin(coating) 12a of thick 35nm at the matrix surface of having implemented the dry method clean.Measure by the Rutherford backscattering method, the result is in this oxide skin(coating) 12a, and in the summation of zinc and titanium (100 atom %), zinc is 80 atom %, and titanium is 20 atom %.In addition, among the oxide skin(coating) 12a, in all atom summations (100 atom %), zinc is 34.3 atom %, and titanium is 8.0 atom %, and oxygen is 57.7 atom %.If it is scaled ZnO and TiO
2, then the summation of oxide is 96.7 quality %.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 50kHz, electrical power density 2.3W/cm with the pressure of 0.73Pa
2, inversion pulse width 10 microseconds the pulse sputter, form the metal level 12b of thick 10nm.
Then, use the zinc oxide target mixed 5 quality % aluminium oxide, import argon gas, carry out frequency 50kHz, electrical power density 2.7W/cm with the pressure of 0.45Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the Zinc oxide film (barrier layer 12c) of thick 5nm.
Then, use zinc oxide and titanium oxide mixings target [zinc oxide: titanium oxide=80: 20 (mass ratio)], in argon gas, import behind the oxygen of mixing 10 volume %, carry out frequency 50kHz, electrical power density 4.5W/cm with the pressure of 0.73Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the zinc oxide titanium oxide hybrid films of thick 65nm.Form oxide skin(coating) 12a with Zinc oxide film and the zinc oxide titanium oxide hybrid films that obtains like this.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 50kHz, electrical power density 2.3W/cm with the pressure of 0.73Pa
2, inversion pulse width 10 microseconds the pulse sputter, form the metal level 12b of thick 14nm.
Then, use the zinc oxide target mixed 5 quality % aluminium oxide, import argon gas, carry out frequency 50kHz, electrical power density 2.7W/cm with the pressure of 0.45Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the Zinc oxide film (barrier layer 12c) of thick 5nm.
Then, use zinc oxide and titanium oxide mixings target [zinc oxide: titanium oxide=80: 20 (mass ratio)], in argon gas, import behind the oxygen of mixing 10 volume %, carry out frequency 50kHz, electrical power density 4.5W/cm with the pressure of 0.73Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the zinc oxide titanium oxide hybrid films of thick 65nm.Form oxide skin(coating) 12a with Zinc oxide film and the zinc oxide titanium oxide hybrid films that obtains like this.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 50kHz, electrical power density 2.3W/cm with the pressure of 0.73Pa
2, inversion pulse width 10 microseconds the pulse sputter, form the metal level 12b of thick 14nm.
Then, use the zinc oxide target mixed 5 quality % aluminium oxide, import argon gas, carry out frequency 50kHz, electrical power density 2.7W/cm with the pressure of 0.45Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the Zinc oxide film (barrier layer 12c) of thick 5nm.
Then, use zinc oxide and titanium oxide mixings target [zinc oxide: titanium oxide=80: 20 (mass ratio)], in argon gas, import behind the oxygen of mixing 10 volume %, carry out frequency 50kHz, electrical power density 4.5W/cm with the pressure of 0.73Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the zinc oxide titanium oxide hybrid films of thick 65nm.Form oxide skin(coating) 12a with Zinc oxide film and the zinc oxide titanium oxide hybrid films that obtains like this.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 50kHz, electrical power density 2.3W/cm with the pressure of 0.73Pa
2, inversion pulse width 10 microseconds the pulse sputter, form the metal level 12b of thick 10nm.
Then, use the zinc oxide target mixed 5 quality % aluminium oxide, import argon gas, carry out frequency 50kHz, electrical power density 2.7W/cm with the pressure of 0.45Pa
2, inversion pulse width 2 microseconds the pulse sputter, form Zinc oxide film (barrier layer 12c) 12c of thick 5nm.
