CN101106048B

CN101106048B - Fluorophor paste and method for manufacturing display device

Info

Publication number: CN101106048B
Application number: CN2007101268154A
Authority: CN
Inventors: 川崎学; 藤原秀行; 平井善英
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2006-06-28
Filing date: 2007-06-27
Publication date: 2011-02-16
Anticipated expiration: 2027-06-27
Also published as: CN101106048A; TW200813186A; TWI417362B; KR20080001635A; KR101370181B1

Abstract

The invention provides a phosphor paste. The hosphor powder evenly and stably disperses over the paste and the time variation of viscosity is small, and the chromaticity variation of phosphor layer is small after burning. The phosphor paste contains phosphor powder, binder resin, primary amine or secondary amine compound with hydroxyl group, and/or an alkoxyl group and with molecular weight of below 300, and an organic solvent.

Description

The manufacture method of fluorophor paste and display

Technical field

The present invention relates to a kind of fluorophor powder and disperse the fluorophor paste that forms equably, particularly be used for the fluorophor paste of plasma display (hereinafter referred to as PDP) and the manufacture method of display.

Background technology

Because PDP compares with liquid crystal panel and can show at high speed, also be easy to realize maximizing, so begin to be applied to fields such as OA machine and bulletin display unit.And then the progress in high-grade TV domain etc. also is worth expectation very much.Along with the expansion of above-mentioned range of application, the color PDP with a plurality of fine display units comes into one's own gradually.

Make in the discharge space that PDP disposes between glass substrate and the back glass substrate in front and produce plasma discharge between electrode, the ultraviolet ray that is produced by the gas of being enclosed in the above-mentioned discharge space makes the light-emitting phosphor in the discharge space, shows thus.When in PDP, forming luminescent coating, owing to, not only all be coated with fluorophor paste in unit bottom but also in the side of dividing plate for high brightnessization, thus need expend time, in order to eliminate brightness disproportionation, must stable and coating equably.Therefore, must make fluorophor paste have desirable viscosity, and then must make the stable and dispersion equably of the fluorophor powder that contains in the fluorophor paste.

The surface of the fluorophor powder that fluorophor paste is used is formed by increment or various surface treatment becomes acidity, alkalescence or state acid and that the alkalescence mixing exists.Above-mentioned fluorophor powder is because of causing its functional group with adhesive gelation reaction to take place, the problem that makes the viscosity rising with adhesive resin combination.

And then generally, in the used redness of PDP device, green, the cyan fluorophor particle, the charging property of green-emitting phosphor particle is a negativity, and is opposite with the fluorophor particle of other colors.Therefore, when being coated with fluorophor paste continuously, because the selection of adhesive resin makes adhesive resin be difficult to be adsorbed on the surface of electronegative green-emitting phosphor particle, so green-emitting phosphor particles aggregate, produce spray nozzle clogging or crawling, problems such as display characteristic deterioration appear in the PDP of gained.

Therefore, disclose a kind of at present by surface with coating fluorophor powders such as the oxide, fluorine compounds or the boron compounds that contain the big element of electronegativity, when preventing each luminescent coating deterioration, make the consistent method (referring to patent documentation 1～4) of charged tendency of each phosphor particles.But, during with above-claimed cpd coating fluorophor powder surperficial, the problem that exists easy aggegation, dispersion stabilization to reduce.

In addition, known by in fluorophor paste, add anion surfactant or non-ionic surface active agent (referring to patent documentation 5～7), alkylamine (referring to patent documentation 8～9), carboxylic acid amine salt (referring to the patent documentation 10) dispersant of etc.ing can make the dispersion stabilization raising.But, when using anion surfactant or non-ionic surface active agent, because molecular weight is big, so there be the problem little with respect to the dispersion effect of addition gained as dispersant.In addition, even use amines such as alkylamine or carboxylic acid amine salt, also exist and be difficult to obtain sufficient stably dispersing effect, or increase addition in order to obtain the stably dispersing effect and cause after burning till, remaining in the fluorophor surface, painted situation takes place, and is difficult to as dispersant.

