CN101237729A - Dispersion type electroluminescence element and manufacturing method thereof - Google Patents
Dispersion type electroluminescence element and manufacturing method thereof Download PDFInfo
- Publication number
- CN101237729A CN101237729A CNA2008100067203A CN200810006720A CN101237729A CN 101237729 A CN101237729 A CN 101237729A CN A2008100067203 A CNA2008100067203 A CN A2008100067203A CN 200810006720 A CN200810006720 A CN 200810006720A CN 101237729 A CN101237729 A CN 101237729A
- Authority
- CN
- China
- Prior art keywords
- layer
- electroluminescence element
- dielectric layer
- dispersion type
- luminescent layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a dispersed electroluminescent component and a manufacturing method thereof. The dispersed electroluminescent component is made from a transparent conductive layer, a luminescent layer, a dielectric layer and a backplane orderly laminating on a transparent base material, characterized by that: between the transparent conductive layer and the luminescent one, arranging a transparent dielectric medium layer with conductive particle contained in resin; and another kind of dispersed electroluminescent component which comprises a transparent conductive layer, a luminescent layer, a dielectric layer and a backplane, characterized by that: the luminescent layer contains phosphor powder and resin having locally presence luminescent centre, and insulating strength more than 0.15MV/cm.
Description
Technical field
The present invention relates to dispersion type electroluminescence (Electroluminescence) element and manufacture method thereof.
Background technology
Electroluminescent cell has all kinds according to the difference of its driving method, component structure.Among them, generally will apply the luminous element of alternating voltage and be called the inorganic electroluminescent element.The inorganic electroluminescent element can be divided into layer dispersion type electroluminescence element as luminescent layer that forms with fluorophor powder and resinous principle according to the difference of manufacture method, and with the film-type electroluminescent cell of Fluoropher thin film as luminescent layer.Because the luminous feature of inorganic electroluminescent component side, so develop use in backlight, the literal dish of clock and watch at LCD, various illumination, the display element etc.
The general structure of dispersion type electroluminescence element such as Japanese kokai publication sho 63-301487 number disclosed, is the structure that stacks gradually luminescent layer, dielectric layer and backplate on transparency electrode.When being said structure because transparency electrode contact with luminescent layer, so the contact portion of luminescent layer go bad in time easily, thereby cause the problem of luminosity reduction or non-uniform light.In addition, when applying AC field between electrode, said structure is easy to generate insulation breakdown.In order to prevent this insulation breakdown, also has the problem that must thicken dielectric layer.
In addition, also disclose in the Japanese kokai publication sho 62-18254 communique and the relevant invention of electroluminescent cell that between transparency electrode and luminescent layer, forms the palladium film.Form the palladium film to luminescent layer in time and effectively rotten, but forming the palladium film will be undertaken by vacuum evaporation, sputter, ion plating etc., easily becomes loaded down with trivial details so have manufacturing process, and the productivity problem of variation slightly.
In addition, also disclose and between transparency electrode and luminescent layer, formed the relevant invention of organic field luminescence of the organic resin layer that forms by cyanoethylation resin or mylar in Japanese kokai publication sho 59-151799 communique and the Japanese kokai publication hei 3-133091 communique.It is effective to going bad in time of luminescent layer to form organic resin layer, but the dielectric constant of organic resin layer self is not very high, so have the problem of the luminosity step-down of electroluminescent cell.
In addition, in TOHKEMY 2000-82584 communique, disclose and the relevant invention of electroluminescent cell that between transparency electrode and luminescent layer, forms fluorine resin film.Form fluorine resin film and have the effect of uniformly light-emitting, but the dielectric constant of fluorine resin film self not very high, so the purposes of the high brightness of also can't fully satisfying the demand.
On the other hand, the luminescent layer of dispersion type electroluminescence element is formed by fluorophor powder and resinous principle usually.Be well known that with zinc sulphide to be parent as fluorophor powder, add such donor-acceptor pair (DA antithesis) the type fluorophor powders of activator promotor such as activator such as copper and chlorine.This dispersion type electroluminescence element has can be by the advantage of simple painting process manufacturing such as printing and spraying.
Following invention is disclosed in TOHKEMY 2007-134121 communique: a kind of dispersion type electroluminescence element, this dispersion type electroluminescence element comprises the luminescent layer that contains inorganic phosphor, and the pair of electrodes that applies voltage toward luminescent layer, wherein inorganic phosphor comprises the 1st different inorganic phosphor particle of average grain diameter and the 2nd inorganic phosphor particle, and the ratio of the average grain diameter of the average grain diameter of the 1st inorganic phosphor particle and the 2nd inorganic phosphor particle is 2～8.The advantage that this invention had is: can access the luminosity that has than higher, and the high dispersion type electroluminescence element of weatherability.But the average grain diameter of the DA pair type fluorophor powder that luminescent layer uses is tens μ m, so be difficult to satisfy the requirement of filming.In addition, even for the requirement of high luminosity, also be difficult to fully satisfy.In addition,, DA pair type fluorophor powder is formed small particle diameter, thereby during with the dispersion type electroluminescence element filming, the luminosity of DA pair type fluorophor powder reduces significantly, so extremely difficulty realizes filming and high luminosity simultaneously by pulverizing etc.
In addition, the general structure such as the Japanese kokai publication sho 53-108293 communique of film-type electroluminescent cell are disclosed, it is characterized in that, for stack gradually the structure of luminescent layer, dielectric layer and electrode on electrode, luminescent layer is by formation films such as evaporations.The film-type electroluminescent cell has the advantage that can form thin electroluminescent cell.But, must use operations such as evaporation, sputter to make luminescent layers, thus manufacturing installation extensive aspect and be difficult to make large-area electroluminescent cell aspect and also have problem.
Summary of the invention
It is luminous even that first purpose of the present invention is to provide, and it is low to suppress brightness, is difficult to produce insulation breakdown, can form than unfertile land, and the simple dispersion type electroluminescence element of manufacturing process.The inventor finds to use specific transparency dielectric layer, can realize this purpose.
In addition, second purpose of the present invention is to provide the luminosity height, can form than unfertile land, and the simple dispersion type electroluminescence element of manufacturing process.The inventor finds by using specific luminescent layer can realize this purpose.
The invention provides following dispersion type electroluminescence element and manufacture method thereof.
1. dispersion type electroluminescence element, this dispersion type electroluminescence element forms by stack gradually transparency conducting layer, luminescent layer, dielectric layer and backplate on transparent base, it is characterized in that: the transparency dielectric layer that contains resinous principle and electrically conductive microparticle is set between transparency conducting layer and luminescent layer.
2. according to above-mentioned 1 dispersion type electroluminescence element of being put down in writing, wherein the static capacity density of transparency dielectric layer is 2 * 10
-9F/cm
2More than.
3. according to above-mentioned 1 dispersion type electroluminescence element of being put down in writing, wherein the relative dielectric constant of transparency dielectric layer is more than 20.
4. according to above-mentioned 1 dispersion type electroluminescence element of being put down in writing, wherein in transparency dielectric layer, contain the electrically conductive microparticle of volumetric concentration 5～40%.
5. according to above-mentioned 1 dispersion type electroluminescence element of being put down in writing, wherein electrically conductive microparticle is formed by metal oxide.
6. according to above-mentioned 1 dispersion type electroluminescence element of being put down in writing, wherein electrically conductive microparticle is formed by indium tin oxide.
7. according to above-mentioned 1 dispersion type electroluminescence element of being put down in writing, wherein electrically conductive microparticle carries out surface treatment formation.
8. the manufacture method of a dispersion type electroluminescence element, this method comprises the operation of following order: the operation that forms transparency conducting layer on transparent base; Coating, drying contain the transparent dielectric composition of resinous principle and electrically conductive microparticle on above-mentioned transparency conducting layer, form the operation of transparency dielectric layer; By coating, dry luminescent layer composition on above-mentioned transparency dielectric layer, form the operation of luminescent layer; By coating, dry dielectric composition on above-mentioned luminescent layer, form the operation of dielectric layer; And the operation that on above-mentioned dielectric layer, forms backplate.
9. dispersion type electroluminescence element, this dispersion type electroluminescence element comprises transparency conducting layer, luminescent layer, dielectric layer and backplate, it is characterized in that: luminescent layer contains and has fluorophor powder and the resinous principle that there is the type luminescence center in the part, and has the above dielectric strength of 0.15MV/cm.
10. according to above-mentioned 9 dispersion type electroluminescence elements of being put down in writing, wherein having the part, to have 50% average grain diameter of volume distributed median of the fluorophor powder of type luminescence center be 0.2～2.0 μ m.
11. according to above-mentioned 9 dispersion type electroluminescence elements of being put down in writing, wherein the thickness of luminescent layer is 0.3～3.0 μ m.
12. according to above-mentioned 9 dispersion type electroluminescence elements of being put down in writing, wherein to contain volumetric concentration be 1～80% the fluorophor powder that there is the type luminescence center in the part that has to luminescent layer.
13. according to above-mentioned 9 dispersion type electroluminescence elements of being put down in writing, wherein dielectric layer contains electrically conductive microparticle and resinous principle.
14. according to above-mentioned 13 dispersion type electroluminescence elements of being put down in writing, wherein electrically conductive microparticle is formed by metal oxide.
15. according to above-mentioned 13 dispersion type electroluminescence elements of being put down in writing, wherein electrically conductive microparticle carries out forming after the surface treatment.
16. according to above-mentioned 13 dispersion type electroluminescence elements of being put down in writing, wherein to contain volumetric concentration be 5～40% electrically conductive microparticle to dielectric layer.
17. a luminescent layer composition is used to form above-mentioned 9 luminescent layers of being put down in writing.
18. the manufacture method of above-mentioned 9 dispersion type electroluminescence elements of being put down in writing, this method comprises the operation of following order: the operation that forms transparency dielectric layer on transparency conducting layer; Coating, dry luminescent layer composition on transparency dielectric layer, the operation of formation luminescent layer; On luminescent layer, form the operation of dielectric layer, and the operation that on dielectric layer, forms backplate.