Then, use zinc oxide and titanium oxide mixings target [zinc oxide: titanium oxide=80: 20 (mass ratio)], in argon gas, import behind the oxygen of mixing 10 volume %, carry out frequency 50kHz, electrical power density 4.5W/cm with the pressure of 0.73Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the zinc oxide titanium oxide hybrid films of thick 30nm.Form oxide skin(coating) 12a with Zinc oxide film and the zinc oxide titanium oxide hybrid films that obtains like this.
Then, use ITO target [indium: tin=90: 10 (mass ratio)], import after in argon gas, mixing the oxygen of 5 volume %, carry out frequency 100kHz, electrical power density 1.3W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, on the oxide skin(coating) 12a of the superiors, form ITO film as the thick 5nm of diaphragm 12d.
Thus, obtained on matrix 11 cross laminate and contained titanium oxide and zinc oxide as the oxide skin(coating) 12a of main component and the electroconductive laminate 10 of the metal level 12b that is formed by gold-silver alloy, oxide skin(coating) 12a is of five storeys, and metal level 12b has 4 layers.
For the electroconductive laminate of embodiment 1, the transmission of visible light (the values Y of regulation among the JIS Z 8701) that records by Tokyo electricity look corporate system color analysis instrument TC1800 is 71.40%, and visible reflectance is 6.50%.In addition, the transmissivity at wavelength 850nm place is 0.96%.
In addition, the sheet resistance (sheet resistance) that records by Nagy corporate system vortex patern resistance measurer SRM12 is 0.942 Ω.The results are shown in table 1.
Then, matrix 11 side surfaces at this electroconductive laminate 10 are provided with bond layer.
Use this electroconductive laminate 10 following baffles shown in Figure 31 of making.
To become the size of regulation as the cutting of the glass plate of support base 20, chamfering, and after the cleaning, the ink screen of colored ceramic layer usefulness will be printed in the glass plate periphery, intensive drying forms colored ceramic layer 30.Then,, this glass plate is heated to 660 ℃ as glass reinforced processing, air-cooled then, implement glass reinforced processing.
Colored ceramic layer 30 side at this glass plate adhere to above-mentioned electroconductive laminate 10 by bond layer 70.Then, in order to protect electroconductive laminate 10, on electroconductive laminate 10, pass through bond layer 70 bonding diaphragms 60 (Asahi Glass corporate system, trade name: ARCTOP CP21).But in order to form electrode, circumference leaves the not part of bonding diaphragm (electrode formation portion).
Then, (sun イ Application キ manufacturing company system AF4810), in 85 ℃ of dryings 35 minutes, forms electrode 50 in recirculation furnace with the condition silk screen printing of nylon screen #180, emulsion thickness 20 μ m silver thickener in electrode formation portion.
Then, at the back side of glass plate (face of the opposition side of a side of bonding electroconductive laminate 10) by polyurethanes soft resin film (Asahi Glass corporate system, the trade name: ARCTOP URP2199) of the anti-film 40 that disperses of adhesive phase 70 bonding conducts.This polyurethanes soft resin film also has anti-reflective function.In addition, in this polyurethanes soft resin film, add colouring agent usually, carry out tint correction, orange toning (Ne カ Star ト), realize the raising of color reprodubility, do not estimate tint correction, orange toning in the present embodiment, therefore not painted.
For the baffle of embodiment 1, the transmission of visible light (the values Y of regulation among the JIS Z 8701) that records by Tokyo electricity look corporate system color analysis instrument TC1800 is 71.5%, and visible reflectance is 1.92%.In addition, the transmissivity at wavelength 850nm place is 0.76%.The results are shown in table 2.The reflection collection of illustrative plates of this baffle is shown in Fig. 6, and the transmission collection of illustrative plates is shown in Fig. 7.