[patent documentation 1] spy opens the 2004-323576 communique

[patent documentation 2] spy opens the 2005-100954 communique

[patent documentation 3] spy opens the 2005-183246 communique

[patent documentation 4] spy opens the 2004-322563 communique

[patent documentation 5] spy opens the 2003-96443 communique

[patent documentation 6] spy opens flat 11-209751 communique

[patent documentation 7] spy opens flat 11-224609 communique

[patent documentation 8] spy opens flat 10-53433 communique

[patent documentation 9] spy opens flat 7-188599 communique

[patent documentation 10] spy opens the 2002-82432 communique

Summary of the invention

The object of the present invention is to provide a kind of fluorophor paste, wherein fluorophor powder evenly and stably is dispersed in the slurry, viscosity through the time change little, and then the luminescent chromaticity that burns till the luminescent coating that the back forms compare with the luminescent chromaticity that does not burn till powder change little.

The molecular weight that the present invention preferably contains fluorophor powder, adhesive resin, have hydroxyl and/or an alkoxyl is primary amine below 300 or secondary amine compound, and the fluorophor paste of organic solvent.

The boiling point of preferred amines compound is 80～350 ℃.

The use level of preferred amines compound in fluorophor paste is 0.2～5 weight %.

The preferred use level of fluorophor powder in fluorophor paste is 40～60 weight %, and the use level of adhesive resin in fluorophor paste is 5～20 weight %.

Preferred organic solvent has hydroxyl.

And, preferably contain acid compound.

In addition, the present invention also relates to a kind of manufacture method of display, described method is included in the above-mentioned fluorophor paste of coating on the substrate, burns till, and forms the operation of luminescent coating thus.

The present invention so fluorophor surface and adhesive resin compatibility to each other increase, makes the fluorophor powder decentralized stabilization owing to contain the amines with hydroxyl and/or alkoxyl in the fluorophor paste.And, because the molecular weight of amines is little,, can forms colourity and change little luminescent coating so amines is not residual when fluorophor paste burns till, the result can reduce the deterioration in brightness of the display that obtains.

Embodiment

Slurry of the present invention must contain fluorophor paste, and the molecular weight that described fluorophor paste contains fluorophor powder, adhesive resin, have hydroxyl and/or an alkoxyl is primary amine below 300 or secondary amine compound, and organic solvent.Concrete example as above-mentioned amines, can enumerate N-(2-methoxy ethyl)-1-butylamine, 4,4-Er Jia Ji oxazolidine, N-(2-methoxy ethyl)-1-propylamine, 3-(methylamino)-1-propyl alcohol, 2-ethyoxyl-N-ethyl-ethamine, N-ethyl-2-methoxyl group-ethamine, N-(2-ethoxyethyl group)-1-butylamine, the N-ethylidene dicarbamate, N-benzylamino methyl formate, 3-methoxyl group piperidines, the butyl methyl carbamate, carbamic acid, 2,2 '-imino group bis-ethanol, 1,1 '-imino group is two-the 2-propyl alcohol, morpholine, 2-(methylamino) ethanol, 2-(ethylamino) ethanol, N-(2-methoxy ethyl) methylamine, diethanol amine, two (2-methoxy ethyl) amine, two (2-ethoxyethyl group) amine, the 2-aminocyclohexanol, 2-methoxyl group-2-methyl isophthalic acid-propylamine, 3-amino-2,2-dimethyl-1-propyl alcohol, 1-amino-2-methyl-2-propyl alcohol, 5-amino-1-amylalcohol, 3-amino-1-propyl alcohol, 1-amino-2-propyl alcohol, the 2-methoxyethyl amine, the 2-ethoxy ethyl amine, 2-(amino ethoxy) ethanol, 1, two (amino ethoxy) ethane of 2-etc.