Description of drawings
Fig. 1 is the cutaway view of the dispersion type electroluminescence element of first embodiment of inventing.In Fig. 1, symbol 1 expression transparent base, 2 expression transparency conducting layers, 3 expression luminescent layers, 4 expression dielectric layers, 5 expression backplates, 6 expression transparency dielectric layers.
Embodiment
With reference to accompanying drawing the first working of an invention scheme of the present invention is described.Fig. 1 is the cutaway view of the related dispersion type electroluminescence element of the first working of an invention scheme.
The dispersion type electroluminescence element of Fig. 1 is to stack gradually the dispersion type electroluminescence element that transparency conducting layer 2, luminescent layer 3, dielectric layer 4 and backplate 5 form on transparent base 1, and the transparency dielectric layer 6 that contains resinous principle and electrically conductive microparticle is set between transparency conducting layer 2 and luminescent layer 3.
Transparent base 1 so long as in this field commonly used transparent base, just can there is no particular limitation the ground use.Can list for example glass, PETG (PET), acrylic panel etc.
Transparency conducting layer 2 is so long as commonly used transparency conducting layer in this field, just can there is no particular limitation the ground use.For example can list indium tin oxide (below, abbreviate " ITO " as), the film that the zinc oxide (GZO) of the tin oxide (ATO) of the tin oxide of indium oxide, tin oxide, doped with fluorine (FTO), antimony dopant, the zinc oxide (AZO) of adulterated al, doped gallium, the zinc oxide (IZO) of doped indium etc. form etc.
In addition, as dielectric composition, can use transparent dielectric composition described later.By choosing the layer that forms by the transparent dielectric composition, can obtain the layer of film and high-k, thereby obtain the electroluminescent cell of high luminosity, so preferably as dielectric layer 4.
Transparency dielectric layer 6 can be formed by the transparent dielectric composition that contains resinous principle and electrically conductive microparticle.Transparency dielectric layer is preferably the structure of dispersed electro-conductive particulate in resinous principle.
Electrically conductive microparticle is so long as in the scope of the transparency of the transparency dielectric layer 6 that does not damage formation, just can use existing known electrically conductive microparticle.Particularly, be preferably indium tin oxide (below, abbreviate " ITO " as), indium oxide, tin oxide, the tin oxide (FTO) of doped with fluorine, the tin oxide (ATO) of antimony dopant, the zinc oxide (AZO) of adulterated al, the zinc oxide (GZO) of doped gallium, the zinc oxide metal oxides such as (IZO) of doped indium.
In addition, electrically conductive microparticle seeks to carry out surface treatment.By electrically conductive microparticle is carried out surface treatment, can make the electrically conductive microparticle insulating, thus can not damage the insulating properties of the transparency dielectric layer of formation, and improve the content of the electrically conductive microparticle in the transparency dielectric layer.The result is to form the transparency dielectric layer with high relative dielectric constant.
There is no particular limitation for the surface-treated method, can use existing known method.Particularly, can list and for example pass through sol gel reaction,, on the surface of electrically conductive microparticle, separate out, carry out the surface-treated method with the form of metal oxide with metal alkoxides such as tetraethoxysilane, tetraisopropoxy titaniums; By making the reaction of electrically conductive microparticle and silane coupler, carry out the surface-treated method; By silane coupler, electrically conductive microparticle is carried out the surface-treated method with resin; With electrically conductive microparticle and resin mechanical mixture, carry out the surface-treated method; The pH of aluminates such as silicate, sodium aluminate such as adjusting sodium metasilicate etc. separates out on the surface of electrically conductive microparticle with the metal oxide form, carries out surface-treated method etc.
50% average grain diameter of the volume distributed median of electrically conductive microparticle is preferably 10nm～2000nm, more preferably 10nm～500nm.As long as the average grain diameter of electrically conductive microparticle just can be kept the transparency of transparency dielectric layer well in this scope.50% average grain diameter of volume distributed median described here (below, abbreviate " average grain diameter " as), be the median particle diameter (D50) of the particle size distribution of the volume distributed median measured of laser Doppler method, for example can use the laser-Doppler mode particle size distribution device (trade name: Na ノ ト ラ ッ Network UPA-EX250) measure that day machine dress company makes.
In addition, from the insulating properties and the dielectric constant aspect of the transparency dielectric layer that forms, the content of electrically conductive microparticle preferably contains with the scope of volumetric concentration 5～40% in transparency dielectric layer, more preferably 10～30% scope.In addition, the content of surface-treated electrically conductive microparticle, just the amount with the electrically conductive microparticle of removing surface treatment is that benchmark calculates.
There is no particular limitation for the resinous principle that contains in the transparent dielectric composition, for example suitably selects in the material that can enumerate from the explanation of luminescent layer 3 to use.Particularly, from the relative dielectric constant aspect, cyanoethylation resins such as preferred cyanoethylation amylopectin, cyanoethylated fibre element, cyanoethylation sucrose, cyanoethylation polyvinyl alcohol, cyanoethylation phenoxy resin.In addition, can also mix curing agent with these resin reactions as resinous principle.As curing agent, can list imidazole curing agent, amine curing agent, isocyanate curing agent, melamine cured dose etc.From the film that can make formation is cross linking membrane, suppresses to set out with the mixing aspect of other layer preferred mixed curing agent.
In addition, the transparent dielectric composition can contain solvent, pigment dispersing agent, surface conditioner etc. as other composition in the scope of not damaging its performance.
From the luminosity aspect, the static capacity density of transparency dielectric layer 6 is preferably 2 * 10
-9F/cm
2(2nF/cm
2) more than, more preferably 4 * 10
-9F/cm
2(4nF/cm
2) more than.Here, static capacity density σ is with AC5V, and the direct capacitance value of measuring under the condition of frequency 1kHz is divided by the value of electrode area, and the value of static capacity can be used and for example put the LCR HiTester 3532-50 mensuration that motor company makes day.
From the luminosity aspect, the relative dielectric constant of transparency dielectric layer 6 is preferably more than 20, more preferably more than 30.Here, relative dielectric constant is with above-mentioned static capacity density σ (F/cm
2), the thickness d (m) and the permittivity of vacuum e of layer
0=8.82 * 10
-12(F/m), the value calculated of the following formula of substitution (1).
Relative dielectric constant=(10,000 * σ * d)/e
0Formula (1)
In addition, from suppressing the variation and the low aspect of luminosity of tone, the transparency dielectric layer 6 preferably light penetration in the luminous wave-length coverage of luminescent layer 3 is more than 80%.
There is no particular limitation for the thickness of transparency dielectric layer 6, from can obtain damaging insulating properties and also have high static capacity density transparency dielectric layer viewpoint and from obtaining being difficult to producing the viewpoint of the high electroluminescent cell of insulation breakdown and luminosity, be preferably the scope of 0.3～50 μ m, the scope of 0.5 μ m～10 μ m more preferably is preferably the scope of 0.8 μ m～7.0 μ m especially.
There is no particular limitation for the manufacture method of the dispersion type electroluminescence element of first invention, can list the manufacture method that for example stacks gradually transparency conducting layer 2, transparency dielectric layer 6, luminescent layer 3, dielectric layer 4 and backplate 5 on transparent base 1; Stack gradually the manufacture method of dielectric layer 4, luminescent layer 3, transparency dielectric layer 6, transparent electrode layer 2 and transparent base 1 overleaf on the electrode 5; With stacked transparent base 1 to the material of each layer of luminescent layer 3 and overleaf on the electrode 5 material of stacked dielectric layer 4 fit and the method made etc.
Particularly, from the flatness aspect at the interface of watching face one side of simple aspect of operation and luminescent layer, preferably has the method for the operation of following order: the operation that on transparent base 1, forms transparency conducting layer 2; Coating, drying contain the transparent dielectric composition of resinous principle and electrically conductive microparticle on above-mentioned transparency conducting layer 2, form the operation of transparency dielectric layer 6; Coating, dry luminescent layer composition on above-mentioned transparency dielectric layer 6, the operation of formation luminescent layer 3; Coating, dry dielectric composition on above-mentioned luminescent layer 3, the operation of formation dielectric layer 4; And the operation that on above-mentioned dielectric layer 4, forms backplate 5.Below, this manufacture method is elaborated.
At first, on transparent base 1, form transparency conducting layer 2.There is no particular limitation for the formation method, can use known method.Particularly, can list for example coating, dry transparent conductivity paste on transparent base 1, form the method for transparency conducting layer 2, on transparent base 1, form the method for transparent conducting film etc. by evaporation.
Then, coating, drying contain the transparent dielectric composition of resinous principle and electrically conductive microparticle on transparency conducting layer 2, form transparency dielectric layer 6.Coating process is so long as uniform film thickness and can obtain the method for the level and smooth face that is coated with, and just there is no particular limitation.Particularly, can list for example air-atomizing coating, spin coating, showering, roller coat, silk screen printing etc.Drying condition be so long as can fully remove the condition of the solvent that contains in the transparent dielectric composition, perhaps when containing curing agent, and the condition of resin and curing agent reaction, just there is no particular limitation, can suitably determine.
Then, coating, dry luminescent layer composition on the transparency dielectric layer 6 of above-mentioned formation form luminescent layer 3.There is no particular limitation for coating process and drying means, can adopt the method identical with the formation method of above-mentioned transparency dielectric layer.
Then, coating, dry dielectric composition on the luminescent layer 3 of above-mentioned formation form dielectric layer 4.There is no particular limitation for coating process and drying means, can adopt the method identical with the formation method of above-mentioned dielectric layer.
In addition, on the dielectric layer 4 of above-mentioned formation, form backplate 5.There is no particular limitation for the formation method of backplate.Particularly, can list for example method of metals such as gold evaporation, aluminium on dielectric layer 4; Method with sheet metals such as aluminium and dielectric layer 4 stacked joints; Conductive metal oxides such as metal dust such as silver, aluminium or ITO are distributed to after the conductivity paste that forms in resin or the solvent is applied on the dielectric layer the dry method that forms etc.