(embodiment 2)
Except zinc oxide and titanium oxide mixing target all use zinc oxide: the target of titanium oxide=50: 50 (mass ratio), electroconductive laminate and baffle are made in operation similarly to Example 1.Among the oxide skin(coating) 12a of embodiment 2, in the summation of zinc and titanium (100 atom %), zinc is 50 atom %, and titanium is 50 atom %.In addition, among the oxide skin(coating) 12a, in all atom summations (100 atom %), zinc is 23.6 atom %, and titanium is 16.7 atom %, and oxygen is 59.7 atom %.If it is scaled ZnO and TiO
2, then the summation of oxide is 97.7 quality %.
For the electroconductive laminate of embodiment 2, the transmission of visible light (the values Y of regulation among the JIS Z 8701) that records by Tokyo electricity look corporate system color analysis instrument TC1800 is 62.94%, and visible reflectance is 4.96%.In addition, the transmissivity at wavelength 850nm place is 0.69%.
In addition, the sheet resistance (sheet resistance) that records by Nagy corporate system vortex patern resistance measurer SRM12 is 0.965 Ω.The results are shown in table 1.
For the baffle of embodiment 2, the transmission of visible light (the values Y of regulation among the JIS Z 8701) that records by Tokyo electricity look corporate system color analysis instrument TC1800 is 62.6%, and visible reflectance is 1.92%.In addition, the transmissivity at wavelength 850nm place is 0.51%.The results are shown in table 2.The reflection collection of illustrative plates of this baffle is shown in Fig. 6, and the transmission collection of illustrative plates is shown in Fig. 7.
(comparative example 1)
Make the electroconductive laminate except following, electroconductive laminate and baffle are made in operation similarly to Example 1.
At first, following be used to clean as the dry method of the employing ion beam on the PET film surface of the thick 100 μ m of matrix 11 clean.Mix earlier about 30% oxygen in argon gas, apply the electric power of 100W, argon ion that will obtain by the ion beam source ionization and irradiation of oxygen are in matrix surface.
Then, use the zinc oxide target mixed 5 quality % aluminium oxide, import after in argon gas, mixing the oxygen of 3 volume %, carry out frequency 100kHz, electrical power density 5.8W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, form the oxide skin(coating) a of thick 40nm at the matrix surface of having implemented the dry method clean.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 100kHz, electrical power density 0.6W/cm with the pressure of 0.5Pa
2, inversion pulse width 5 microseconds the pulse sputter, form the metal level of thick 9nm.
Then, use the zinc oxide target mixed 5 quality % aluminium oxide, import after in argon gas, mixing the oxygen of 3 volume %, carry out frequency 100kHz, electrical power density 5.8W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, form the oxide skin(coating) of thick 80nm.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 100kHz, electrical power density 0.9W/cm with the pressure of 0.5Pa
2, inversion pulse width 5 microseconds the pulse sputter, form the metal level of thick 11nm.
Then, use the zinc oxide target mixed 5 quality % aluminium oxide, import after in argon gas, mixing the oxygen of 3 volume %, carry out frequency 100kHz, electrical power density 5.8W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, form the oxide skin(coating) of thick 80nm.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 100kHz, electrical power density 1.0W/cm with the pressure of 0.5Pa
2, inversion pulse width 5 microseconds the pulse sputter, form the metal level of thick 13nm.
Then, use the zinc oxide target mixed 5 quality % aluminium oxide, import after in argon gas, mixing the oxygen of 3 volume %, carry out frequency 100kHz, electrical power density 5.8W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, form the oxide skin(coating) of thick 80nm.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 100kHz, electrical power density 1.0W/cm with the pressure of 0.5Pa
2, inversion pulse width 5 microseconds the pulse sputter, form the metal level of thick 13nm.
Then, use the zinc oxide target mixed 5 quality % aluminium oxide, import after in argon gas, mixing the oxygen of 3 volume %, carry out frequency 100kHz, electrical power density 5.8W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, form the oxide skin(coating) of thick 80nm.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 100kHz, electrical power density 0.9W/cm with the pressure of 0.5Pa
2, inversion pulse width 5 microseconds the pulse sputter, form the metal level of thick 11nm.
