CN1278136C - Laminate and filter of display using the same laminate - Google Patents
Laminate and filter of display using the same laminate Download PDFInfo
- Publication number
- CN1278136C CN1278136C CN 200410069275 CN200410069275A CN1278136C CN 1278136 C CN1278136 C CN 1278136C CN 200410069275 CN200410069275 CN 200410069275 CN 200410069275 A CN200410069275 A CN 200410069275A CN 1278136 C CN1278136 C CN 1278136C
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- transparent
- layer
- laminated body
- film
- window
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/445—Organic continuous phases
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
Landscapes
- Laminated Bodies (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
A transparent and conductive laminate that is substantially decreased in reactive defects, and a display filter, a heat-ray reflecting film and an electromagnetic wave-shielding film comprising the laminate are provided. The laminate includes a transparent substrate, a transparent conductive thin-film layer containing silver, and a protective layer containing a binder material and inorganic fine particles, wherein the transparent conductive thin-film layer is in contact with the protective layer. The generation of reflective defects can be outstandingly reduced. Therefore, a laminate superior in electromagnetic wave-shielding ability, heat-ray reflecting ability and visibility for a long period of time and products comprising the laminate can be obtained.
Description
Technical field
The invention relates to laminated body, is about filter of display in addition.In more detail, be about transparent conductive laminate high-quality, that permanance is good and filter of display.
Background technology
Along with the progress of multimedia society, numeral society, transmission, information releasing or processed image information or numerical information are all increasing by leaps and bounds.Therefore, the display device that shows the monitor of their usefulness connects people and communication facilities, vision facilities, computing machine etc., and as interfacing equipment, perhaps as key equipment, its importance more and more increases.
As such display device, replace weight in the past, the thick and cathode ray tube (CRT) monitor that is difficult to maximize, just concentrating one's energy to study various thin displays, especially, slimming, big drawingization can just come on the scene than the plasma display panel that is easier to realize (PDP) or field-emitter display (FED) etc.
Especially, PDP has entered a large amount of production stages, and the plan of volume increase significantly of multiplication is every year got by manufacturing company.On the other hand, because the fabricator who also has new statement to add, so newspaper etc. is gone up its market of prediction and will promptly be enlarged from now on.
As mentioned above, it is favourable such advantage that PDP has in slimming, maximization, but because it utilizes the cause of discharge, so the strong such problem of electromagnetic-wave leakage that produces is arranged in theory.Therefore, the secure reference value that will be suppressed at regulation from the electromagnetic-wave leakage that plasma display takes place [for example, in Japan, VCCI (Voluntary Control Council for Interference by dataprocessing equipment electronic office machine), in the U.S., FCC (FederalCommunication Commission)] just necessitate with interior.
In addition, PDP also produces strong near infrared light.WLAN, cordless telephone, infrared remote controller etc. are to utilize near infrared machine, so PDP also is subjected to causing the censure of possibility of the misoperation of these machines.Because the above fact, in PDP, electromagnetic-wave leakage is reduced in the scope of afore mentioned rules, just need to implement necessary means, cutting down the grade that does not produce misoperation to the practicality at the light of 800～1000nm of near infrared range wavelength region may.
By using conductive material covering PDP all,, need use the material that except that having electric conductivity, also has the transparency in image displaying part though can suppress as above-mentioned electromagnetic wave and near infrared emitting as the metal.For this reason, be fit to use light filter in the display part of PDP with transparent conductivity.As the suitable example of using such filter of display, can enumerate the matrix of glass plate etc. comprehensively on the optical filter of transparent conducting film type of configuration transparent conducting film.The optical filter of transparent conducting film type, known structure have to have on matrix by the transparent conducting film that is used for shielding electromagnetic wave and having and prevent to reflect the rhythmo structure that the light filter of function or dimming function constitutes.
Though it is self-evident filter of display being had the requirement of electromagnetic wave shielding ability, but because the face resistance value of this filter of display is low more good more, therefore, in the pure material with than the minimum silver of resistance value or be suitable as above-mentioned transparent conducting film based on the metallic film of silver and use.In fact, further transmissivity rises and the stability-enhanced purpose of metal film layer in order to reach, normally with utilize the clamping of transparent high refractive index film layer based on the laminated body of the metal film layer of silver as transparent conducting film.
But, well-known, be suitable as the silver that the metallic film layer material uses, there is the so big problem of aggegation of as easy as rolling off a log generation atom.In case the silver atoms generation aggegation of silver-colored thin layer except the low resistive of infringement as metallic film, also can produce argenteous point (being also referred to as spot defect, perhaps reflectivity defective, white point).Give birth to the occasion of reflectivity defective at this fecund of filter of display, above-mentioned reflectivity defective, become white point on the many gripping image of showing out on the large-scale plasma display of this light filter and occur having fixed, thereby produce the disadvantage that reduces image quality.Like this, above-mentioned reflectivity defective becomes the high transparent that this metallic film material has and the big problem of low resistive forfeiture, meanwhile, also just descends significantly as the commodity value of light filter.
Past is just known, the aggegation of the silver atoms of so silver-colored thin layer for example takes place in the presence of chlorion or foreign matter (particle) etc. easily.Be accompanied by the urgent desired images in market and maximize, the number of estimating to sneak into particle in per 1 light filter etc. will increase.Therefore the white point number that produces on every light filter can increase, and estimates that the qualification rate that light filter is produced will reduce.Therefore, for optical filter, what will further consider from now on is the technology that more effectively prevents to produce white point on its silver-colored thin layer for the PDP of more and more large-scale change.
Reported in the flat 9-331488 communique and removed at public clear 59-44993 communique of spy or special opening, but, required under higher level, to suppress the aggegation of silver atoms in order to produce large-scale filter of display with high qualification rate as above-mentioned foreign matter, the trial of chlorine.
On the other hand, also attempt, prevent the silver-colored thin layers of arrival such as this chlorion by transparent high refractive index film layer is thickened.But, as mentioned above, because therefore the demanding transparency of optical filter just to the thickness generation restriction of transparent high refractive index film layer, also just is restricted thereby use said method.
As other trial, also having has corrosion proof metallic film to be stacked in method on the silver-colored thin layer copper or platinum etc., but has the problem that the transparency reduces, face resistance rises that produces that is accompanied by.
As mentioned above, easily the filter of display of the formation of inhibitory reflex generation of defects does not also have so far.
On the other hand, in recent years, the development of wireless device and electronic equipment is surprising, and its demand increases anxious.Wireless device is no doubt convenient, but employed electromagnetic wave has by other people intercept, obtains the danger of the information that this electromagnetic wave is loaded with.In addition, wireless device not only, and in electronic equipment except that body, wireless kind equipment also has electromagnetic generation, therefore and wireless device the intercept by other people is similarly arranged, easily read the danger of its information.Leakage for the information that suppresses to follow this electromagnetic-wave leakage in recent years, is improving the requirement to electromagnetic shielding material.Though the enough conductive material shielding electromagnetic wave as the metal of energy, the display part of the window of various buildingss and automotive window, various display devices grades, and except that the electromagnetic wave shielding performance, also requires to have the material of the transparency.In addition, for the purposes of window etc., for the efficient of the air-cooling system in the buildings that improves midsummer with conserve energy, also require it to have reflecting properties to heat ray.
In order to realize these electromagnetic wave shielding performances and heat ray reflecting properties, should have suitable performance based on the film of silver.But, identical with above-mentioned display, in these purposes, also be problem, thereby require the aggegation of descending the inhibition silver atoms high-grade by commodity value whereaboutss that white point causes, qualification rate reductions, durable years reduction etc. take place.