By said method, can make the related dispersion type electroluminescence element of first invention.
Then, second invention of the present invention is elaborated.The dispersion type electroluminescence element of second invention is the dispersion type electroluminescence element with transparency conducting layer, luminescent layer, dielectric layer and backplate, it is characterized in that: luminescent layer contains and has fluorophor powder and the resinous principle that there is the type luminescence center in the part, and has the above dielectric strength of 0.15MV/cm.
The dispersion type electroluminescence element of second invention is so long as have the dispersion type electroluminescence element of luminescent layer, dielectric layer and backplate of transparency conducting layer, second invention, and the stepped construction of its element is just unqualified.The dispersion type electroluminescence element of second invention can have only 1 layer of dielectric layer, also can have 2 layers of dielectric layer.The dispersion type electroluminescence element of second invention for example can list (I) particularly dispersion type electroluminescence element that the luminescent layer, dielectric layer that stack gradually transparency dielectric layer, second invention on the transparency conducting layer and backplate form (below, abbreviate " dispersion type electroluminescence element (I) " as); (II) dispersion type electroluminescence element that the luminescent layer, dielectric layer that stack gradually second invention on the transparency conducting layer and backplate form (below, abbreviate " dispersion type electroluminescence element (II) " as); (III) at the luminescent layer that stacks gradually transparency dielectric layer, second invention on the transparency conducting layer and the dispersion type electroluminescence element of backplate (below, abbreviate " dispersion type electroluminescence element (III) " as) etc.
Transparency conducting layer is so long as this field transparency conducting layer commonly used just can be not particularly limited use.Can list the film that for example forms by the tin oxide (FTO) of indium tin oxide (ITO), indium oxide, tin oxide, doped with fluorine, the tin oxide (ATO) of antimony dopant, the zinc oxide (AZO) of adulterated al, the zinc oxide (GZO) of doped gallium, the zinc oxide (IZO) of doped indium etc.
Luminescent layer is characterised in that to contain to have fluorophor powder and the resinous principle that there is the type luminescence center in the part, and has the above dielectric strength of 0.15MV/cm.
Having the part, to have the fluorophor powder of type luminescence center be the fluorophor powder that has luminescence centers such as terres rares and transition metal ions in fertile material, and its luminescence center exists in the part.Having the part, to have the lighting means of the fluorophor powder of type luminescence center be that this fluorophor powder is positioned in the electric field, when high energy electron that quickens by electric field and luminescence center conflict, the electron excitation that ground state had of above-mentioned luminescence center is an excited state, by relaxing, produce luminous lighting means afterwards for ground state.
With respect to this, the donor-acceptor pair of using in the luminescent layer of existing dispersion type electroluminescence element (DA antithesis) type fluorophor powder be by the alms giver and the energy transfer between being led luminous, luminescence center is non-local.The lighting means of DA pair type fluorophor powder is according to the paper (A.G.Fischer:J.Electrochem.Soc. of A.G.Fischer, 109 (1962) 1043, A.G.Fischer:J.Electrochem.Soc., 110 (1963) 733) report, zinc sulphide fluorophor (ZnS:Cu with work in copperization, Cl) be example, can be inferred as following lighting means.In the zinc sulphide fluorophor of work in copperization, a part of adding the copper (Cu) in the zinc sulphide (ZnS) to enters in the lattice, forms acceptor level, and chlorine (Cl) etc. forms the impurity energy level as donor level respectively, and the migration between them becomes luminescence center.On the other hand, do not enter the remaining Cu of lattice with needle-like copper sulfide (Cu
xS) form exists.If on fluorophor, apply voltage, then the copper sulfide ejected electron and the hole of needle-like, electronics is caught by the alms giver, and the hole is subjected to main catching.Because alms giver's energy level is superficial, so if polarity of electrode changes, then the electronics of being caught by the alms giver flies out and engaged once more by main hole of catching, this moment is luminous.
As mentioned above, having the part exists the lighting means of employed DA pair type fluorophor powder of the lighting means of fluorophor powder of type luminescence center and existing dispersion type electroluminescence element different.
There is the fluorophor powder of type luminescence center as having the part, for example can list with the element more than at least a kind in transition metal and the rare earth element as luminescence center, be entrained in the fluorophor powder that there is the type luminescence center in the part that has that forms in the fertile material.As transition metal, can list for example Mn, Cr etc.As rare earth element, can list for example Ce, Eu, Tb etc.As fertile material, can list for example sulfide-based fertile material, oxide-based fertile material etc.As sulfide-based fertile material, can list for example ZnS, CaS, SrS, BaS, MgAl
2S
4, CaAl
2S
4, SrAl
2S
4, BaAl
2S
4, ZnAl
2S
4, MgGa
2S
4, CaGa
2S
4, SrGa
2S
4, BaGa
2S
4, ZnGa
2S
4, MgIn
2S
4, CaIn
2S
4, SrIn
2S
4, BaIn
2S
4, ZnIn
2S
4, MgY
2S
4, CaY
2S
4, SrY
2S
4, BaY
2S
4, ZnY
2S
4, Ba
2ZnS
3Deng.As oxide-based fertile material, can list for example Ga
2O
3, CaGa
2O
4, ZnGa
2O
4, BeGa
2O
4, Ge
2O
3, CaGeO
3, Ca
2Ge
2O
7, Zn
2GeO
4, MgGeO
3, Y
2GeO
5, Y
4GeO
8, Y
2Ge
2O
7, CaO, Y
2O
3, SnO
2, Zn
2SiO
4, Y
2SiO
5Deng.
There is the fluorophor powder of type luminescence center as having the part, can lists for example ZnS:Mn, ZnS:Tb, CaS:Eu, CaS:Ce, SrS:Ce, SrS:Cu, BaAl particularly
2S
4: Eu, Ba
2ZnS
3: Mn, Zn
2SiO
4: Mn, ZnGa
2O
4: Mn etc.
There is no particular limitation to have the manufacture method of fluorophor powder of local type luminescence center.List the organic complex thermal decomposition that for example will contain the regulation metal, make the complex compound thermal decomposition method of oxynitride based phosphor powder; To contain constitute fluorophor powder compound element, that play the compound of fuel effect and play the oxidant effect as initiation material, utilize the transmission certainly reaction of high temperature, make the combustion synthesis method of fluorophor powder; After the solution that will contain slaine became fine droplet, the spray heating decomposition of fluorophor powder was made in heat treatment; After mixing the powder stock of regulation, the solid reaction process of fluorophor powder etc. is made in heat treatment.In addition, can also list liquid phase synthesizing methods such as coprecipitation, sol-gel process, hydrothermal synthesis method; Evaporative condenser (PVD) method, gas-phase reaction are separated out gas phase synthesis methods such as (CVD) method.
From obtaining high luminosity aspect, have the fluorophor powder that there is the type luminescence center in the part except above-mentioned manufacture method, preferably increase the pulverizing process manufacturing again.Increased the fluorophor powder that there is the type luminescence center in the part that has of pulverizing process manufacturing by use, the reason of available high luminosity is also uncertain.Above-mentioned reason inventor infers it is because by adding pulverizing process, change the crystallinity on fluorophor powder surface etc., so the insulating properties of fluorophor powder self uprises, therefore, even apply high voltage by the luminescent layer that the part exists the fluorophor powder of type luminescence center to form that has that has increased the pulverizing process manufacturing, also be difficult to produce insulation breakdown, can obtain high luminosity.Pulverizing process can be a waterproof pulverization, also can be dry pulverization process, but from can when pulverizing, be distributed to solvent etc. to shorten the operation aspect, preferred waterproof pulverization.When waterproof pulverization, can be solvent in material powder, carry out waterproof pulverization, also can be that solvent and resinous principle are mixed in the material powder, carry out waterproof pulverization.In addition, also can use the pulverizing assistant.Resinous principle can list for example resinous principle described later etc.
There is no particular limitation to have the average grain diameter of fluorophor powder that there is the type luminescence center in the part.50% average grain diameter that preferred volume distributes is 0.2～2.0 μ m, more preferably 0.3～0.7 μ m.The lower limit of this scope has the meaning of luminosity aspect.The higher limit of this scope makes aspect the dispersion type electroluminescence element thinning and is making the driving voltage lower voltage aspect of dispersion type electroluminescence element have meaning.Here, 50% average grain diameter of described volume distributed median (below, abbreviate " average grain diameter " as) be the median particle diameter (D50) of the particle size distribution of the volume distributed median measured of laser Doppler method, for example can use the laser-Doppler mode particle size distribution device (trade name: Na ノ ト ラ ッ Network UPA-EX250) measure that day machine dress company makes.
It is 1～80% the fluorophor powder that there is the type luminescence center in the part that has that luminescent layer preferably contains volumetric concentration, more preferably contains 15～55%.The lower limit of this scope face luminous be speckless, can obtain aspect the high luminosity meaningful.In addition, the higher limit of this scope be difficult to produce aspect the insulation breakdown meaningful.
There is no particular limitation for resinous principle.Can list for example epoxy resin such as bisphenol A type epoxy resin, phenol novolak type epoxy resin as resinous principle; Cyanoethylation resins such as cyanoethylation amylopectin, cyanoethylated fibre element, cyanoethylation sucrose, cyanoethylation polyvinyl alcohol, cyanoethylation phenoxy resin; Fluororesin such as vinylidene fluoride-hexafluoropropylene copolymer resins, tetrafluoroethylene resin etc.In addition, can also mix curing agent with reaction such as above-mentioned resin as resinous principle.As curing agent, can list imidazole curing agent, amine curing agent, isocyanate curing agent, melamine cured dose etc.Be cross linking membrane from the layer that makes formation, suppress to set out, preferably add curing agent with the aspect of mixing of other layer.