Then, use the zinc oxide target mixed 5 quality % aluminium oxide, import after in argon gas, mixing the oxygen of 3 volume %, carry out frequency 100kHz, electrical power density 5.8W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, form the oxide skin(coating) of thick 80nm.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 100kHz, electrical power density 0.6W/cm with the pressure of 0.5Pa
2, inversion pulse width 5 microseconds the pulse sputter, form the metal level of thick 9nm.
Then, use the zinc oxide target mixed 5 quality % aluminium oxide, import after in argon gas, mixing the oxygen of 3 volume %, carry out frequency 100kHz, electrical power density 5.2W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, form the oxide skin(coating) of thick 35nm.
Then, use ITO target [indium: tin=90: 10 (mass ratio)], import after in argon gas, mixing the oxygen of 5 volume %, carry out frequency 100kHz, electrical power density 0.5W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, on the oxide skin(coating) of the superiors, form ITO film as the thick 5nm of diaphragm.
Thus, obtained on matrix cross laminate by the electroconductive laminate of AZO oxide skin(coating) that forms and the metal level that is formed by gold-silver alloy, oxide skin(coating) has 7 layers, and metal level has 6 layers.
For the electroconductive laminate of comparative example 1, the transmission of visible light (the values Y of regulation among the JIS Z 8701) that records by Tokyo electricity look corporate system color analysis instrument TC1800 is 59.75%, and visible reflectance is 5.79%.In addition, the transmissivity at wavelength 850nm place is 0.5%.
In addition, the sheet resistance (sheet resistance) that records by Nagy corporate system vortex patern resistance measurer SRM12 is 0.957 Ω.The results are shown in table 1.
For the baffle of comparative example 1, the transmission of visible light (the values Y of regulation among the JIS Z 8701) that records by Tokyo electricity look corporate system color analysis instrument TC1800 is 60.3%, and visible reflectance is 1.98%.In addition, the transmissivity at wavelength 850nm place is 0.28%.The results are shown in table 2.The reflection collection of illustrative plates is shown in Fig. 6, and the transmission collection of illustrative plates is shown in Fig. 7.
(comparative example 2)
Make the electroconductive laminate except following, electroconductive laminate and baffle are made in operation similarly to Example 1.
At first, following be used to clean as the dry method of the employing ion beam on the PET film surface of matrix clean.In argon gas, mix about 30% oxygen earlier, apply the electric power of 100W.Argon ion that will obtain by the ion beam source ionization and irradiation of oxygen are in matrix surface.
Then, use the zinc oxide target mixed 5 quality % aluminium oxide, import after in argon gas, mixing the oxygen of 3 volume %, carry out frequency 100kHz, electrical power density 5.7W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, form the oxide skin(coating) of thick 40nm at the matrix surface of having implemented the dry method clean.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 100kHz, electrical power density 0.6W/cm with the pressure of 0.5Pa
2, inversion pulse width 5 microseconds the pulse sputter, form the metal level of thick 13nm.
Then, use the zinc oxide target mixed 5 quality % aluminium oxide, import after in argon gas, mixing the oxygen of 3 volume %, carry out frequency 100kHz, electrical power density 4.7W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, form the oxide skin(coating) of thick 80nm.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 100kHz, electrical power density 0.9W/cm with the pressure of 0.5Pa
2, inversion pulse width 5 microseconds the pulse sputter, form the metal level of thick 16nm.
Then, use the zinc oxide target mixed 5 quality % aluminium oxide, import after in argon gas, mixing the oxygen of 3 volume %, carry out frequency 100kHz, electrical power density 4.7W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, form the oxide skin(coating) of thick 80nm.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 100kHz, electrical power density 1.0W/cm with the pressure of 0.5Pa
2, inversion pulse width 5 microseconds the pulse sputter, form the metal level of thick 16nm.