Summary of the invention
Therefore, the purpose of this invention is to provide, few take place as (transparent conductivity) laminated body of above-mentioned reflectivity defective and use filter of display, electromagnetic shielding film, heat ray reflection film and the window material of this laminated body.
The result that the inventor studies with keen determination from such viewpoint; be surprised to find especially; the laminated body that protective seam that is made of inorganic fine particles and adhesive material and transparent conducting film layer constitute has solved problem of the present invention, thereby has finished the present invention.
According to the present invention, provide following invention.
Be that the present invention is a kind of laminated body; it is characterized in that; at least comprise: the transparent conducting film layer (B) of transparent base (A), argentiferous and contain adhesive material (C1) and the protective seam (C) of inorganic fine particles (C2), transparent conducting film layer (B) contacts with protective seam (C).
In addition, laminated body of the present invention is that preferentially to select with inorganic fine particles (C2) be that metal oxide is the laminated body of feature.
In addition, laminated body of the present invention is that preferential the selection with inorganic fine particles (C2) is that the hopcalite that contains the composite oxides of antimony oxide or contain antimony oxide is the laminated body of feature at least.
In addition, laminated body of the present invention is that preferentially to select with adhesive material (C1) be that at least a resin that is selected from silicones, vibrin, the urethane resin is the laminated body of feature.
In addition, laminated body of the present invention is preferentially to select the transparent conducting film layer (B) of argentiferous to comprise at least: transparent high refractive index film layer (B1) and silver or contain the above-mentioned laminated body of the transparent metal film layer (B2) of silver alloy.
According to the present invention, can access have high conductivity, high transparent, high near infrared reflectivity, be more preferably and not only had high infrared reflectivity, and have the laminated body of the considerably less such excellent characteristic of the generation of white point.
In addition, the present invention is to comprise above-mentioned laminated body at least and functional hyaline layer (D) is the filter of display of feature.
In addition, filter of display of the present invention is preferential the selection with expose 24 hours under 60 ℃, the condition of 90% relative humidity (RH) after, and diameter is to be less than or equal to 2/m more than or equal to the occurrence frequency of the spot defect of 0.1mm
2Aforementioned display device light filter for feature.
In addition, the present invention is to use the display of above-mentioned filter of display.
According to the present invention, because the generation of white point is few, so the filter of display and the display of the image that for example can provide beautiful continuously for a long time can be provided.
In addition, the present invention is to use the electromagnetic shielding film of above-mentioned laminated body.According to the present invention, the generation that can access white point less, the continuously long-time good electromagnetic shielding film of visibility.
In addition, the present invention is to use the heat ray reflection film of above-mentioned laminated body.Can access the continuously long-time good heat ray reflection film of visibility according to the present invention.
In addition, the present invention is the window electromagnetic shielding film, it is characterized in that, comprises above-mentioned laminated body and functional hyaline layer (D) at least.
In addition, the present invention is the window heat ray reflection film, it is characterized in that, comprises above-mentioned laminated body and functional hyaline layer (D) at least.
In addition, the present invention has above-mentioned window is used the rhythmo structure of substrate with electromagnetic shielding film and transparency window window at least.
In addition, the present invention has above-mentioned window is used the rhythmo structure of substrate with heat ray reflection film and transparency window window at least.
According to the present invention, the generation that white point can be provided less, continuously long-time visibility is good and window that can make with easy method.
In addition, the present invention is to use the semiconductor device of above-mentioned laminated body.Be not subjected to the semiconductor device that yet can use at high temperature etc. even can provide by the semiconductor device that the obstacle that electromagnetic wave produces influences according to the present invention.
Description of drawings
Fig. 1 is the figure that the layer of the transparent conducting film laminated body film among expression the present invention constitutes an example.
Fig. 2 is the figure of expression electromagnetic wave shielding with an example of the layer formation of display optical light filter.
Fig. 3 is the window among expression the present invention constitutes an example with the layer of electromagnetic shielding film figure.
Fig. 4 is the sectional drawing that the layer of expression window of the present invention constitutes an example.
Embodiment
Below, explain the present invention.So-called in the present invention binding material often comprises the implication of jointing material.
Laminated body of the present invention is with electrical conductance metal laminate thin film (B) that comprises transparent base (A), argentiferous and protective seam (C), and transparent conducting film layer (B) contacts the laminated body into feature with protective seam (C).And protective seam (C) is to contain adhesive material (C1) and inorganic fine particles (C2) is a feature.
Filter of display of the present invention has the formation that comprises above-mentioned laminated body and functional hyaline layer (D).As functional hyaline layer (D), can enumerate anti-reflection layer, dimming layer and hard conating, UV-absorbing layer, anti-contamination layer, anti-static electrification layer etc.In addition, also can contain sticky material layer (E) as required.
Electromagnetic shielding film of the present invention and heat ray reflection film are feature to contain laminated body of the present invention.For example, can be with laminated body of the present invention intactly as electromagnetic shielding film and heat ray reflection film, or make up laminated body of the present invention and above-mentioned functional hyaline layer (D) etc., also can be as electromagnetic shielding film and heat ray reflection film.As with the first-selected purposes of the above-mentioned film of these functional hyaline layers (D) combination, can enumerate window with electromagnetic shielding film and window with heat ray reflection film etc.Functional hyaline layer (D) as using in film at above-mentioned window specifically, preferably can use UV-absorbing layer, hard conating etc.
Window of the present invention constitutes feature with film and transparency window with the lamination of substrate to have above-mentioned window.
Below, these each inscapes are described.
Transparent base (A)
As above-mentioned transparent base (A), plastic plate or glass plate all can be fit to use.As the object lesson of plastic plate, can be polymethylmethacrylate (PMMA) and acryl resin, polycarbonate resin, transparent ABS resin etc., but be not limited to these resins.The thickness of plastic plate, though have no particular limits, normally about 1mm～10mm.When using glass plate, wish to use half strengthening glass sheets or the strengthening glass sheets that carry out chemical enhanced processing or air-cooled reinforcement processing.As considering that from weight its thickness is preferably about 1～4mm.In addition, the part of periphery on these glass plates or plastic plate, that become filter of display is a purpose to improve appearance design, also can implement coloured appearance decoration printings such as black.
In addition, also the macromolecule membrane that can use when being adapted at transparent conducting film layer described later (B) and making is as transparent base (A), or also can be with the transparent sheet of softness with resistance to impact as transparent base (A).Use these optical filters that obtains, can directly be fitted on the PDP module and use.
The transparent sheets of above-mentioned plastic plate, glass plate, polymeric membrane, softness etc. can be also with more than 2 kinds or 2 kinds.At this moment, except with its direct lamination combination, also can use sticky material layer described later (E) use of fitting.
The transparent conductivity light filter layer (B) of argentiferous
The transparent conducting film layer (B) of argentiferous of the present invention can unrestrictedly use known transparent conducting film layer.For example, except go up the formation of directly formation at transparent base (A), even on the polymeric membrane described later or have prevent to reflect or the film of dimming function on the formation that forms do not mind yet.Among these, from production efficiency or qualitative control aspect etc., the method for using as transparent conducting film layer (B) with the transparent conducting film laminated body film of the transparent conducting film that forms argentiferous on polymeric membrane is preferential especially the selection.Fig. 1 is the example that the layer of the laminated body among expression the present invention constitutes.That is be that the transparent conductivity metallic film 15 and the transparent high refractive index film 17 of argentiferous alternatively carries out lamination on transparent polymer film 13,, so that with transparent high refractive index film 17 clamping metallic films 15, the formation of lamination protective seam 20 described later again.