The dielectric strength of luminescent layer is more than the 0.15MV/cm, to be preferably 0.25～0.75MV/cm.By having this dielectric strength, when luminescent layer is thin layer,, also be difficult to produce insulation breakdown even apply high voltage, can obtain high luminosity.Here, described dielectric strength is the value of the higher limit of the finger to finger test body voltage that can not produce insulation breakdown that can apply divided by the thickness of test body.Dielectric strength can be measured by for example following method.(electrode area: 1cm * 1cm) go up coating, dry luminescent layer composition described later, making thickness is 3 μ m, forms luminous tunic at the glass baseplate that forms the ITO electrode.Then, (electrode area 1cm * 1cm), to overlap on the position identical with above-mentioned ITO electrode, the manufacturing electrode area is 1cm to form gold electrode by evaporation on luminous tunic
2The test body of capacitor-like.The electrode of test body is contact terminal respectively, is connected to picoammeter 6487 (ケ one ス レ ィ company makes, trade name, current-voltage determinator), Yi Bian the each 1V of voltage ground is risen, up to maximum 500V, Yi Bian read the current value of this moment.In the way that voltage rises, the voltage when current value is surpassed 2.5mA or gold electrode destroyed, the voltage in the time of can not measuring electric current is as breakdown voltage.The ratio of this breakdown voltage and thickness is dielectric strength.
Above-mentioned dielectric strength can suitably select the back combination to obtain by the composition that above-mentioned in the luminescent layer is had average grain diameter, volumetric concentration and the resinous principle that there be the fluorophor powder of type luminescence center in the part.Particularly, for example can exist 50% average grain diameter of volume distributed median of the fluorophor powder of type luminescence center suitably to select the part that has in the luminescent layer from the scope of 0.2～2.0 μ m, and the volumetric concentration of fluorophor powder that there is the type luminescence center in the part that has in the luminescent layer suitably selected, thereby can obtain the scope of above-mentioned dielectric strength in 1～80% scope.
There is no particular limitation for the thickness of luminescent layer.The thickness of luminescent layer is preferably 0.3～3.0 μ m, more preferably 0.7～2.5 μ m.The lower limit of this scope be difficult to produce aspect the insulation breakdown meaningful.In addition, the higher limit of this scope is meaningful aspect the lower voltage of driving voltage.
Dielectric layer can use dielectric layer commonly used in this area.For example, can list the layer that film, resinous principle by the high dielectric material form, by high dielectric material and resinous principle forms layer etc.As the high dielectric material, can list for example silica (SiO
2), oxidized silicon nitride (SiON), silicon nitride (Si
3N
4), aluminium oxide (Al
2O
3), yittrium oxide (Y
2O
3), barium tantalate (BaTa
2O
6), tantalum oxide (Ta
2O
5), strontium titanates (SrTiO
3), barium titanate (BaTiO
3), lead titanates (PbTiO
3), lead niobate (PbNb
2O
6) etc.As resinous principle, can enumerate identical those of the resinous principle put down in writing in the explanation with luminescent layer.
In addition, dielectric layer can use the dielectric layer that contains electroconductive particle and above-mentioned resinous principle.It is preferred that this dielectric layer can obtain aspect the high luminosity under low-voltage.Particularly, dielectric layer is preferred from the configuration aspects that the formation electrically conductive microparticle is distributed to the resinous principle.
In addition, dielectric layer can also contain the high dielectric material except electrically conductive microparticle and resinous principle.
Electrically conductive microparticle can use existing known electrically conductive microparticle.Particularly, preferred indium tin oxide (below, abbreviate " ITO " as), the lead oxide (GZO) of the tin oxide (ATO) of the tin oxide of indium oxide, tin oxide, doped with fluorine (FTO), antimony dopant, the zinc oxide (AZO) of adulterated al, doped gallium, the zinc oxide metal oxides such as (IZO) of doped indium.
In addition, electrically conductive microparticle seeks to carry out surface treatment.By electrically conductive microparticle is carried out surface treatment, can make the electrically conductive microparticle insulating, thereby can not damage the insulating properties of the dielectric layer of formation, and the content of the electrically conductive microparticle in the raising dielectric layer.The result is to form the dielectric layer with high relative dielectric constant.
There is no particular limitation for the surface-treated method, can use existing known method.Particularly, can list and for example pass through sol gel reaction,, on the surface of electrically conductive microparticle, separate out, carry out the surface-treated method with the form of metal oxide with metal alkoxides such as tetraethoxysilane, tetraisopropoxy titaniums; By making the reaction of electrically conductive microparticle and silane coupler, carry out the surface-treated method; By silane coupler, electrically conductive microparticle is carried out the surface-treated method with resin; With electrically conductive microparticle and resin mechanical mixture, carry out the surface-treated method; The pH of aluminates such as silicate, sodium aluminate such as adjusting sodium metasilicate etc. separates out on the surface of electrically conductive microparticle with the form of metal oxide, carries out surface-treated method etc.
50% average grain diameter of the volume distributed median of electrically conductive microparticle is preferably 10nm～2000nm, more preferably 10nm～500nm.
In addition, from the insulating properties and the dielectric constant aspect of the dielectric layer that forms, the content of electrically conductive microparticle preferably contains with the scope of volumetric concentration 5～40% in dielectric layer, more preferably 10～30% scope.In addition, the content of surface-treated electrically conductive microparticle, just the amount with the electrically conductive microparticle of removing surface treatment is that benchmark calculates.
From the luminosity aspect, the static capacity density σ of dielectric layer is preferably 2 * 10
-9F/cm
2(2nF/cm
2) more than, more preferably 4 * 10
-9F/cm
2(4nF/cm
2) more than.Here, static capacity density σ is with AC5V, and the direct capacitance value of measuring under the condition of frequency 1kHz is divided by the value of electrode area, and the value of static capacity can be used and for example put the LCR HiTester 3532-50 mensuration that motor company makes day.
From the luminosity aspect, the relative dielectric constant of dielectric layer is preferably more than 20, more preferably more than 25.Here, relative dielectric constant is with above-mentioned static capacity density σ (F/cm
2), the thickness d (m) and the permittivity of vacuum e of layer
0=8.82 * 10
-12(F/m) value calculated of the following formula of substitution (1).
Relative dielectric constant=(10,000 * σ * d)/e
0Formula (1)
Dielectric layer can be transparent, also can be opaque, but when dielectric layer is layered between above-mentioned transparency conducting layer and the above-mentioned luminescent layer, and this dielectric layer is preferably dielectric layer with transparency (below, abbreviate " transparency dielectric layer " as).From obtaining high luminosity aspect, transparency dielectric layer is preferably the transparency dielectric layer that is formed by above-mentioned electrically conductive microparticle and above-mentioned resinous principle.In addition, from tone variations with suppress the low aspect of luminosity, the light penetration in the luminous wave-length coverage of the preferred luminescent layer of transparency dielectric layer is more than 90%.
There is no particular limitation for the thickness of dielectric layer.Be preferably 0.3～5.0 μ m, more preferably 0.5～1.5 μ m.The lower limit of this scope be difficult to produce aspect the insulation breakdown meaningful.In addition, the higher limit of this scope is meaningful aspect the lower voltage of driving voltage.
Backplate is so long as this field backplate commonly used, and just there is no particular limitation.For example, can list for example sheet metal such as aluminium; The vapor-deposited film of conductive metal oxides such as metals such as gold, aluminium or ITO or the plastic sheet of stacked this vapor-deposited film; Conductive metal oxides such as metal dusts such as silver, aluminium or ITO are distributed to coated film of the conductivity paste that forms in resin or the solvent etc.
There is no particular limitation for the manufacture method of the dispersion type electroluminescence element of second invention.If with above-mentioned dispersion type electroluminescence element (I) is example, its manufacture method can list the manufacture method of the luminescent layer, dielectric layer and the backplate that for example stack gradually transparency dielectric layer, second invention on transparency conducting layer; Stack gradually the manufacture method of dielectric layer, second luminescent layer of inventing, transparency dielectric layer, transparency conducting layer overleaf on the electrode; Will be at the material that has stacked gradually each layer formation till the luminescent layer of transparency dielectric layer to the second invention on the transparency conducting layer and stacked dielectric layer forms on the electrode overleaf the material manufacture method of fitting etc.
Particularly, in dispersion type electroluminescence element (I), from the flatness aspect at the interface of watching face one side of simple aspect of operation and luminescent layer, the method for the operation of preferred following order: the operation that on transparency conducting layer, forms transparency dielectric layer; Coating, dry luminescent layer composition on transparency dielectric layer, the operation of the luminescent layer of formation second invention; On luminescent layer, form the operation of dielectric layer; And the operation that on dielectric layer, forms backplate.Below, this manufacture method is elaborated.
From the operability aspect, transparency conducting layer preferably forms on transparent base.Transparent base is so long as the transparent base that uses in this field just can be not particularly limited use.Can list for example glass, PETG (PET), acrylic panel etc.There is no particular limitation for the method for formation transparency conducting layer on transparent base, can use known method.Particularly, can list for example coating, dry transparent conductivity paste on transparent base, form the method for transparency conducting layer; On transparent base, form the method for transparent conductive film etc. by evaporation.
Transparency dielectric layer forms on transparency conducting layer.There is no particular limitation for the formation method of transparency dielectric layer, can use known method.For example, behind coating, dry dielectric composition, forming the method for transparency dielectric layer, is preferred from the simple aspect of operation.Can list the dielectric composition that for example contains above-mentioned resinous principle as dielectric composition, and contain dielectric composition of above-mentioned electrically conductive microparticle and above-mentioned resinous principle etc.In addition, dielectric composition can contain solvent, pigment dispersing agent, surface conditioner etc. as other composition in the scope of not damaging its performance.From obtaining high luminosity aspect, be preferably the dielectric composition that contains above-mentioned electrically conductive microparticle and above-mentioned resinous principle as dielectric composition.Coating process is so long as can obtain uniform film thickness and the method for the level and smooth face that is coated with, and just there is no particular limitation.Coating process can list for example air-atomizing coating, spin coating, showering, roller coat, silk screen printing etc. particularly.Drying condition is so long as when dielectric composition contains solvent, and fully except that the condition of desolvating, perhaps the condition of resin and curing agent reaction when containing curing agent with regard to there is no particular limitation, can suitably determine.