Because used amines has hydroxyl and/or alkoxyl in the fluorophor paste of the present invention, so can improve the compatibility of fluorophor surface and adhesive resin.Have the amines of alkoxyl and compare with the amines that only has hydroxyl, boiling point easily reduces, and the amines when burning till easily burnouts (burn-out), and is therefore preferred.As alkoxyl, can enumerate methoxyl group, ethyoxyl, butoxy, propoxyl group etc., but consider preferred methoxyl group, ethyoxyl from viewpoints such as the effect that improves for low-molecular-weight, compatibility burnouting property big, fluorophor paste are good.

Preferred primary amine of the amines that uses in the fluorophor paste of the present invention or secondary amine.By using primary amine or secondary amine compound, compare with tertiary amine, use less addition can easily produce the decentralized stabilization effect.Though its mechanism is still indeterminate, deducibility is more relevant than tertiary amine height with the alkalescence of primary amine or secondary amine compound.Generally speaking preferred primary amine in primary amine or the secondary amine, as above-claimed cpd, can enumerate 2-methoxyl group-2-methyl isophthalic acid-propylamine, 3-amino-2,2-dimethyl-1-propyl alcohol, 1-amino-2-methyl-2-propyl alcohol, 5-amino-1-amylalcohol, 3-amino-1-amylalcohol, 1-amino-2-propyl alcohol, 2-ethylaminoethanol, 2-methoxyethyl amine, 2-ethoxy ethyl amine, 2-(amino ethoxy) ethanol etc.

The molecular weight of the amines that uses in the fluorophor paste of the present invention is below 300, is preferably below 200, more preferably below 100.Molecular weight was greater than 300 o'clock, because the amido content of per unit weight is little, so have following tendency, promptly be difficult to produce decentralized stabilization effect, burnouting property variation due to the amines, become the deterioration in brightness of burning till the back luminescent coating, the reason that colourity changes etc.The lower limit of the molecular weight of amines does not have special qualification, but since boiling point as described below reduce, in slurry manufacturing process, be easy to wave diffusing, so be preferably more than 60.Molecular weight can use TOF-MASS (flight time type quality analysis apparatus) etc. to estimate.As molecular weight is the concrete example of the amines below 100 more than 60, can enumerate 1-amino-2-methyl-2-propyl alcohol, 3-(methylamino)-1-propyl alcohol, morpholine, 2-(methylamino) ethanol, 2-(ethylamino)-ethanol, N-(2-methoxy ethyl) methylamine, 3-amino-1-propyl alcohol, 1-amino-2-propyl alcohol, 2-ethylaminoethanol, 2-methoxyethyl amine, 2-ethoxy ethyl amine etc.

Carbochain in the skeleton is compared with heterocycle, cycloaliphatic ring, alkyl chain, the alkylene oxide chain of preferred straight or branched.As carbon number, be preferably 2～10, more preferably 2～5.Carbon number was greater than 10 o'clock, because burnouting property variation, so can use alkylene oxide chains such as ethylene oxide chain or expoxy propane chain.Particularly carbon number is less, is about at 2～5 o'clock, also can more easily not obtain good burnouting property even do not import the alkylene oxide chain, so more preferred.It as carbon number the concrete example of 2～5 amines, can enumerate N-(2-methoxy ethyl)-1-butylamine, N-(2-methoxy ethyl)-1-propylamine, 3-(methylamino)-1-propyl alcohol, 2-ethyoxyl-N-ethyl-ethamine, N-ethyl-2-methoxyl group-ethamine, N-(2-ethoxyethyl group)-1-butylamine, 2,2 '-imino group bis-ethanol, 2-(methylamino) ethanol, 2-(ethylamino) ethanol, N-(2-methoxy ethyl) methyl amine, diethanol amine, two (2-methoxy ethyl) amine, two (2-ethoxyethyl group) amine, 2-methoxyl group-2-methyl isophthalic acid-propylamine, 3-amino-2,2-dimethyl-1-propyl alcohol, 5-amino-1-amylalcohol, 2-(amino ethoxy) ethanol, 1-amino-2-methyl-2-propyl alcohol, 3-amino-1-propyl alcohol, 1-amino-2-propyl alcohol, the 2-ethylaminoethanol, 2-methoxy ethyl amine, 2-ethoxyethyl group amine etc.