Then, use the zinc oxide target mixed 5 quality % aluminium oxide, import after in argon gas, mixing the oxygen of 3 volume %, carry out frequency 100kHz, electrical power density 4.7W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, form the oxide skin(coating) of thick 80nm.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 100kHz, electrical power density 0.6W/cm with the pressure of 0.5Pa
2, inversion pulse width 5 microseconds the pulse sputter, form the metal level of thick 13nm.
Then, use the zinc oxide target mixed 5 quality % aluminium oxide, import after in argon gas, mixing the oxygen of 3 volume %, carry out frequency 100kHz, electrical power density 5.2W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, form the oxide skin(coating) of thick 35nm.
Then, use ITO target [indium: tin=90: 10 (mass ratio)], import after in argon gas, mixing the oxygen of 3 volume %, carry out frequency 100kHz, electrical power density 1.0W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, on the oxide skin(coating) of the superiors, form ITO film as the thick 5nm of diaphragm.
Thus, obtained on matrix cross laminate by the electroconductive laminate of AZO oxide skin(coating) that forms and the metal level that is formed by gold-silver alloy, oxide skin(coating) is of five storeys, and metal level has 4 layers.
For the electroconductive laminate of comparative example 2, the transmission of visible light (the values Y of regulation among the JIS Z 8701) that records by Tokyo electricity look corporate system color analysis instrument TC1800 is 60.9%, and visible reflectance is 6.85%.In addition, the transmissivity at wavelength 850nm place is 0.40%.
In addition, the sheet resistance (sheet resistance) that records by Nagy corporate system vortex patern resistance measurer SRM12 is 0.981 Ω.The results are shown in table 1.
For the baffle of comparative example 2, the transmission of visible light (the values Y of regulation among the JIS Z 8701) that records by Tokyo electricity look corporate system color analysis instrument TC1800 is 61.8%, and visible reflectance is 4.22%.In addition, the transmissivity at wavelength 850nm place is 0.27%.The results are shown in table 2.The reflection collection of illustrative plates of this baffle is shown in Fig. 6, and the transmission collection of illustrative plates is shown in Fig. 7.
To contain silver alloy as main component, metal level be 4 layers as the quantity of the baffle metal level of the embodiment 1 of main component though oxide skin(coating) contains zinc oxide and titanium oxide, the Transflective bandwidth, and also conductivity and visible light transmission are good.
Relative with it, it is that 6 layers the transmission of visible light of baffle of comparative example 1 is low as the quantity of main component, metal level that oxide skin(coating) contains AZO.
It is that 4 layers the Transflective band of baffle of comparative example 2 is narrow as the quantity of main component, metal level that oxide skin(coating) contains AZO.
(embodiment 3)
Followingly make electroconductive laminate shown in Figure 1.
At first, following be used to clean as the dry method of the employing ion beam on the PET film surface of the thick 100 μ m of matrix 11 clean.In argon gas, mix about 30% oxygen earlier, apply the electric power of 100W.Argon ion that will obtain by the ion beam source ionization and irradiation of oxygen are in matrix surface.
Then, use zinc oxide and titanium oxide mixings target [zinc oxide: titanium oxide=85: 15 (mass ratio)], in argon gas, import behind the oxygen of mixing 15 volume %, carry out frequency 50kHz, electrical power density 4.5W/cm with the pressure of 0.73Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the oxide skin(coating) 12a of thick 40nm at the matrix surface of having implemented the dry method clean.Measure by the Rutherford backscattering method, the result is in this oxide skin(coating) 12a, and in the summation of zinc and titanium (100 atom %), zinc is 85 atom %, and titanium is 15 atom %.In addition, among the oxide skin(coating) 12a, in all atom summations (100 atom %), zinc is 37.0 atom %, and titanium is 6.2 atom %, and oxygen is 56.8 atom %.If it is scaled ZnO and TiO
2, then the summation of oxide is 96.7 quality %.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 50kHz, electrical power density 2.3W/cm with the pressure of 0.73Pa
2, inversion pulse width 10 microseconds the pulse sputter, form the metal level 12b of thick 10nm.