Then, coating, dry luminescent layer composition on transparency dielectric layer form second luminescent layer of inventing.The luminescent layer composition is to contain to have fluorophor powder and the toner that there is the type luminescence center in the part, and the luminescent layer that forms has the luminescent layer composition of the above dielectric strength of 0.15MV/cm.Coating process is so long as can obtain uniform film thickness and the method for the level and smooth face that is coated with, and just there is no particular limitation.Can list for example air-atomizing coating, spin coating, showering, roller coat, silk screen printing etc.Drying condition be so long as when luminescent layer contains solvent in composition, can fully remove the condition of desolvating, perhaps when containing curing agent, the condition of resin and curing agent reaction, just can there is no particular limitation make suitable decision.Particularly, for example when luminescent layer contains solvent with composition, can list after the coating luminescent layer is with composition, under 40～150 ℃, carry out 5～60 minutes dry drying conditions.
Luminescent layer in the scope of not damaging its performance, can also contain pigment dispersing agent, surface conditioner etc. as other composition with composition.
Then, on the luminescent layer of above-mentioned formation, form dielectric layer.There is no particular limitation for the method for formation dielectric layer.After for example can listing coating, dry dielectric composition, form the method for dielectric layer.Can list the dielectric composition that contains above-mentioned resinous principle as dielectric composition, and contain dielectric composition of above-mentioned electrically conductive microparticle and above-mentioned resinous principle etc.There is no particular limitation for coating process and drying means, for example can adopt the method identical with the method that forms above-mentioned transparency dielectric layer.
And then, on the dielectric layer of above-mentioned formation, form backplate.There is no particular limitation for the formation method of backplate.Particularly, can list for example method of metal such as gold evaporation, aluminium on dielectric layer; Method with sheet metals such as aluminium and the stacked joint of dielectric layer; Conductive metal oxides such as metal dust such as silver, aluminium or ITO are distributed to after conductivity paste in resin or the solvent is applied on the dielectric layer the dry method that forms etc.
In addition, when forming dispersion type electroluminescence element (II), flatness aspect from the interface of watching face one side of simple aspect of operation and luminescent layer, the method that preferably has the operation of following order: coating, dry luminescent layer composition on transparency conducting layer, the operation of the luminescent layer of formation second invention; In the operation that forms the operation of dielectric layer and on dielectric layer, form backplate on the luminescent layer.The method of each layer of formation in this manufacture method can adopt with the method for making dispersion type electroluminescence element (I) in the identical method of formation method described in detail.
In addition, when forming dispersion type electroluminescence element (III), from the flatness aspect at the interface of watching face one side of simple aspect of operation and luminescent layer, preferably has the method for the operation of following order: the operation that on transparency conducting layer, forms transparency dielectric layer; Coating, dry luminescent layer composition on transparency dielectric layer form the operation of second luminescent layer; On luminescent layer, form the operation of backplate.The method of each layer of formation in this manufacture method can adopt with the method for making dispersion type electroluminescence element (I) in the identical method of formation method described in detail.
The dispersion type electroluminescence element of second invention is owing to obtaining high luminosity, so very useful as the dispersion type electroluminescence element that applies the luminous electroluminescent type of alternating voltage.
The dispersion type electroluminescence element of first invention is characterised in that: have the transparency dielectric layer that contains resinous principle and electrically conductive microparticle between transparency conducting layer and luminescent layer, can obtain having high luminosity with simple manufacturing process according to first invention, luminous even, be difficult to produce insulation breakdown, and dispersion type electroluminescence element that can thin layerization.In addition, this manufacture method is owing to watch transparent base one side of face stacked from conduct, so can make the interface of watching face one side of luminescent layer level and smooth, the brightness of the light-emitting area of the dispersion type electroluminescence element that obtains does not thus have deviation, can obtain luminous uniformly.
The dispersion type electroluminescence element of second invention is the dispersion type electroluminescence element that contains transparency conducting layer, luminescent layer, dielectric layer and backplate, it is characterized in that: luminescent layer contains and has fluorophor powder and the resin composition that there is the type luminescence center in the part, and has an above dielectric strength of 0.15MV/cm, therefore, this dispersion type electroluminescence element has very high luminosity, be difficult to produce insulation breakdown, can thin layerization, but also can obtain by simple operation.
Below, the present invention will be described in more detail to enumerate embodiment.In addition, " part ", " % " there is no particular limitation, expression " mass parts " and " quality % ".
Production Example 1
The preparation of surface-treated electrically conductive microparticle (a)
The ITO particulate of 10g (シ one ァ ィ changes into company and makes, trade name: NanoTekITO-R, average grain diameter 30nm) is added in the 90g deionized water, after being adjusted to pH and being 4 with nitric acid, carry out 2 hours ultrasonic waves and disperse.After the dispersion, dispersion liquid is remained under 40 ℃, and stir, in this dispersion liquid, slowly drip the 13g tetraethoxysilane.After dripping end, remain on 40 ℃, stirred 4 hours again, afterwards, use the washing of deionized water and acetone, drying under reduced pressure obtains surface-treated electrically conductive microparticle (a).Surface-treated electrically conductive microparticle (a) to gained is formed by the photoelectron spectroscopy analysis, confirms to carry out silica surface and handle on the ITO particulate.
Production Example 2
The preparation of surface-treated electrically conductive microparticle (b)
The NanoTek ITO-R of 10g is added in the solvent of 90g isopropyl alcohol, 0.1g deionized water, carry out 2 hours ultrasonic waves and disperse.After the dispersion, add the 3.5g tetraisopropoxy titanium, carry out 2 hours ultrasonic waves again and disperse.Afterwards, use washed with isopropyl alcohol, drying under reduced pressure obtains surface-treated electrically conductive microparticle (b).Surface-treated electrically conductive microparticle (b) to gained is formed by the photoelectron spectroscopy analysis, confirms to carry out titania surface and handle on the ITO particulate.
Production Example 3
The preparation of surface-treated electrically conductive microparticle (c)
NanoTek ITO-R, 4g acrylic resin (trade name: ジ ョ Application Network リ Le 862, the manufacturing of ジ ョ Application ソ Application ヮ ッ Network ス company) and the 100g sodium chloride of 10g are mixed, disperseed 5 hours with planetary ball mill.Afterwards, join in 80 ℃ the warm water, stirred 1 hour, make the sodium chloride dissolving.After the dissolving, filter, use deionized water wash, drying again, obtain surface-treated electrically conductive microparticle (c).Surface-treated electrically conductive microparticle (c) with infiltration type electron microscope observation gained is confirmed to be with resin the ITO particulate is carried out surface treatment.
Production Example 4
The manufacturing of transparent dielectric composition (A-1)
40.5g has been dissolved the cyanoethylation amylopectin in cyclohexanone (chemical industrial company of SHIN-ETSU HANTOTAI makes, trade name: solid constituent シ ァ ノ レ ジ Application CR-S) is 20% resin solution and 6.2g surface-treated electrically conductive microparticle (a) mixing, disperseed 12 hours by oscillator, obtain transparent dielectric composition (A-1).
Production Example 5
The manufacturing of transparent dielectric composition (A-2)
26.6g has been dissolved シ ァ ノ レ ジ Application CR-S in cyclohexanone solid constituent is that 20% resin solution, 9.2g surface-treated electrically conductive microparticle (a) and 14.7g cyclohexanone mix, disperseed 12 hours by oscillator, obtain transparent dielectric composition (A-2).
Production Example 6
The manufacturing of transparent dielectric composition (A-3)
40.5g has been dissolved シ ァ ノ レ ジ Application CR-S in cyclohexanone solid constituent is that 20% resin solution and 5.9g surface-treated electrically conductive microparticle (b) mix, and disperses 12 hours by oscillator, obtains transparent dielectric composition (A-3).
Production Example 7
The manufacturing of transparent dielectric composition (A-4)
26.6g has been dissolved シ ァ ノ レ ジ Application CR-S in cyclohexanone solid constituent is that 20% resin solution, 8.8g surface-treated electrically conductive microparticle (b) and 14.7g cyclohexanone mix, disperseed 12 hours by oscillator, obtain transparent dielectric composition (A-4).
Production Example 8
The manufacturing of transparent dielectric composition (A-5)
40.5g has been dissolved シ ァ ノ レ ジ Application CR-S in cyclohexanone solid constituent is that 20% resin solution and 6.1g surface-treated electrically conductive microparticle (c) mix, and disperses 12 hours by oscillator, obtains transparent dielectric composition (A-5).
Production Example 9
The manufacturing of transparent dielectric composition (A-6)
The solid constituent that will dissolve シ ァ ノ レ ジ Application CR-S in the 26.6g cyclohexanone is that 20% resin solution, 9.0g surface-treated electrically conductive microparticle (c) and 14.7g cyclohexanone mix, disperseed 12 hours by oscillator, obtain transparent dielectric composition (A-6).
Production Example 10
The manufacturing of transparent dielectric composition (A-7)
40.5g has been dissolved シ ァ ノ レ ジ Application CR-S in cyclohexanone solid constituent is that 20% resin solution and the NanoTek ITO-R of 5.9g mix, and disperses 12 hours by oscillator, obtains transparent dielectric composition (A-7).
Production Example 11
The manufacturing of dielectric composition (A-8)
43.6g has been dissolved シ ァ ノ レ ジ Application CR-S in cyclohexanone solid constituent is that 20% resin solution and 5.3g barium titanate (making with the pure medicine of light company) mix, and disperses 12 hours by oscillator, obtains dielectric composition (A-8).
Production Example 12
The luminescent layer manufacturing of composition
The solid constituent that 7.4g has been dissolved シ ァ ノ レ ジ Application CR-S in cyclohexanone is 20% resin solution, luminescent material (the ォ ス ラ system シ Le バ ニ ァ company manufacturing of 5.5g, trade name: Glacier GLO GGS42) and after the 22.1g cyclohexanone mixes, stir, obtain the luminescent layer composition.