As above-mentioned polymeric membrane, preferential use about thick 10～300 μ m, flexible transparent high polymeric membrane arranged, for example, can enumerate polyethylene terephthalate (PET), polyimide (PI), polysulfones (PS), polyethersulfone (PES), polymethylmethacrylate (PMMA), polycarbonate (PC), polyetheretherketone (PEEK), polypropylene (PP), triacetyl cellulose (TAC).Especially polyethylene terephthalate (PET) and triacetyl cellulose (TAC) are particularly suitable for using.
The transparent conducting film layer (B) of Shi Yonging preferentially adopts to comprise transparent high refractive index film layer (B1) and contain silver or the laminated body of the transparent metal film layer (B2) that the alloy of argentiferous constitutes in the present invention.The ratio resistance of silver is 1.59 * 10
-6(Ω cm), and electrical conductance is the best in all materials, and also the transmission of visible light of film is good, therefore the most suitable use.On the other hand, silver deficient in stability during as film, have and vulcanized easily or problem that chlorination is such, therefore in order to improve its stability, argentiferous, promptly specifically, based on the silver alloy of silver, for example can use the alloy that closes gold, silver and platinum that closes gold, silver and copper and palladium that closes gold, silver and palladium that closes gold, silver and copper of silver and gold etc.
The thickness of such transparent metal film layer (B2) is though by all permeability of multi-layer transparent conductive membrane layer and electric conductivity and determine, generally, be about 0.5～100nm with regard to one deck.
Moreover, the most surperficial when metal film layer is set, be silver element composition 3～99% (atomic ratios) preferably of the major metal in the most surperficial.
Transparent high refractive index film layer (B1) can use known material without restriction.The transparency is high forming, for example during the film about thickness 100nm, preferentially select this film to the optical transmission rate of wavelength 400～700nm more than or equal to 60% such, transparent excellent material.In addition, preferentially select refractive index to 550nm more than or equal to 1.4 such, high-index materials.Material as being adapted at using in so transparent high refractive index film layer (B1) usefulness for example, preferentially uses oxide (ITO), zinc paste (ZnO), the titania (TiO of indium and tin
2), oxide (CTO), the aluminium oxide (Al of cadmium and tin
2O
3), oxide (AZO), magnesium oxide (MgO), the thoria (ThO of zinc and aluminium
2), tin oxide (SnO
2), lanthana (La
2O
3), silicon dioxide (SiO
2), indium oxide (In
2O
3), antimony oxide (Sb
2O
3), zirconia (ZrO
2) etc.In addition, also can use transparent high index of refraction sulfide,, can enumerate zinc sulphide (ZnS), cadmium sulfide (CdS), antimonous sulfide (Sb as illustrative words particularly
2S
3) etc.Use material as transparent high refractive index film layer (B1), in the above-mentioned material, ITO, ZnO and TiO
2Be best.This is because ITO and ZnO hold electric conductivity, and the refractive index height in the viewing area is to 2.0 degree, and then keeps absorbing hardly in the viewing area.TiO
2Be megohmite insulant,, cause to 2.3 degree greatly by refractive index to visible light though hold absorption a little in the viewing area.
The above-mentioned transparent metal film layer (B2) and the multilayer laminate of transparent high refractive index film layer (B1) can utilize known method formation in the past such as sputtering method, ion plating method, vacuum vapour deposition.Special sputtering method is suitable for controlling the multilayer laminated formation of thickness, can make the lamination of metal film layer and high refractive index film layer, for example therefore metal film layer that is made of the alloy of silver or argentiferous and the transparent high refractive index film layer that mainly constitutes with indium oxide film forming continuously repeatedly easily be desirable.
Specifically, in the formation of transparent metal film layer of the present invention (B2), example as the best, can enumerate alloy with silver or argentiferous as target, sputter gas uses inert gases such as argon, usually at pressure 0.01～3.0Pa, adopt direct current (DC) or high frequency (RF) magnetron sputtering system.
In addition, in the formation of transparent high refractive index film layer of the present invention (B1), for example use with indium as the metallic target of major component or with the sintered body target of indium oxide as major component, sputter gas uses inert gases such as argon, reactant gas uses oxygen, usually at pressure 0.01～3.0Pa, utilize the reactive sputtering method of direct current (DC) or high frequency (RF) magnetron sputtering system to use.
About other more detailed contents, can adopt the spy and open flat 10-217380 communique or the special content of putting down in writing in the 2002-323861 communique etc. of opening.
Protective seam (C)
Protective seam of the present invention (C) is the layer that is made of adhesive material (C1) and inorganic fine particles (C2).
Especially, by contain the coating fluid that disperses inorganic fine particles (C2) in the solution that adhesive material (C1) and water or organic solvent grade liquid constitutes and obtain be coated with, dry and layer that obtain is desirable especially as protective seam (C).In addition, above-mentioned coating fluid also can be that bonding agent (C1) inorganic fine particles (C2) is dispersed in the emulsion in the liquid.Also can preferentially use the form of in the liquid of the emulsion state that contains bonding agent (C1) and liquid, disperseing inorganic fine particles (C2).
Below, describe inorganic fine particles (C2) in detail and be dispersed in coating fluid in the former solution of adhesive material (C1).
As the solution by above-mentioned adhesive material (C1) and liquid formation, what preferentially select is to be fit to the solution of the favorable dispersibility of colourless, the transparent height of use, inorganic fine particles.
Adhesive material of the present invention (C1) is preferential, and what select is resin, more particularly, for example can enumerate acrylic resin, silicon is resin, polyester based resin, polyurethane series resin, fluorine resin etc.In these resins, be selected from silicon and be the resin more than a kind or a kind in resin, polyester based resin, the polyurethane series resin, from easiness in one's hands, adhesive material (C1) viewpoints such as dispersiveness, be preferential the selection to inorganic fine particles described later (C2).As the resin as above-mentioned resin, also can use material with stickability or cementability, the function of giving sticky material layer described later (E) on protective seam (C) also is possible.In addition, above-mentioned resin also can be also with more than 2 kinds or 2 kinds.
Protective seam of the present invention (C) generally uses bonding material layer described later (E), just can be easily and other laminating close.Therefore and functional hyaline layer described later (D) when carrying out lamination, it is unrestricted using the use of the laminating method (applying method) of adhesives in the past.
As solvent, can make known liquid such as water, alcohol, acetone, toluene.
In the present invention, as described later, the preferential selection of inorganic fine particles (C2) can cover the transparent conducting film layer as much as possible and be configured.For this reason, the best favorable dispersibility of inorganic fine particles (C2) in adhesive material (C1) solution, inorganic fine particles (C2) keeps the not state of free settling.According to the kind of inorganic fine particles, just can realize this state by selecting resin or liquid aptly.For example, preferentially select the high resin of proportion, or become than higher resin or liquid as the viscosity of solution for the inorganic fine particles that is not easy sedimentation.
Relevant inorganic fine particles of the present invention (C2), as mentioned above, being preferably in as protective seam (C) does not have the gap, fine and close contains with filling in the transparent conducting film layer.In addition, relevant inorganic fine particles of the present invention (C2), if according to the deduction mechanism that prevents white point described later, the preferential selection is the low inorganic fine particles of permeability of chlorine or chloride, sulphur or sulfide etc.Inorganic fine particles (C2) is if the good inorganic fine particles of the absorptive character of chlorine or chloride, sulphur or sulfide etc. is then best.As suitable example, for example can enumerate the particulate of metal oxide.Metal oxide has and the such general tendency of reaction etc. easily such as hydrogen chloride, and therefore having the muriatic character of easy absorption is above-mentioned reason.As the example of metal-oxide powder more specifically, can enumerate silicon dioxide, tin oxide, zinc paste, indium oxide, antimony oxide, aluminium oxide, zirconia etc., the metal oxide identical when forming transparent high refractive index film layer (B1) with suitable material.These materials also can make up more than 2 kinds or 2 kinds and use.For example, can use as composite oxides again, can use as hopcalite again.In addition, above-mentioned metal oxide also can use with metallic combination.As the object lesson of above-mentioned composite oxides, can enumerate indium oxide-Xi etc.