Then, use zinc oxide and titanium oxide mixings target [zinc oxide: titanium oxide=85: 15 (mass ratio)], in argon gas, import behind the oxygen of mixing 15 volume %, carry out frequency 50kHz, electrical power density 4.5W/cm with the pressure of 0.73Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the oxide skin(coating) 12a of thick 80nm.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 50kHz, electrical power density 2.3W/cm with the pressure of 0.73Pa
2, inversion pulse width 10 microseconds the pulse sputter, form the metal level 12b of thick 14nm.
Then, use zinc oxide and titanium oxide mixings target [zinc oxide: titanium oxide=85: 15 (mass ratio)], in argon gas, import behind the oxygen of mixing 15 volume %, carry out frequency 50kHz, electrical power density 4.5W/cm with the pressure of 0.73Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the oxide skin(coating) 12a of thick 80nm.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 50kHz, electrical power density 2.3W/cm with the pressure of 0.73Pa
2, inversion pulse width 10 microseconds the pulse sputter, form the metal level 12b of thick 10nm.
Then, use zinc oxide and titanium oxide mixings target [zinc oxide: titanium oxide=85: 15 (mass ratio)], in argon gas, import behind the oxygen of mixing 15 volume %, carry out frequency 50kHz, electrical power density 4.5W/cm with the pressure of 0.73Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the oxide skin(coating) 12a of thick 35nm.
Then, use ITO target [indium: tin=90: 10 (mass ratio)], import after in argon gas, mixing the oxygen of 5 volume %, carry out frequency 100kHz, electrical power density 1.3W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, on the oxide skin(coating) 12a of the superiors, form ITO film as the thick 5nm of diaphragm 12d.
Thus, obtained on matrix 11 cross laminate and contained titanium oxide and zinc oxide as the oxide skin(coating) 12a of main component and the electroconductive laminate 10 of the metal level 12b that is formed by gold-silver alloy, oxide skin(coating) has 4 layers, and metal level haves three layers.
For the electroconductive laminate of embodiment 3, the transmission of visible light (the values Y of regulation among the JIS Z 8701) that records by Tokyo electricity look corporate system color analysis instrument TC1800 is 77.25%, and visible reflectance is 5.07%.In addition, the transmissivity at wavelength 850nm place is 12.3%.
In addition, the sheet resistance (sheet resistance) that records by Nagy corporate system vortex patern resistance measurer SRM12 is 1.815 Ω.The results are shown in table 1.
Use this electroconductive laminate 10, similarly operate, make baffle shown in Figure 31 with embodiment.
For the baffle of embodiment 3, the transmission of visible light (the values Y of regulation among the JIS Z 8701) that records by Tokyo electricity look corporate system color analysis instrument TC1800 is 76.99%, and visible reflectance is 3.45%.In addition, the transmissivity at wavelength 850nm place is 9.6%.The results are shown in table 2.
(embodiment 4)
Followingly make electroconductive laminate shown in Figure 1.
At first, following be used to clean as the dry method of the employing ion beam on the PET film surface of the thick 100 μ m of matrix 11 clean.In argon gas, mix about 30% oxygen earlier, apply the electric power of 100W.Argon ion that will obtain by the ion beam source ionization and irradiation of oxygen are in matrix surface.
Then, use zinc oxide and titanium oxide mixings target [zinc oxide: titanium oxide=85: 15 (mass ratio)], in argon gas, import behind the oxygen of mixing 15 volume %, carry out frequency 50kHz, electrical power density 4.5W/cm with the pressure of 0.73Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the oxide skin(coating) 12a of thick 40nm at the matrix surface of having implemented the dry method clean.Measure by the Rutherford backscattering method, the result is in this oxide skin(coating) 12a, and in the summation of zinc and titanium (100 atom %), zinc is 85 atom %, and titanium is 15 atom %.In addition, among the oxide skin(coating) 12a, in all atom summations (100 atom %), zinc is 37.0 atom %, and titanium is 6.2 atom %, and oxygen is 56.8 atom %.If it is scaled ZnO and TiO
2, then the summation of oxide is 96.7 quality %.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 50kHz, electrical power density 2.3W/cm with the pressure of 0.73Pa
2, inversion pulse width 10 microseconds the pulse sputter, form the metal level 12b of thick 10nm.