Embodiment 1～7
The manufacturing of dispersion type electroluminescence element
Formed by the glass baseplate of the electrode of the film formed transparency conducting layer of ITO (on the ITO face of 3cm * 3cm) having, pass through spin-coating method, each transparent dielectric composition of coating table 1, dry on 140 ℃ hot plate, the transparency dielectric layer of formation thickness 5 μ m.Then, by the air-atomizing rubbing method, the luminescent layer composition that the above-mentioned Production Example 12 of coating is made on transparency dielectric layer, dry on 140 ℃ hot plate.Then, carry out 8 times coating, drying altogether, form the luminescent layer of thickness 50 μ m.Then, once more by spin-coating method, each the transparent dielectric composition shown in the coating table 1, dry on 140 ℃ hot plate, the dielectric layer of formation thickness 5 μ m.Then, gold evaporation on dielectric layer, the dispersion type electroluminescence element of manufacturing embodiment 1～7.
Comparative example 1
Except not forming transparency dielectric layer and embodiment 1 similarly make the dispersion type electroluminescence element of comparative example 1.
Comparative example 2
Except in transparency dielectric layer, use the resin solution of the solid constituent 20% in cyclohexanone, dissolved シ ァ ノ レ ジ Application CR-S to replace beyond the transparent dielectric composition and embodiment 1 similarly, make the dispersion type electroluminescence element of comparative example 2.
Comparative example 3
Except in transparency dielectric layer and dielectric layer, the solid constituent 20% of シ ァ ノ レ ジ Application CR-S has been dissolved in use in cyclohexanone resin solution replaces beyond the transparent dielectric composition, with embodiment 1 similarly, make the dispersion type electroluminescence element of comparative example 3.
Comparative example 4
Except in transparency dielectric layer and dielectric layer, use dielectric composition (A-8) to replace beyond the transparent dielectric composition and embodiment 1 similarly makes the dispersion type electroluminescence element of comparative example 4.
Table 1
| Embodiment | Comparative example | ||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 1 | 2 | 3 | 4 | |
| (transparent) dielectric coating composition that uses in the transparency dielectric layer | A-1 | A-2 | A-3 | A-4 | A-5 | A-6 | A-7 | - | シァノレジンCR-S | シァノレジンCR-S | A-8 |
| (transparent) dielectric coating composition that uses in the dielectric layer | A-1 | A-2 | A-3 | A-4 | A-5 | A-6 | A-7 | A-1 | A-1 | シァノレジンCR-S | A-8 |
| Electrically conductive microparticle content (volumetric concentration: %) in the transparency dielectric layer | 10 | 20 | 10 | 20 | 10 | 20 | 10 | - | 0 | 0 | 10 (annotating 1) |
| Static capacity density (the nF/cm of transparency dielectric layer 2) | 4.9 | 9.5 | 5.1 | 9.2 | 5.5 | 9.0 | 4.8 | - | 1.8 | 1.8 | 6.2 |
| The relative dielectric constant of transparency dielectric layer | 28 | 54 | 29 | 52 | 31 | 51 | 27 | - | 10 | 10 | 35 |
| The light penetration of transparency dielectric layer (%) | 90 | 85 | 85 | 82 | 90 | 85 | 90 | - | 95 | 95 | Below 1 |
| Luminosity (cd/m 2) | 80 | 120 | 70 | 120 | 85 | 115 | 75 | 150 | 20 | 20 | 20 |
| The uniformity that face is luminous | Evenly | Evenly | Evenly | Evenly | Evenly | Evenly | Evenly | Inhomogeneous | Evenly | Evenly | Evenly |
Content (the volumetric concentration: %) of (annotating 1) barium titanate.
Evaluation experimental
Carry out various evaluation experimentals by following method.Evaluation result is as shown in table 1.
(1) the static capacity density of transparency dielectric layer and the calculating of relative dielectric constant
Make and measure the sample that static capacity is used
By rotary coating, at the glass baseplate that forms the ITO electrode (electrode area: 1cm * 1cm) go up the various dielectric compositions shown in the coating table 1, drying on 140 ℃ hot plate, the transparency dielectric layer of formation thickness 5 μ m.Then, (electrode area: 1cm * 1cm) and ITO electrode are paired, make and measure the sample that static capacity is used for gold evaporation on transparency dielectric layer.
The calculating of the mensuration of static capacity and static capacity density
To the sample that the mensuration static capacity of above-mentioned manufacturing is used, under the condition of AC5V, frequency 1kHz, measure static capacity.Use day to put the LCRHiTester 3532-50 that motor company makes during mensuration.Then, the value of static capacity divided by electrode area, is calculated static capacity density σ.
The calculating of relative dielectric constant
From value and the dielectric layer thickness d (m) of the static capacity density σ that tries to achieve before, calculate the relative dielectric constant of each sample by following formula (1).
Relative dielectric constant=(10,000 * σ * d)/e
0Formula (1)
The dielectric constant e of vacuum
0=8.82 * 10
-12(F/m)
(2) mensuration of the light penetration of transparency dielectric layer
Use rotary coating, on the glass plate of thickness 2mm, the various transparent dielectric compositions of coating table 1, dry on 140 ℃ hot plate, the transparency dielectric layer of formation thickness 5 μ m.Gas field analysis instrument (the ス ペ Network ト ロ Off ォ ト メ one one) U-3000 that uses the instrumentation サ of Hitachi one PVC ス (strain) to make during mensuration, the light penetration of mensuration wavelength 550nm.Use identical glass plate as reference, try to achieve the light penetration of transparency dielectric layer by following formula.
(light penetration of transparency dielectric layer)=[(light penetration of the transparency dielectric layer of band glass plate)/(light penetration of glass plate)] * 100
(3) luminosity of dispersion type electroluminescence element is measured
Dispersion type electroluminescence element is applied the alternating voltage of 100V effective voltage, 1kHz respectively, measure the luminosity at initial stage.The luminance meter LS-110 that the mensuration of luminosity is to use コ ニ カ ミ ノ Le company to make measures from the position of the misalignment 5cm of the light-emitting area of dispersion type electroluminescence element in vertical direction.
(4) the luminous uniformity of face
When the alternating voltage of 100V effective voltage, 1kHz that dispersion type electroluminescence element is applied 1000 hours respectively, the uniformity that the visual valuation face is luminous.Metewand is as follows.
Evenly: light-emitting area integral body is luminous with uniform brightness.
Inhomogeneous: as on each position of light-emitting area, non-luminous position to be arranged.
Production Example 13
Have the part and have the preparation of the fluorophor powder of type luminescence center
The KX-605A that mixes 60g (changes into the manufacturing of ォ プ ト ニ Network ス company, trade name, have the part and have the fluorophor powder of type luminescence center, ZnS:Mn, average grain diameter 5 μ m) and 140g ethanol, use YTZ ball (the ニ ッ カ ト one company manufacturing of diameter 0.5mm, trade name), after 3 hours, drying under reduced pressure obtains having the fluorophor powder (P-1) that there is the type luminescence center in the part with the oscillator pulverizing.The average grain diameter of this fluorophor powder is 0.40 μ m.
Embodiment 8
The luminescent layer manufacturing of composition (L-1)
31g has been dissolved the cyanoethylation amylopectin in cyclohexanone (chemical industrial company of SHIN-ETSU HANTOTAI makes, trade name: solid constituent シ ァ ノ レ ジ Application CR-S) is that 20% resin solution, 23.8g have the part and exist the fluorophor powder (P-1) of type luminescence center and 45.1g cyclohexanone to mix, disperseed 2 hours by oscillator, obtain luminescent layer composition (L-1).Luminescent layer by gained is 0.27MV/cm with the dielectric strength of the luminescent layer that composition (L-1) forms.
Embodiment 9
The luminescent layer manufacturing of composition (L-2)
56.8g has been dissolved シ ァ ノ レ ジ Application CR-S in cyclohexanone solid constituent is that 20% resin solution, 18.6g have the part and exist the fluorophor powder (P-1) of type luminescence center and 24.6g cyclohexanone to mix, disperseed 2 hours by oscillator, obtain luminescent layer composition (L-2).Luminescent layer by gained is 0.35MV/cm with the dielectric strength of the luminescent layer that composition (L-2) forms.
Embodiment 10
The luminescent layer manufacturing of composition (L-3)
76.7g has been dissolved シ ァ ノ レ ジ Application CR-S in cyclohexanone solid constituent is that 20% resin solution, 14.7g have the part and exist the fluorophor powder (P-1) of type luminescence center and 8.7g cyclohexanone to mix, disperseed 2 hours by oscillator, obtain luminescent layer composition (L-3).Luminescent layer by gained is 0.50MV/cm with the dielectric strength of the luminescent layer that composition (L-3) forms.
Embodiment 11
The luminescent layer manufacturing of composition (L-4)
22.2g has been dissolved シ ァ ノ レ ジ Application CR-S in cyclohexanone solid constituent is that 20% resin solution, 25.5g have the part and exist the fluorophor powder (P-1) of type luminescence center and 52.2g cyclohexanone to mix, disperseed 2 hours by oscillator, obtain luminescent layer composition (L-4).Luminescent layer by gained is 0.21MV/cm with the dielectric strength of the luminescent layer that composition (L-4) forms.
Embodiment 12
The luminescent layer manufacturing of composition (L-5)
The solid constituent that 31g has been dissolved シ ァ ノ レ ジ Application CR-S in cyclohexanone is that 20% resin solution, KX-605A and the 45.1g cyclohexanone of 23.8g mix, use the YTZ ball of diameter 0.5mm, carry out 3 hours pulverizing, dispersion by oscillator, obtain luminescent layer composition (L-5).Measure this luminescent layer with contain in the composition (L-5) to have the average grain diameter that there is the fluorophor powder of type luminescence center in the part be 0.48 μ m.Luminescent layer by gained is 0.27MV/cm with the dielectric strength of the luminescent layer that composition (L-5) forms.