Among these, preferential select by the composite oxides that contain antimony oxide or contain the particulate that the hopcalite of antimony oxide constitutes, preferential especially selective oxidation antimony-tin oxide composite oxides, antimony oxide-zinc paste composite oxides.
These metal oxides are compared with the thin layer of metal oxide that is an example of above-mentioned high refractive index transparent thin layer (B1), and the normal daylight transmissivity is low, but by its small particle diameter, can realize not influencing the practical transparency.
In addition, inorganic fine particles (C2) if particle diameter excessive, and the dispersiveness of adhesive material (C1) just degenerates.In addition, the particle diameter one of inorganic fine particles (C2) becomes big, just often can not cover the transparent conductivity light filter layer densely.
On the other hand, if particle diameter is too small, just the become possibility of difficulty of processing as particle is arranged.
Therefore, the mean grain size of inorganic fine particles (C2) better is 1～1000nm, is more preferably 5～500nm, preferably 5～200nm.
Have, as described later, it is all that inorganic fine particles (C2) preferably covers transparent conducting film layer (B) equably, so inorganic fine particles (C2) preferably has narrow size-grade distribution again.
Inorganic fine particles of the present invention (C2), for example by and adhesive material (C1) be used in combination, as mentioned above can realization transparency, and surprisingly, as described later, preventing to have very good extremely useful characteristic on the white point effect.
Above-mentioned coating fluid, preferably the solution of adhesive material (C1) and liquid formation mixes in fact equably with inorganic fine particles (C2).In order to obtain such coating fluid, the dispersion liquid that preferably solvent and inorganic fine particles (C2) is in homogeneously dispersed state mixes with the solution that is made of adhesive material (C1) and solvent.
In addition, in described coating fluid, also can be added to the levelling agent etc. that the stabilizing agent of the dispersiveness that improves inorganic fine particles or be used to improves coating.
As using the coating fluid of making like this and obtaining, form the method for protective seam (C), can unrestrictedly use known coating process, for example can enumerate the excellent knife coating of coiling, reverse rubbing method, engraved roll rubbing method, rolling method etc.The kind of coating fluid, viscosity, coating weight etc. but can be chosen in the condition that becomes suitable coating fluid in the above-mentioned rubbing method also without limits aptly.
As the thickness of protective seam (C), if consider to keep the function of adhesive material, better be to be less than or equal to 100 μ m, be preferably less than or equal 80 μ m.Usually it is enough being less than or equal to 2 μ m, preferably is less than or equal to 1 μ m, particularly preferably is more than or equal to 0.05 μ m, is less than or equal to 0.5 μ m.
In addition, make like this and the average transmittance of seeing of the protective seam that obtains is preferably more than or equal to 50%, be more preferably more than or equal to 70%, good especially is more than or equal to 80%.
In the present invention, as described later, inorganic fine particles (C2) preferably can cover the configuration of transparent conductivity light filter layer ground as much as possible.
Therefore, about the composition of adhesive material in the protective seam of the present invention (C1) and inorganic fine particles (C2), preferentially select the relative adhesive resin of amount (C1) of inorganic fine particles (C2) more.But, inorganic fine particles (C2) if containing ratio too high, inorganic fine particles (C2) just can not be fixed fully, and causes peeling off or crackle etc. taking place of protective seam, often can not get protecting fully effect.
The only ratio of adhesive material (C1) and inorganic fine particles (C2), the dispersiveness decision by employed adhesive material (C1) and inorganic fine particles (C2) can have change leeway in a big way.Therefore, preferably obtain aptly the adhesive material (C1) that adapt to use and inorganic fine particles (C2) kind contain proportional.In general, the preferred weight ratio of adhesive material (C1) and inorganic fine particles (C2) (inorganic fine particles (C2)/adhesive material (C1)) is 0.01～100, is more preferably 0.03～30, and good especially is 0.05～20.
Functional hyaline layer (D)
As functional hyaline layer (D), can enumerate as preferred example and to prevent reflection horizon or dimming layer.And can adopt hard conating or anti-contamination layer, UV-absorbing layer, anti-static electrification layer, color emission layer etc.The polymeric membrane that these layers can use in the formation of above-mentioned transparent conducting film layer (B), transparent base (A), above-mentioned protective seam (C) are gone up and are formed, and also can use the film or the sticky material layer of the above-mentioned function with picture antireflection film or anti-shake eye mask etc.About these functional hyaline layers, can adopt in more detail the spy and open the functional hyaline layer of putting down in writing in flat 10-217380 communique and the Te Kai 2002-323861 communique.
Be to be adapted at window of the present invention with electromagnetic shielding film and window UV-absorbing layer or hard conating with the functional hyaline layer of using in the heat ray reflection film (D), if have the performance of the transparency and window construction can be anti-described later, just can unrestrictedly use material known.As hard conating, specifically, its suitable example can be enumerated the material of the good acrylic acid series of the transparency, price, application property.In addition, as the method that forms hard conating, can unrestrictedly use known method.Specifically, can enumerate the excellent knife coating of coiling, reverse rubbing method, engraved roll rubbing method, rolling method etc.On the kind of coating fluid, viscosity, coating weight, also without limits, can select to be fit to the condition of above-mentioned rubbing method aptly.In addition, the pencil hardness of resulting hard conating (Japanese Industrial Standards (JIS) K5400 standard) is preferably more than or equal to H, and good especially is more than or equal to 2H.
As above UV-absorbing layer,, just can unrestrictedly use material known if transparent.In addition, on the formation method of UV-absorbing layer, also be not particularly limited.As concrete example, can be so that the UVA film of giving the UVA function on the polymeric membrane or the transparent base (A) of giving the UVA function, protective seam (C), hard conating, sticky material layer forms such as (E) described later be used.
Sticky material layer (E)
In the present invention, transparent base (A), transparent conducting film layer (B), protective seam (C) and functional hyaline layer (D) are fitted by sticky material layer (E) as required.As concrete example, in the applying that forms between the polymeric membrane of transparent base (A)-transparent conducting film layer (B), between transparent base (A)-protective seam (C), between transparent base (A)-functional hyaline layer (D), between protective seam (C)-functional hyaline layer (D), forms between the polymeric membrane-functional hyaline layer (D) of transparent conducting film layer (B) etc., use.
Moreover said sticker of the present invention also comprises the implication of bonding agent and uses.
As sticky material layer of the present invention (E),, just can unrestrictedly use known binding material if transparent.In addition, by in sticky material layer (E), containing the function that pigment also can have color emission layer.Also can contain antirust composition in addition.In addition, as mentioned above, by disperseing inorganic fine particles (C2), the function that also can give protective seam.
As sticky material layer (E), content can adopt the spy and open flat 10-217380 communique or the special content of putting down in writing in the 2002-323861 communique of opening more specifically.
The making of laminated body
Laminated body of the present invention; at least the transparent conducting film layer (B), adhesive material (C1) and the inorganic fine particles (C2) that comprise transparent base (A), argentiferous; the preferential protective seam of selecting to be less than or equal to 2 μ m by thickness (C) constitutes, and contacts with protective seam (C) with transparent conducting film layer (B) to be feature.As long as transparent conducting film layer (B) contacts with protective seam (C), the position of transparent base (A) is exactly arbitrarily.Also can go up and directly form transparent conducting film layer (B) at transparent base (A).Also can use sticky material layer (E) applying transparent base (A) and transparent conducting film layer (B).In addition, also can use sticky material layer (E) applying transparent base (A) and protective seam (C).