Then, use zinc oxide and titanium oxide mixings target [zinc oxide: titanium oxide=85: 15 (mass ratio)], in argon gas, import behind the oxygen of mixing 15 volume %, carry out frequency 50kHz, electrical power density 4.5W/cm with the pressure of 0.73Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the oxide skin(coating) 12a of thick 80nm.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 50kHz, electrical power density 2.3W/cm with the pressure of 0.73Pa
2, inversion pulse width 10 microseconds the pulse sputter, form the metal level 12b of thick 14nm.
Then, use zinc oxide and titanium oxide mixings target [zinc oxide: titanium oxide=85: 15 (mass ratio)], in argon gas, import behind the oxygen of mixing 15 volume %, carry out frequency 50kHz, electrical power density 4.5W/cm with the pressure of 0.73Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the oxide skin(coating) 12a of thick 80nm.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 50kHz, electrical power density 2.3W/cm with the pressure of 0.73Pa
2, inversion pulse width 10 microseconds the pulse sputter, form the metal level 12b of thick 14nm.
Then, use zinc oxide and titanium oxide mixings target [zinc oxide: titanium oxide=85: 15 (mass ratio)], in argon gas, import behind the oxygen of mixing 15 volume %, carry out frequency 50kHz, electrical power density 4.5W/cm with the pressure of 0.73Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the oxide skin(coating) 12a of thick 80nm.
Then, use the silver alloy target mixed 1.0 quality % gold, import argon gas, carry out frequency 50kHz, electrical power density 2.3W/cm with the pressure of 0.73Pa
2, inversion pulse width 10 microseconds the pulse sputter, form the metal level 12b of thick 10nm.
Then, use zinc oxide and titanium oxide mixings target [zinc oxide: titanium oxide=85: 15 (mass ratio)], in argon gas, import behind the oxygen of mixing 15 volume %, carry out frequency 50kHz, electrical power density 4.5W/cm with the pressure of 0.73Pa
2, inversion pulse width 2 microseconds the pulse sputter, form the oxide skin(coating) 12a of thick 35nm.
Then, use ITO target [indium: tin=90: 10 (mass ratio)], import after in argon gas, mixing the oxygen of 5 volume %, carry out frequency 100kHz, electrical power density 1.3W/cm with the pressure of 0.35Pa
2, inversion pulse width 1 microsecond the pulse sputter, on the oxide skin(coating) 12a of the superiors, form ITO film as the thick 5nm of diaphragm 12d.
Thus, obtained on matrix 11 cross laminate and contained titanium oxide and zinc oxide as the oxide skin(coating) 12a of main component and the electroconductive laminate 10 of the metal level 12b that is formed by gold-silver alloy, oxide skin(coating) is of five storeys, and metal level has 4 layers.
For the electroconductive laminate of embodiment 4, the transmission of visible light (the values Y of regulation among the JIS Z 8701) that records by Tokyo electricity look corporate system color analysis instrument TC1800 is 67.7%, and visible reflectance is 5.88%.In addition, the transmissivity at wavelength 850nm place is 0.78%.
In addition, the sheet resistance (sheet resistance) that records by Nagy corporate system vortex patern resistance measurer SRM12 is 0.968 Ω.The results are shown in table 1.
Use this electroconductive laminate 10, baffle shown in Figure 31 is made in operation similarly to Example 1.