Embodiment 13
The luminescent layer manufacturing of composition (L-6)
The solid constituent that 31g has been dissolved シ ァ ノ レ ジ Application CR-S in cyclohexanone is that 20% resin solution, KX-605A and the 45.1g cyclohexanone of 23.8g mix, use the YTZ ball of diameter 1.0mm, carry out 3 hours pulverizing, dispersion by oscillator, obtain luminescent layer composition (L-6).Measure this luminescent layer with contain in the composition (L-6) to have the average grain diameter that there is the fluorophor powder of type luminescence center in the part be 0.92 μ m.Luminescent layer by gained is 0.25MV/cm with the dielectric strength of the luminescent layer that composition (L-6) forms.
Embodiment 14
The luminescent layer manufacturing of composition (L-7)
The solid constituent that 31g has been dissolved シ ァ ノ レ ジ Application CR-S in cyclohexanone is that 20% resin solution, KX-605A and the 45.1g cyclohexanone of 23.8g mix, use the YTZ ball of diameter 0.5mm, carry out 12 hours pulverizing, dispersion by oscillator, obtain luminescent layer composition (L-7).Measure this luminescent layer with contain in the composition (L-7) to have the average grain diameter that there is the fluorophor powder of type luminescence center in the part be 0.15 μ m.Luminescent layer by gained is 0.30MV/cm with the dielectric strength of the luminescent layer that composition (L-7) forms.
Embodiment 15
The luminescent layer manufacturing of composition (L-8)
31g has been dissolved シ ァ ノ レ ジ Application CR-S in cyclohexanone solid constituent is 20% resin solution, (change into オ プ ト ニ Network ス company and make, trade name has the fluorophor powder that there is the type luminescence center in the part, Zn to the P1-G1 of 23.8g
2SiO
4: Mn) mix, use the YTZ ball of diameter 0.5mm, carry out 3 hours pulverizing, dispersion, obtain luminescent layer composition (L-8) by oscillator with the 45.1g cyclohexanone.Measure this luminescent layer with contain in the composition (L-8) to have the average grain diameter that there is the fluorophor powder of type luminescence center in the part be 0.52 μ m.Luminescent layer by gained is 0.26MV/cm with the dielectric strength of the luminescent layer that composition (L-8) forms.
Embodiment 16
The luminescent layer manufacturing of composition (L-9)
31g has been dissolved AER ECN-1299 in cyclohexanone (the ケ ミ カ of Asahi Chemical Industry Le ズ company makes, trade name, epoxy resin) solid constituent is that 20% resin solution, KX-605A and the 45.1g cyclohexanone of 23.8g mix, use the YTZ ball of diameter 0.5mm, carry out 3 hours pulverizing, dispersion by oscillator, obtain luminescent layer composition (L-9).Measure this luminescent layer with contain in the composition (L-9) to have the average grain diameter that there is the fluorophor powder of type luminescence center in the part be 0.45 μ m.Luminescent layer by gained is 0.30MV/cm with the dielectric strength of the luminescent layer that composition (L-9) forms.
Comparative example 5
The luminescent layer manufacturing of composition (CL-1)
9.2g has been dissolved シ ァ ノ レ ジ Application CR-S in cyclohexanone solid constituent is that 20% resin solution, 28.2g have the part and exist the fluorophor powder (P-1) of type luminescence center and 62.6g cyclohexanone to mix, disperseed 2 hours by oscillator, obtain luminescent layer composition (CL-1).Luminescent layer by gained is 0.13MV/cm with the dielectric strength of the luminescent layer that composition (CL-1) forms.
Production Example 14
The manufacturing of dielectric composition (D-1)
40.5g has been dissolved シ ァ ノ レ ジ Application CR-S in cyclohexanone solid constituent is that the surface-treated electrically conductive microparticle (a) of preparation in 20% resin solution and the 6.2g Production Example 1 mixes, disperseed 12 hours by oscillator, obtain dielectric composition (D-1).
Production Example 15
The manufacturing of dielectric composition (D-2)
シ ァ ノ レ ジ Application CR-S has been dissolved in preparation in cyclohexanone solid constituent is 20% resin solution, as dielectric composition (D-2).
Embodiment 17
The manufacturing of dispersion type electroluminescence element (EL-1)
Have formed by the glass baseplate of the film formed transparency conducting layer of ITO (on the ITO face of 3cm * 3cm), by spin coating, coating dielectric composition (D-1), dry on 140 ℃ hot plate, form the transparency dielectric layer of thickness 1.0 μ m.Then, by spin coating, coating luminescent layer composition (L-1) is dry on 140 ℃ hot plate on transparency dielectric layer, forms the luminescent layer of thickness 1.0 μ m.Then, by spin coating, coating dielectric composition (D-1), dry on 140 ℃ hot plate, the dielectric layer of formation thickness 1.0 μ m.Then, gold evaporation on dielectric layer is made dispersion type electroluminescence element (EL-1).The luminosity of the character of luminescent layer, transparency dielectric layer and the dielectric layer of the dispersion type electroluminescence element of gained (EL-1) and dispersion type electroluminescence element (EL-1) is as shown in table 2.
Embodiment 18～30, comparative example 6
Dispersion type electroluminescence element (EL-2)～(EL-14) and manufacturing (CEL-1)
Except with the dielectric composition among the embodiment 17 and luminescent layer composition change be table 2 put down in writing those, make dispersion type electroluminescence element (EL-2)～(EL-14) and (CEL-1) by same method.In addition, in each dispersion type electroluminescence element, transparency dielectric layer uses identical dielectric composition with dielectric layer.The character of the luminescent layer of the dispersion type electroluminescence element of gained, transparency dielectric layer and dielectric layer and the luminosity of dispersion type electroluminescence element are as shown in table 2.
Table 2
| Embodiment 17 | Embodiment 18 | Embodiment 19 | Embodiment 20 | Example 21 | Example 22 | Embodiment 23 | Embodiment 24 | Embodiment 25 | Embodiment 26 | Embodiment 27 | Embodiment 28 | Embodiment 29 | Embodiment 30 | Comparative example 6 | ||
| Dispersion type electroluminescence element | EL-1 | EL-2 | EL-3 | EL-4 | EL-5 | EL-6 | EL-7 | EL-8 | EL-9 | EL-10 | EL-11 | EL-12 | EL-13 | EL-14 | CEL-1 | |
| Luminescent layer | The luminescent layer composition | L-1 | L-2 | L-3 | L-4 | L-5 | L-6 | L-7 | L-8 | L-9 | L-5 | L-5 | L-5 | L-5 | L-5 | CL-1 |
| Thickness (μ m) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 0.8 | 2.0 | 1.0 | 0.8 | 2.0 | 1.0 | |
| The volumetric concentration of fluorophor powder (%) | 50 | 30 | 20 | 60 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 80 | |
| Average grain diameter (D50) (μ m) | 0.40 | 0.40 | 0.40 | 0.40 | 0.48 | 0.92 | 0.15 | 0.52 | 0.45 | 0.48 | 0.48 | 0.48 | 0.48 | 0.48 | 0.40 | |
| Dielectric strength (MV/cm) | 0.27 | 0.35 | 0.50 | 0.21 | 0.27 | 0.26 | 0.30 | 0.26 | 0.30 | 0.27 | 0.27 | 0.27 | 0.27 | 0.27 | 0.13 | |
| Transparent dielectric layer and dielectric layer | Dielectric composition | D-1 | D-1 | D-1 | D-1 | D-1 | D-1 | D-1 | D-1 | D-1 | D-1 | D-1 | D-2 | D-2 | D-2 | D-1 |
| Thickness (μ m) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | |
| The volumetric concentration (%) of surface-treated electrically conductive microparticle (a) | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 0 | 0 | 0 | 10 | |
| Static capacity density (nF/m 2) | 23 | 23 | 23 | 23 | 23 | 23 | 23 | 23 | 23 | 23 | 23 | 12 | 12 | 12 | 23 | |
| Relative dielectric constant | 26 | 26 | 26 | 26 | 26 | 26 | 26 | 26 | 26 | 26 | 26 | 14 | 14 | 14 | 26 | |
| Luminosity ( *) | AC100V(cd/m 2) | 35 | 35 | 35 | 40 | 41 | Below 1 | Below 1 | Below 1 | Below 1 | 30 | 30 | Below 1 | Below 1 | Below 1 | 40 |
| AC125V(cd/m 2) | 410 | 450 | 420 | 400 | 520 | 25 | 7 | Below 1 | Below 1 | 390 | 410 | Below 1 | Below 1 | Below 1 | × | |
| AC150V(cd/m 2) | 950 | 1050 | 970 | - | 1550 | 250 | 70 | Below 1 | 7 | 950 | 1010 | 7 | 6 | 7 | × | |
| AC200V(cd/m 2) | - | - | - | - | - | 325 | 132 | 15 | 200 | - | - | 35 | 30 | 35 | × | |
| AC250V(cd/m 2) | - | - | - | - | - | - | - | 500 | 1550 | - | - | 610 | 600 | 600 | × | |
(
*): "-" expression undetermined, " * " expression produces insulation breakdown, can't measure.
Evaluation experimental
The luminosity of the dielectric strength of above-mentioned luminescent layer, the static capacity of dielectric layer and relative dielectric constant and dispersion type electroluminescence element is by following determination of experimental method.
(5) mensuration of the dielectric strength of luminescent layer
By spinner, (on electrode area: the 1cm * 1cm), the various luminescent layer compositions of coating embodiment 8～16, comparative example 5 so that thickness is 3 μ m, 140 ℃ of dryings 30 minutes down, form luminous tunic at the glass baseplate that forms the ITO electrode.Then, and evaporation formation gold electrode on luminous tunic (electrode area: 1cm * 1cm), and this electrode is overlapped on the position identical with above-mentioned ITO electrode, the manufacturing electrode area is 1cm
2The test body of capacitor-like.The electrode of test body is contact terminal respectively, and (ケ one ス レ ィ company makes, trade name: ピ コ ァ Application メ one 1), make the maximum 500V of rising to of the each 1V of voltage on one side, Yi Bian read current value at this moment to be connected to the current-voltage determinator.Voltage when current value surpasses 2.5mA in rising voltage on the way, perhaps gold electrode destroys, and the voltage in the time of can't measuring electric current is as breakdown voltage.This breakdown voltage divided by thickness, is tried to achieve dielectric strength.