The sectional drawing that the layer of the relevant such laminated body of the present invention of expression constitutes an example is above-mentioned Fig. 1.In more detail; transparent conducting film layer that laminated body shown in Figure 1, this laminated body are repeated to form by the transparent conductivity light filter layer 15 and the transparent high index of refraction light filter layer 17 of the argentiferous that forms on transparent polymeric film matrix 13 and the protective seam that forms thereon constitute.
The combination of optical filter
Optical filter of the present invention by transparent base (A),
The conductive metal laminate film (B) of argentiferous,
Protective seam (C),
Functional hyaline layer (D) and
Sticky material layer (E) as required constitutes.Except the method for in the making of laminated body, using, when use prevents the functional clear filter of reflecting filter or dimming light filter etc. as functional hyaline layer (D), can in closing, use sticky material layer (E) with other laminatings.
In filter of display of the present invention; as long as transparent conducting film layer (B) contacts with protective seam (C); the formation of these layers is exactly arbitrarily, but uses when preventing reflecting filter or dimming light filter as functional hyaline layer (D), preferentially selects these layers to form at outermost layer.
As the concrete formation of filter of display of the present invention, for example can enumerate,
1. fit as the glass plate of transparent base (A) and the composite transparent substrate of polymeric membrane with sticky material layer (E); the transparent conducting film that on above-mentioned polymeric membrane, forms as transparent conducting film layer (B); as the layer of the protective seam (C) that contacts with electrical conductance metal laminate thin film layer (B) by adhesive material (C1) and inorganic fine particles (C2) formation; has the film that prevents to reflect function or dimming function as functional hyaline layer (D); and with the fit formation of above-mentioned substrate and layer of sticky material layer (E)
As transparent base (A) glass plate, on above-mentioned glass plate, form protective seam (C) that transparent conductivity light filter, conduct and the above-mentioned transparent conductivity light filter of transparent conducting film layer (B) contact the layer that constitutes by adhesive material (C1) and inorganic fine particles (C2), prevent to reflect the light filter of function or dimming function as having of functional hyaline layer (D), and with the above-mentioned substrate of sticky material layer (E) applying with layer formation.
Fig. 2 is the sectional drawing of a layer example that constitutes of the relevant filter of display of the present invention of expression.In more detail; what represent in Fig. 2 is; the transparent conducting film laminated body film that constitutes by transparent polymeric film matrix 13 and multi-layer transparent conductive membrane layer 18 and protective seam 20 with 35 pairs on sticky material layer, have the film 30 that prevents to reflect function (below; be called and prevent reflectance coating) or have the film 30 of dimming function ' (below; often be called the dimming film) and transparent support substrate 33 fit, make the electromagnetic wave shielding display optical light filter that forms electrode 50 contiguously with multi-layer transparent conductive membrane layer 18.In the case, the transparent support substrate 33 and the transparent polymeric film matrix 13 of fitting with sticky material layer 35 is equivalent to transparent base (A).
Above-mentioned electrode preferentially is chosen in the light filter with electromagnetic wave shielding function etc. and uses, and therefore can unrestrictedly adopt known electrode.In order from big area, to take out electric current expeditiously as far as possible, preferentially select above-mentioned electrode on frame, to form at outer peripheral portion.As the formation method of electrode, can use coating, the printing of conductive coating paint, the known means such as attaching of electric conductivity band.In more detail, can adopt the spy and open flat 10-217380 communique or the special content of putting down in writing in the 2002-323861 communique etc. of opening.
As other example, the preferential example of selecting can be enumerated does not have the membranaceous electromagnetic wave shielding of transparent support substrate 33 display optical light filter in Fig. 2.At this moment, transparent polymeric film matrix 13 becomes transparent base (A).In addition, above-mentioned optical filter also can directly be fitted on the PDP module by sticky material layer 35 and use.
As other example, replace transparent support substrate 33, can enumerate the transparent sheet that uses as transparent base (A) with resistance to impact.Such optical filter is preferentially selected directly to be fitted on the PDP module by sticky material layer 35 and is used.If direct applying filter of display on the PDP module; though then the PDP module is subject to damaged possibility owing to outside bump exists; but because above-mentioned optical filter has resistance to impact; even therefore directly be fitted on the PDP module; the PDP module that yet has the protection high price is not subjected to the good function of outside bump, can prevent the breakage of PDP module.
Form the member of each above-mentioned layer, also can have several functions.For example, form the reflectance coating that prevents of foregoing transparent conducting film layer, have 3 kinds of functions of transparent base (A), transparent conducting film layer (B), functional hyaline layer (D).If use such member, just can expect that the more slimming of laminated body of the present invention or filter of display or the process number when making shorten and the raising of the throughput rate that produces.
Electromagnetic shielding film, heat ray reflection film, window
Electromagnetic shielding film of the present invention or heat ray reflection film, can be adapted at because electromagnetic wave makes affected machine of its function or the restricted machine of use at high temperature, for example have in the window etc. of buildingss such as semiconductor device, office formula of the various precision machineries etc. of semiconductor circuit etc. and use.As semiconductor device, in particular, can the machine that pachinko platform, game machine etc. require visibility be shown example.
Window electromagnetic shielding film of the present invention, with comprise transparent base (A), transparent conducting film layer (B) at least, contain adhesive material (C1) and the protective seam (C) of inorganic fine particles (C2), functional hyaline layer (D) is feature.As functional hyaline layer (D), the preferential selection is feature with the adhesive phase that comprises hard conating and UV-absorbing layer and use as required.Constitute as its concrete layer; transparent base (A), transparent conducting film layer (B), protective seam (C), hard conating to be to have the order of hard conating/transparent base (A)/transparent conducting film layer (B)/protective seam (C), perhaps have transparent base (A)/transparent conducting film layer (B)/protective seam (C)/hard conating order constitute feature.In described formation, the position of the sticky material layer (E) of UV-absorbing layer and use as required etc. is arbitrarily.
Window of the present invention shown in Figure 3 one example of the formation of electromagnetic shielding film.
Window electromagnetic shielding film shown in Figure 3 for example uses the method as following to make.In the one side of transparent polymeric film matrix 13, form with sputtering method and alternatively carry out the lamination of transparent conductivity metal film layer 15 of 4 layers of transparent high refractive index film layer 17 and 3 layers of argentiferous and the multi-layer transparent conductive membrane layer 18 that obtains, and obtain laminated body 10.Then, transparent polymeric film matrix 13 sides in laminated body 10 are provided with hard conating 40.On multi-layer transparent conductive membrane layer 18, form the protective seam 20 that constitutes by adhesive resin and inorganic fine particles.On protective seam 20, form the adhesive layer 70 that comprises ultraviolet light absorber again, just obtain window electromagnetic shielding film of the present invention.
Window electromagnetic shielding film of the present invention has foregoing transparent conducting film layer, so excellent in electromagnetic wave shielding property.Window electromagnetic shielding film of the present invention, the preferential electromagnetic wave shielding performance of selecting to determine with ァ De バ Application テ ス ト method is better more than or equal to 30dB at the frequency field of 30MHz～6000MHz.Be more preferably more than or equal to 35dB, preferably more than or equal to 40dB in addition, emissivity better is to be less than or equal to 0.25, is preferably less than or equals 0.20.