For the baffle of embodiment 4, the transmission of visible light (the values Y of regulation among the JIS Z 8701) that records by Tokyo electricity look corporate system color analysis instrument TC1800 is 68.0%, and visible reflectance is 2.52%.In addition, the transmissivity at wavelength 850nm place is 0.68%.The results are shown in table 2.
[table 1]
| | Embodiment | 1 | | Comparative example 1 | Comparative example 2 | | Embodiment 4 |
| Transmission of visible light (%) | 71.40 | 62.94 | 59.75 | 60.9 | 77.25 | 67.7 | |
| Visible reflectance (%) | 6.50 | 4.96 | 5.79 | 6.85 | 5.07 | 5.88 | |
| The reflectivity of 850nm (%) | 0.96 | 0.69 | 0.5 | 0.40 | 12.3 | 0.78 | |
| Sheet resistance (Ω) | 0.942 | 0.965 | 0.957 | 0.981 | 1.815 | 0.968 |
[table 2]
| | Embodiment | 1 | | Comparative example 1 | Comparative example 2 | | Embodiment 4 |
| Transmission of visible light (%) | 71.5 | 62.6 | 60.3 | 61.8 | 76.99 | 68.0 | |
| Visible reflectance (%) | 1.92 | 1.92 | 1.98 | 4.22 | 3.45 | 2.52 | |
| The reflectivity of 850nm (%) | 0.76 | 0.51 | 0.28 | 0.27 | 9.6 | 0.68 |
The possibility of utilizing on the industry
The electric conductivity of electroconductive laminate of the present invention (electromagnetic wave shielding performance), visible light transmission and near-infrared shielding are good; and lamination is in the situation of support base; because the Transflective band broadens, so can be as plasma display electromagnetic shielding film, baffle. In addition, electroconductive laminate of the present invention can be as transparency electrode, windshield, heat mirror, the electromagnetic wave shielding glass pane of liquid crystal display cells etc.
In addition, quote the announcement of all the elements of Japanese patent application 2004-345877 number of filing an application on November 30th, 2004 and Japanese patent application 2005-254907 number specification, claims, accompanying drawing and the summary of filing an application on September 2nd, 2005 here as specification of the present invention.
Claims (7)
1. electroconductive laminate, it is the electroconductive laminate that has matrix and be formed at the conducting film on the matrix, it is characterized in that, conducting film is the multilayer structure making from matrix side (2n+1) layer oxide skin(coating) that amounted to cross laminate and metal level, wherein, n is the integer more than 1, oxide skin(coating) contain zinc oxide and refractive index at the high refractive index metal oxide more than 2.3 as main component, metal level contains silver or silver alloy as main component.
2. electroconductive laminate as claimed in claim 1 is characterized in that, high refractive index metal oxide is titanium oxide and/or niobium oxide.
3. electroconductive laminate as claimed in claim 1 or 2 is characterized in that, metal level is provided with 2～8 layers.
4. as each described electroconductive laminate in the claim 1～3, it is characterized in that metal level is fine silver or contains gold and/or the silver alloy of bismuth.
5. the plasma display electromagnetic shielding film is characterized in that, is made of each described electroconductive laminate in the claim 1～4.
6. plasma display baffle; it is characterized in that having support base, be arranged at the electrode that the described plasma display of claim 5 on this support base is electrically connected with the conducting film of electromagnetic shielding film with electromagnetic shielding film, with this plasma display.
7. plasma display baffle as claimed in claim 6 is characterized in that, also has the conductive grid film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004345877 | 2004-11-30 | ||
| JP345877/2004 | 2004-11-30 | ||
| JP254907/2005 | 2005-09-02 |
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| CN2010102934544A Division CN101945564A (en) | 2004-11-30 | 2005-10-31 | Producing method of electroconductive laminate |
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| CN101066011A true CN101066011A (en) | 2007-10-31 |
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| CN 200580040719 Pending CN101066011A (en) | 2004-11-30 | 2005-10-31 | Electroconductive laminate, and electromagnetic wave shielding film and protective plate for plasma display |
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