(6) the static capacity density of dielectric layer and the calculating of relative dielectric constant
Make and measure the sample that static capacity is used
By rotary coating, at the glass baseplate that forms the ITO electrode (electrode area: 1cm * 1cm) go up the various dielectric compositions that are coated with Production Example 14 and Production Example 15, drying on 140 ℃ hot plate, the dielectric layer of formation thickness 1 μ m.Then, gold evaporation on dielectric layer (electrode area: 1cm * 1cm), so that paired with the ITO electrode, make and measure the sample that static capacity is used.
The calculating of the mensuration of static capacity and static capacity density
To the sample that the mensuration static capacity of above-mentioned manufacturing is used, under the condition of AC5V, frequency 1kHz, measure static capacity.Use day to put the LCRHiTester 3532-50 that motor company makes during mensuration.Then, the value of static capacity divided by electrode area, is calculated static capacity density σ.
The calculating of relative dielectric constant
From value and the dielectric layer thickness d (m) of the static capacity density σ that tries to achieve before, calculate the relative dielectric constant of each sample by following formula (1).
Relative dielectric constant=(10,000 * σ * d)/e
0Formula (1)
The dielectric constant e of vacuum
0=8.82 * 10
-12(F/m)
(7) luminosity of dispersion type electroluminescence element is measured
On each dispersion type electroluminescence element of embodiment 17～30, comparative example 6, apply effective alternating voltage of frequency 1kHz, measure the initial stage luminosity under 100V, 125V, 150V, 200V, the 250V.The luminance meter LS-110 that the mensuration of luminosity is to use コ ニ カ ミ ノ Le company to make measures from the position of the misalignment 5cm of the light-emitting area of dispersion type electroluminescence element in vertical direction.
Claims (18)
1. dispersion type electroluminescence element, this dispersion type electroluminescence element forms by stack gradually transparency conducting layer, luminescent layer, dielectric layer and backplate on transparent base, it is characterized in that: the transparency dielectric layer that contains resinous principle and electrically conductive microparticle is set between transparency conducting layer and luminescent layer.
2. the dispersion type electroluminescence element of putting down in writing according to claim 1, wherein the static capacity density of transparency dielectric layer is 2 * 10
-9F/cm
2More than.
3. the dispersion type electroluminescence element of putting down in writing according to claim 1, wherein the relative dielectric constant of transparency dielectric layer is more than 20.
4. the dispersion type electroluminescence element of putting down in writing according to claim 1 wherein contains the electrically conductive microparticle of volumetric concentration 5～40% in transparency dielectric layer.
5. the dispersion type electroluminescence element of putting down in writing according to claim 1, wherein electrically conductive microparticle is formed by metal oxide.
6. the dispersion type electroluminescence element of putting down in writing according to claim 1, wherein electrically conductive microparticle is formed by indium tin oxide.
7. the dispersion type electroluminescence element of putting down in writing according to claim 1, wherein electrically conductive microparticle carries out surface treatment and forms.
8. the manufacture method of a dispersion type electroluminescence element, this method comprises the operation of following order: the operation that forms transparency conducting layer on transparent base; By the transparent dielectric composition that on above-mentioned transparency conducting layer, is coated with, drying contains resinous principle and electrically conductive microparticle, form the operation of transparency dielectric layer; By coating, dry luminescent layer composition on above-mentioned transparency dielectric layer, form the operation of luminescent layer; By coating, dry dielectric composition on above-mentioned luminescent layer, form the operation of dielectric layer; And the operation that on above-mentioned dielectric layer, forms backplate.
9. dispersion type electroluminescence element, this dispersion type electroluminescence element comprises transparency conducting layer, luminescent layer, dielectric layer and backplate, it is characterized in that: luminescent layer contains and has fluorophor powder and the resinous principle that there is the type luminescence center in the part, and has the above dielectric strength of 0.15MV/cm.
10. the dispersion type electroluminescence element of putting down in writing according to claim 9, wherein having the part, to have 50% average grain diameter of volume distributed median of the fluorophor powder of type luminescence center be 0.2～2.0 μ m.
11. according to the dispersion type electroluminescence element that claim 9 is put down in writing, wherein the thickness of luminescent layer is 0.3～3.0 μ m.
12. the dispersion type electroluminescence element of putting down in writing according to claim 9, wherein to contain volumetric concentration be 1～80% the fluorophor powder that there is the type luminescence center in the part that has to luminescent layer.
13. according to the dispersion type electroluminescence element that claim 9 is put down in writing, wherein dielectric layer contains electrically conductive microparticle and resinous principle.
14. according to the dispersion type electroluminescence element that claim 13 is put down in writing, wherein electrically conductive microparticle is formed by metal oxide.
15. according to the dispersion type electroluminescence element that claim 13 is put down in writing, wherein electrically conductive microparticle carries out forming after the surface treatment.
16. the dispersion type electroluminescence element of putting down in writing according to claim 13, wherein to contain volumetric concentration be 5～40% electrically conductive microparticle to dielectric layer.
17. a luminescent layer composition is used to form the luminescent layer that claim 9 is put down in writing.
18. the manufacture method of the dispersion type electroluminescence element that claim 9 is put down in writing, this method comprises the operation of following order: the operation that forms transparency dielectric layer on transparency conducting layer; Coating, dry luminescent layer composition on transparency dielectric layer, the operation of formation luminescent layer; On luminescent layer, form the operation of dielectric layer, and the operation that on dielectric layer, forms backplate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007021521 | 2007-01-31 | ||
| JP2007021521 | 2007-01-31 | ||
| JP2007312992 | 2007-12-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101237729A true CN101237729A (en) | 2008-08-06 |
Family
ID=39786884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100067203A Pending CN101237729A (en) | 2007-01-31 | 2008-01-28 | Dispersion type electroluminescence element and manufacturing method thereof |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2008210780A (en) |
| CN (1) | CN101237729A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578306A (en) * | 2021-09-06 | 2021-11-02 | 上海市普陀区人民医院(上海纺织第一医院) | Preparation method of 2D/1D heterojunction photocatalyst and application thereof in hydrogen production |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100276675A1 (en) * | 2007-12-05 | 2010-11-04 | Reiko Taniguchi | Light-emitting device |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02223191A (en) * | 1989-02-23 | 1990-09-05 | Alps Electric Co Ltd | Electroluminescent device |
| JPH05266980A (en) * | 1992-03-18 | 1993-10-15 | Sumitomo Chem Co Ltd | Electroluminescence lamp |
| JP4910225B2 (en) * | 1999-11-09 | 2012-04-04 | 東洋紡績株式会社 | Transparent conductive film, and electroluminescence panel and touch panel using the same |
| JP4748940B2 (en) * | 2003-02-13 | 2011-08-17 | 富士フイルム株式会社 | AC operation electroluminescence element |
| EP1667089A4 (en) * | 2003-08-19 | 2009-04-08 | Fuji Electric Holdings | Display and method for driving same |
| JP2008065984A (en) * | 2006-09-04 | 2008-03-21 | Shin Etsu Polymer Co Ltd | El sheet and cover member for push-button switch |
-
2007
- 2007-12-12 JP JP2007321281A patent/JP2008210780A/en active Pending
-
2008
- 2008-01-28 CN CNA2008100067203A patent/CN101237729A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578306A (en) * | 2021-09-06 | 2021-11-02 | 上海市普陀区人民医院(上海纺织第一医院) | Preparation method of 2D/1D heterojunction photocatalyst and application thereof in hydrogen production |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008210780A (en) | 2008-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4867055B2 (en) | Dispersive electroluminescence device | |
| JP2015057786A (en) | Laminated thick film dielectric structure for thick film dielectric electroluminescent display | |
| US20050189518A1 (en) | Method of producing a fluorescent particle | |
| KR20060114387A (en) | Field-emission phosphor, its manufacturing method, and field-emission device | |
| CN102138365B (en) | Inorganic light-emitting device | |
| WO2006093095A1 (en) | Dispersion-type electroluminescent element | |
| US6579631B2 (en) | Electroluminescence device and method for manufacturing the same | |
| CN101237729A (en) | Dispersion type electroluminescence element and manufacturing method thereof | |
| CN1965615B (en) | Electroluminescence device | |
| US20070210708A1 (en) | Light-Emitting Element and Display Apparatus | |
| US20060255718A1 (en) | Dispersion type electroluminescent element | |
| DE602005004593T2 (en) | Electroluminescent phosphor | |
| US20050052129A1 (en) | Electroluminescent material | |
| KR20080071932A (en) | Dispersion type el element and method of preparation thereof | |
| JP2009140624A (en) | Composition for light-emitting layer, and dispersion type el element | |
| JP2008123780A (en) | Dispersed type inorganic electroluminescent element and lighting system equipped with it | |
| EP1993326A1 (en) | Particle with an electro-luminescent element containing nano structures | |
| KR100638809B1 (en) | Compositions of Silver electrode Paste and Electroluminescence device parepared from them | |
| JP5197641B2 (en) | Dispersion-type inorganic EL device and manufacturing method thereof | |
| KR101064166B1 (en) | Inorganic Electro Luminescence device and manufacturing method thereof | |
| JP2002289359A (en) | Distributed type el element | |
| JP5824944B2 (en) | Dispersion type inorganic electroluminescence device | |
| JP2005272798A (en) | Method of producing phosphor particle | |
| JP5197653B2 (en) | Dispersion-type inorganic EL element, manufacturing method thereof, and manufacturing apparatus of inorganic EL light emitting layer | |
| JP2006236924A (en) | Inorganic dispersion type electroluminescent element and luminescent element system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080806 |