In addition, window electromagnetic shielding film of the present invention by selecting, control the formation of above-mentioned transparent conducting film layer aptly, also can be given the heat ray reflecting properties.This heat ray reflecting properties for example can be estimated with insolation reflectivity (JIS A 5759).Window of the present invention better is more than or equal to 25% with the insolation reflectivity of electromagnetic shielding film, preferably more than or equal to 30%.
Use the display device of filter of display of the present invention that for example various displays such as plasma display, LCD, OLED display are arranged, owing to use above-mentioned filter of display, therefore long-time electromagnetic leakage is few continuously, do not cause the misoperation of remote control etc. yet, and beautiful image can be provided.
(window)
Window of the present invention has the structure of above-mentioned window being used substrate joining with electromagnetic shielding film and transparency window.As transparency window substrate of the present invention, can unrestrictedly use known window substrates such as glass plate, acrylic panel.The sectional drawing of the example that the layer of window of the present invention shown in Figure 4 constitutes.Promptly; be that hard conating 60 is set on the laminated body identical with Fig. 3 10; forming the protective seam 20 that constitutes by adhesive resin and inorganic fine particles, the sticky material layer 70 that contains ultraviolet light absorber, the formation of the glazing substrate 80 of fitting again with hard conating 60 opposition sides.
Below be illustrated in transparency window and use the conventional method of electromagnetic shielding film with the window of the present invention of fitting on the substrate.As the window electromagnetic shielding film, preferentially use the window electromagnetic shielding film that has the binder material layer on its surface.At first, transparency window substrate and the window binder material layer side surface of electromagnetic shielding film, the mixing material of water and surfactant is got wet, follows above-mentioned transparency window and temporarily fits with electromagnetic shielding film with substrate and window.Use rubber flap that water is scraped at last, window and film are fitted securely.
According to the water law from the beginning of Japan, the cl concn of the end of city's tap water is defined as more than or equal to 0.1ppm (being 1 microgram in 1 liter).Like this, because the chlorine component that exists in the water perhaps enters small dirt and hinders foreign matter between transparency window is with substrate and film when construction, so, just often produce the reflectivity defective if the transparent conducting film layer comes in contact with the chlorine component of invading from the outside.
But window of the present invention has transparent conducting film layer (B) and the contacted formation of protective seam (C) with electromagnetic shielding film, and therefore the generation of reactive defective is considerably less.Be fitted on glass with electromagnetic shielding film or laminated body of the present invention window of the present invention in order to method with above-mentioned city's tap water, be fixed in 60 ℃, the hot and humid degree treating apparatus of relative humidity 90%, after 24 hours, by microphotograph can confirm according to the promotion evaluation assessment of observe measuring since the diameter that the aggegation of silver produces more than or equal to the reflectivity defective occurrence frequency of 0.1mm.Be fitted in above-mentioned evaluation assessment on glass according to laminated body of the present invention or laminated body, the number of the reactive defective that is produced can shockingly be reduced to and be less than or equal to 10/10cm
2, better be reduced to and be less than or equal to 8/10cm
2, preferably be reduced to and be less than or equal to 6/10cm
2
In addition, when transparent base (A) is insufficient to ultraviolet permanance, the preferential use UV-absorbing layer of selecting.At this moment, wish that UV-absorbing layer is positioned at as far as possible the window substrate near the glass typical example of constructing with electromagnetic shielding film as window.Reflection is arranged on transparent conducting film layer (B) or absorb ultraviolet function, but be not subjected to ultraviolet ray often insufficient influencing from protection transparent base (A).On the other hand, window of the present invention normally is configured in the outside with transparency window with substrate, and window is configured in the indoor with electromagnetic shielding film.Therefore preferentially between the transparent base (A) and the glass pane of constructing select to be provided with UV-absorbing layer (E).
Laminated body of the present invention or filter of display have the formation that transparent conducting film layer (B) and protective seam (C) come in contact, and therefore the generation of above-mentioned reactive defective is considerably less.Laminated body of the present invention or filter of display are fixed in 60 ℃, the hot and humid degree treating apparatus of relative humidity 90%, after 24 hours, by microphotograph can confirm according to the promotion evaluation assessment of observe measuring since the diameter that the aggegation of silver produces more than or equal to the reflectivity defective occurrence frequency of 0.1mm.According to the above-mentioned evaluation assessment of laminated body of the present invention or filter of display, the number of the reactive defective that is produced can shockingly be reduced to and be less than or equal to 2/10cm
2, better be reduced to and be less than or equal to 1/10cm
2, preferably be reduced to and be less than or equal to 0.5/10cm
2
About the reason that the generation of above-mentioned reactive defective is suppressed significantly, not clear.But, think that this is because protective seam (C), special inorganic fine particles (C2) has makes the composition of giving birth to aggegation attached to the silver hair on the transparent conducting film layer, the effect that is captured such as chloride for example, or suppress and reactive effect of silver.In addition, by inference, protective seam (C) has shielded and has made silver-colored aggegation, or and the composition of silver reaction from the intrusion of outside, thereby mentioned component can not arrive metallic film neither a reason.Therefore in protective seam of the present invention (C), preferentially select inorganic fine particles (C2) seamlessly to distribute.In addition, inorganic fine particles (C2) is preferably formed as thin and distributes uniformly.If above-mentioned homogeneity is too poor, on the transparency of laminated body, often take place irregularly, inorganic fine particles (C2) is if crossing heavy back distributes in addition, and visible light transmittance tends to reduce.
In the such use of laminated body of the present invention and this laminated body of use, what is called is transparent, be meant according to the visible light transmittance of Japanese Industrial Standards (JIS) R3106 regulation (10)～(98) % preferably, be more preferably (20)～(95) % preferably (20)～(90) %.
Analytical approach
The analytical approach of the laminated body among the present invention is as follows.
The atom on laminated body surface is formed, and can use Auger electron optical spectroscopy (AES), fluorescent X-ray method (XRF), X-ray microanalysis method (XMA), Rutherford backscattering spectroscopy analysis (RBS), X ray electronics optical spectroscopy (XPS), vacuum-ultraviolet light electronic analysis method (UPS), infrared absorption optical spectroscopy (IR), raman spectroscopy method, 2 secondary ion mass analyses (SIMS), low-energy ion scattering optical spectroscopy mensuration such as (ISS).In addition, form and thickness by implement the atom that X ray electronics optical spectroscopy (XPS) or Auger electron optical spectroscopy (AES) or 2 secondary ion quality analyses (SIMS) can investigate in the laminated body along depth direction.
Use optical microscope, scanning electron microscope (SEM), the transmission electron microscope (TEM) of section, can survey the formation of laminated body and the state of each layer.
Application possibility on the industry
Laminated body of the present invention and filter of display, the generation of reactive defective is few.Therefore, compare with product in the past, the qualification rate height promptly can provide the filter of display of PDP etc. with high productivity.In addition, because the throughput rate height, so the aforementioned display device light filter can be provided at an easy rate.In addition, estimate that the generation of the reactive defective after after a while is few, therefore the utmost point provides high quality images for a long time continuously.
Use electromagnetic wave shielding end, the heat ray reflection film of laminated body of the present invention, even contact with tap water etc., the generation of reactive defective is also few.Therefore, even use the construction method manufacturing of general tap water in the past to have the window of electromagnetic wave shielding function and heat ray reflection function, also can provide except electromagnetic wave shielding function, heat ray reflecting properties the window that visual sense is also good continuously for a long time.
From as can be known above, industrial significance of the present invention is great.
Below, with embodiment the present invention is described.In an embodiment, only otherwise specify that % person is arranged, be weight %, the person that has the umber is parts by weight.
Embodiment 1
(1) formation of transparent conductivity light filter laminated body film
Make the transparent conducting film layer laminate body film identical with formation shown in Figure 1.Promptly, as transparent base, use polyethylene terephthalate film (thick 75 μ m), interarea in one side, use direct current magnetron sputtering process, lamination obtains transparent conducting film laminated body film by ITO light filter layer (transparent high refractive index film layer) and silver-colored thin layer (transparent metal film layer) that the oxide of indium and tin constitutes successively.The formation of transparent conducting film laminated body film is hyaline membrane matrix (75 μ m)/ITO (40nm)/Ag (15nm)/ITO (80nm)/Ag (20nm)/ITO (80nm)/Ag (15nm)/ITO (80nm).
At this, in the formation of ITO, use indium oxide tin oxide sintered body (In as target
2O
3: SnO
2=90: 10 (mass ratioes)), use argon oxygen gas mixture (stagnation pressure 266mPa, partial pressure of oxygen 5mPa) as sputter gas.In addition, in the formation of silver-colored thin layer, use silver as target, sputter gas uses argon gas (stagnation pressure 266mPa).
In addition, control the thickness of each layer by the system film time.This is because in advance obtaining film forming speed under the condition identical with the film forming condition of each layer, thereby this aspect is possible.
(2) (formation of protective seam)
As adhesive material, cooperate silicones (clear and electrician makes glass resin), as the zinc paste/antimony oxide particulate (daily output chemistry system セ Le Na ッ Network ス) of inorganic fine particles with as the isopropyl alcohol of solvent (reagent with), obtain the suspending liquid (below, with the suspending liquid that obtains like this as coating fluid) of silicones 3%, zinc paste/antimony oxide particulate 3%.
Use microscopic carvings to carve the cylinder rubbing method and be coated with the coating fluid that obtains on the outermost transparent high refractive index film layer of transparent conducting film laminated body film, 120 ℃ of dryings 1 minute, the protective seam of formation thickness 0.2 μ m just obtained laminated body.
(3) combination of filter of display
Make the filter of display identical with formation shown in Figure 2.At first, on the face of protective seam 20 sides of above-mentioned laminated body, use the fit film (PET system) that prevents to reflect function that has of thick 100 μ m of binding material (containing 0.2% benzotriazole).In addition, use cementing agent fit this laminated body the transparent polymeric film matrix a side and as the PMMA substrate of the 2mm of transparent support substrate.Carry out serigraphy silver again and stick with paste, carry out drying and form the electrode of thick 15 μ m, as filter of display.
(4) quicken Kesternich test
The filter of display that obtains as above is fixed in 60 ℃, the hot and humid degree treating apparatus of relative humidity 90%, after 24 hours, by microphotograph can confirm according to the promotion evaluation assessment of observe measuring since the diameter that the aggegation of silver produces more than or equal to the reflectivity defective occurrence frequency of 0.1mm.
The results are shown in the table 1.
Table 1
| Protective seam | Reactive defective generation number density is (individual/m 2) | |||
| Inorganic fine particles | Adhesive material | Thickness (μ m) | ||
| Embodiment 1 | Zinc paste/antimony oxide | Silicones | 0.2 | 0.2 |
| Embodiment 2 | Zinc paste/antimony oxide | Silicones | 1 | 0.1 |
| Embodiment 3 | Tin oxide/antimony oxide | Vibrin | 0.1 | 0.1 |
| Embodiment 4 | Zinc paste/antimony oxide | Vibrin | 0.1 | 0.4 |
| Embodiment 5 | Zinc paste/antimony oxide | Urethane resin | 0.1 | 0.6 |
| Comparative Examples 1 | Do not use | Do not use | - | 9.5 |
| Comparative Examples 2 | Do not use | Silicones | 0.2 | 6.6 |
Embodiment 2
Except the dried thickness of the coating of protective seam is 1 μ m and embodiment 1 make in the same manner, make the display optical light filter, this light filter is similarly quickened the results are shown in the table 1 of Kesternich test.
Embodiment 3
Osaka, Sumitomo セ メ Application ト ス ミ セ Off ァ ィ Application), the thickness of protective seam is the 0.1 μ m except using as coating fluid by the coating fluid that constitutes as the vibrin of adhesive material, as the zinc paste/antimony oxide of inorganic fine particles (trade name:; similarly make the display optical light filter with embodiment 1, this optical filter is similarly quickened the results are shown in the table 1 of Kesternich test.
Embodiment 4
Except using vibrin (ュ ニ チ カ system ェ リ one テ Le) as adhesive material, toluene (reagent with) coating fluid as solvent; the thickness of protective seam is beyond the 0.1 μ m and embodiment 1 similarly carries out the making of display optical light filter and quickens Kesternich test.The results are shown in the table 1.
Embodiment 5
Except using urethane resin (Mitsui Chemicals system ォ レ ス one) as adhesive material, toluene (reagent usefulness) coating fluid as solvent; the thickness of protective seam is beyond the 0.1 μ m and embodiment 1 similarly carries out the making of display optical light filter and quickens Kesternich test.The results are shown in the table 1.
Comparative Examples 1
Except the process that does not form protective seam and embodiment 1 combined display optical filter similarly, it is similarly quickened the results are shown in the table 1 of Kesternich test.
Comparative Examples 2
Silicones in coating fluid is 3%, zinc paste-antimony particulate is 0% and embodiment 1 combined display light filter similarly, and it is similarly quickened the results are shown in the table 1 of Kesternich test.
As from table 1 clear; when forming filter of display; owing on the part of the multilayer conductive metal laminate thin film that contacts this laminated body film, form the protective seam that constitutes by adhesive material and inorganic fine particles; with do not form protective seam; the occasion that forms with adhesive material is compared separately, and the occurrence frequency of the spot defect that is caused by silver-colored aggegation reduces significantly.
(1) formation of transparent electromagnetic wave screened film
As the transparent polymeric film matrix, use polyethylene terephthalate (PET) film (thick 75 μ m), on the interarea of one side, as transparent high refractive index film layer, use direct current magnetron sputtering process, successively the ito thin film layer that constitutes by the oxide of indium and tin of lamination, as the silver-colored thin layer of the transparent conductivity metal film layer of argentiferous, and obtain the transparent electromagnetic wave screened film.The formation of transparent electromagnetic wave screened film is PET film (75 μ m)/ITO (40nm)/Ag (10nm)/ITO (80nm)/Ag (10nm)/ITO (80nm)/Ag (10nm)/ITO (80nm).
The performance of transparent electromagnetic wave screened film in the above-described configuration is, surface resistivity is 2 Ω/, electromagnetic wave shielding energy (assay method: be 42dB ァ De バ Application テ ス ト method), emissivity (JIS A5759) is 0.10, and insolation reflectivity (JIS A 5759) is 32% (annotate: 32% unit of left side note is the unit of insolation reflectivity).
At this, in the formation of ito thin film layer, use indium oxide antimony oxide sintered body (In as target
2O
3: SnO
2=90: 10 (mass ratioes)), use argon oxygen gas mixture (stagnation pressure is 266mPa, and partial pressure of oxygen is 5mPa) as sputter gas.In addition, in the formation of silver-colored film, use silver, for sputter gas, use argon gas (stagnation pressure is 266mPa) as target.
(2) formation of protective seam
Be identically formed protective seam with embodiment 1.
(3) formation of adhesive layer and hard conating
The acrylic acid series cementing agent (Toyo Ink corporate system) that contains ultraviolet light absorber on above-mentioned protective seam as adhesive-coated 80 ℃ of dryings 2 minutes, forms the adhesive layer of thickness 25 μ m.
In addition, on the face of the opposition side of the face that has been coated with above-mentioned cementing agent,,, be cured, form the hard conating of thickness 3 μ m by the ultraviolet ray irradiation 80 ℃ of dryings 2 minutes as hard coating agent coating acrylic acid series hard coating agent (JSR corporate system).
(4) formation of window sample
At first, the day that is modulated at 500ml is mixed the water of the water applying usefulness of 1ml surfactant in this city tap water.With get wet glass substrate (A4 size) and give the transparent electromagnetic wave screened film of above-mentioned protective seam, sticky material layer of the previous described water of making, form fitting body, as transparent electromagnetic wave shielding windows sample with their applyings.
(5) quicken Kesternich test
60 ℃, the hot and humid degree treating apparatus internal fixation of relative humidity 90% as more than the transparent electromagnetic wave shielding sample that obtains, after 24 hours, by microphotograph observe to measure since the diameter that the aggegation of silver produces more than or equal to the reflectivity defective occurrence frequency of 0.1mm.This value is to carry out 10 samples to measure the mean value that obtains.
Table 2
| Protective seam | Reactive defective generation density is (individual/10m 2) | |||
| Inorganic fine particles | Bonding agent | Thickness (μ m) | ||
| | Zinc paste/antimony oxide | Silicones | 0.2 | 5 |
| Embodiment 7 | Zinc paste/antimony oxide | Silicones | 1 | 1 |
| Embodiment 8 | Tin oxide/antimony oxide | Vibrin | 0.1 | 4 |
| Comparative Examples 3 | Do not use | Do not use | - | 20 |
| Comparative Examples 4 | Do not use | Silicones | 0.2 | 15 |
Embodiment 7
Except the dried thickness of the coating of protective seam is 1 μ m and embodiment 6 similarly make the transparent electromagnetic wave screened film, it is similarly quickened the results are shown in the table 2 of Kesternich test.
Embodiment 8
Except use the coating fluid (trade name: Osaka, Sumitomo セ メ Application ト ス ミ セ Off ァ ィ Application) that constitutes by as the vibrin of adhesive material, as the tin oxide/antimony oxide of inorganic fine particles as coating fluid; and the thickness of protective seam is beyond the 0.1 μ m; similarly make the transparent electromagnetic wave screened film with embodiment 6, it is similarly quickened the results are shown in the table 2 of Kesternich test.
Comparative Examples 3
Except the process that does not form protective seam and embodiment 6 similarly make the transparent electromagnetic wave screened film, it is similarly quickened the results are shown in the table 2 of Kesternich test.
Comparative Examples 4
Silicones in coating fluid is 3%, use zinc paste-antimony particulate and embodiment 6 combined display light filter similarly, and it is similarly quickened the results are shown in the table 2 of Kesternich test.
From table 2, be clear that, owing to form the protective seam that contains inorganic fine particles in the part of the multilayer conductive metal laminate thin film that contacts this laminated body film, and the window that the occurrence frequency of the spot defect that obtains being produced by the aggegation of silver reduces significantly.
Claims (14)
1. laminated body is characterized in that, comprise at least transparent base (A),
The transparent conducting film layer (B) of argentiferous,
The protective seam (C) that contains adhesive material (C1) and inorganic fine particles (C2), described transparent conducting film layer (B) and protective seam (C) contact,
Wherein said inorganic fine particles (C2) is a metal oxide.
2. laminated body according to claim 1 is characterized in that, described inorganic fine particles (C2) is the hopcalite that contains the composite oxides of antimony oxide at least or contain antimony oxide.
3. laminated body according to claim 1 is characterized in that, described adhesive material (C1) is the resin of selecting from silicones, vibrin, urethane resin more than a kind or a kind.
4. laminated body according to claim 1 is characterized in that, the transparent metal film layer (B2) that the transparent conducting film layer (B) of described argentiferous comprises transparent high refractive index film layer (B1) at least and is made of the alloy of silver or argentiferous.
5. filter of display is characterized in that, comprises described laminated body of claim 1 and functional hyaline layer (D) at least.
6. filter of display according to claim 5 is characterized in that, under 60 ℃, the condition of relative humidity 90%, expose 24 hours after, diameter is to be less than or equal to 2/m more than or equal to the occurrence frequency of the spot defect of 0.1mm
2
7. use the display of the described filter of display of claim 5.
8. use the electromagnetic shielding film of the described laminated body of claim 1.
9. use the heat ray reflection film of the described laminated body of claim 1.
10. the window electromagnetic shielding film is characterized in that, comprises described laminated body of claim 1 and functional hyaline layer (D) at least.
11. window is characterized in that with heat ray reflecting barrier film, comprises described laminated body of claim 1 and functional hyaline layer (D) at least.
12. window, this window have the described window of claim 10 is used substrate with electromagnetic shielding film and transparency window rhythmo structure at least.
13. window, this window have the described window of claim 11 is used substrate with heat ray reflection film and transparency window rhythmo structure at least.
14. use the semiconductor device of the described laminated body of claim 1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003276559 | 2003-07-18 | ||
| JP2003276559 | 2003-07-18 | ||
| JP2004113766 | 2004-04-08 | ||
| JP2004113766 | 2004-04-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1576886A CN1576886A (en) | 2005-02-09 |
| CN1278136C true CN1278136C (en) | 2006-10-04 |
Family
ID=34593889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410069275 Expired - Fee Related CN1278136C (en) | 2003-07-18 | 2004-07-15 | Laminate and filter of display using the same laminate |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1278136C (en) |
| TW (1) | TWI295233B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101894670A (en) * | 2010-06-11 | 2010-11-24 | 杜月良 | Method for preparing zinc-evaporated metallized polypropylene film capacitor |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100462749C (en) * | 2006-08-31 | 2009-02-18 | 甘国工 | Filter plate having electromagnetic radiation prevention and light filtering function of plasma display |
| TWI454361B (en) * | 2009-12-25 | 2014-10-01 | Ulvac Inc | A method for manufacturing a decorative film for insert molding |
| JP5808966B2 (en) * | 2011-07-11 | 2015-11-10 | 富士フイルム株式会社 | Conductive laminate, touch panel and display device |
| CN104109843A (en) * | 2014-08-01 | 2014-10-22 | 苏州普京真空技术有限公司 | Method for eliminating white spots on evaporation coating |
| JP6184579B2 (en) * | 2015-12-14 | 2017-08-23 | 日東電工株式会社 | Electromagnetic wave absorber and molded body with electromagnetic wave absorber provided with the same |
| CN107686695A (en) * | 2016-08-04 | 2018-02-13 | 法国圣戈班玻璃公司 | Layered product |
| CN108767492B (en) * | 2018-04-25 | 2020-12-04 | 北京邮电大学 | Tunable THz Broadband Absorber |
| CN110426769A (en) * | 2019-08-30 | 2019-11-08 | 宁波吉欧光电科技有限公司 | A kind of high true color filter and its processing method |
| CN112420236B (en) * | 2020-10-27 | 2022-02-18 | 苏州欧莱仕电子科技有限公司 | An ultra-low resistance transparent conductive substrate |
| CN117621570A (en) * | 2023-10-27 | 2024-03-01 | 晋中学院 | A colorless and transparent visual window that combines radiant cooling and sunshade |
-
2004
- 2004-07-15 CN CN 200410069275 patent/CN1278136C/en not_active Expired - Fee Related
- 2004-07-15 TW TW93121117A patent/TWI295233B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101894670A (en) * | 2010-06-11 | 2010-11-24 | 杜月良 | Method for preparing zinc-evaporated metallized polypropylene film capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI295233B (en) | 2008-04-01 |
| CN1576886A (en) | 2005-02-09 |
| TW200508032A (en) | 2005-03-01 |
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