The boiling point of the amines that uses in the fluorophor paste of the present invention is preferably 80～350 ℃, more preferably 100～200 ℃, when boiling point is higher than 350 ℃, has burnouting property variation when burning till, easily the tendency that brightness reduction or colourity change (yellowing) takes place.On the other hand, when boiling point is lower than 80 ℃, when making fluorophor paste or during dry fluorophor paste film, has the tendency that the easy slurries such as incendivity rising that produce into foul smell, slurry are handled the difficulty that becomes.In addition, when boiling point was lower than 200 ℃, amines was easy to wave diffusing in following drying process, and amines is difficult to burn in burning till, and was difficult for causing the brightness reduction of fluorophor or colourity variation etc., so preferred.As boiling point is the concrete example of 100～200 ℃ amines, can enumerate 4,4-Er Jia Ji oxazolidine, N-(2-methoxy ethyl)-1-propylamine, 2-ethyoxyl-N-ethyl-ethamine, N-ethyl-2-methoxyl group-ethamine, 2-(methylamino) ethanol, 2-(ethylamino) ethanol, N-(2-methoxy ethyl)-1-butylamine, 3-(methylamino)-1-propyl alcohol, N-(2-ethoxyethyl group)-1-butylamine, the N-ethylidene dicarbamate, 3-methoxyl group piperidines, the butyl methyl carbamate, carbamic acid, morpholine, 2-methoxyl group-2-methyl isophthalic acid-propylamine, 1-amino-2-methyl-2-propyl alcohol, the 2-ethoxy ethyl amine, the 2-methoxyethyl amine, 3-amino-2,2-dimethyl-1-propyl alcohol, 3-amino-1-propyl alcohol, 1-amino-2-propyl alcohol, 2-ethylaminoethanol etc.

Except that above-mentioned preferred feature, the burnouting property when burning till, the size of viscosity stabilization effect, handle the easiness aspect, preferred especially 2-methoxyethyl amine, 2-(methylamino) ethanol, 2-(2-amino ethoxy) ethanol.

The use level of the amines that uses in the fluorophor paste of the present invention preferably is 0.2～5 weight % in fluorophor paste, more preferably is 0.2～2 weight %, more preferably 0.5～1 weight %.When use level is lower than 0.2 weight %, has the tendency that is difficult to produce the decentralized stabilization effect.In addition, along with the increase of content, the stably dispersing effect improves, and is saturated under certain level, and use level is during greater than 5 weight %, and amines burns incompletely and residual in the firing process, has the easy tendencies such as back fluorescent membrane deterioration in brightness, colourity variation of burning till.

In addition, by the combination of fluorophor powder in the fluorophor paste and adhesive resin, reactions such as acid-base reaction take place sometimes, gelation, the viscosity stability of slurry reduces.Because above-mentioned amines be an alkalescence, can adjust the pH in the fluorophor paste, so, also can suppress unnecessary reaction even be the fluorophor powder for example under acid condition, react and the combination of adhesive resin.Therefore, can suppress the viscosity that the reaction by fluorophor powder and adhesive resin causes rises.

As the fluorophor powder that uses among the present invention, for example, redness can be enumerated Y ₂O ₃: Eu, YVO ₄: Eu, (Y, Gd) BO ₃: Eu, Y ₂O ₃S:Eu, γ-Zn ₃(PO ₄) ₂: Mn, (Zn, Cd) S:Ag+In ₂O ₃, Y (P, V) O ₄: Eu etc.Green can be enumerated Zn ₂GeO ₂: Mn, BaAl ₁₂O ₁₉: Mn, Zn ₂SiO ₄: Mn, LaPO ₄: Tb, ZnS:Cu, Al, ZnS:Au, Cu, Al, (Zn, Cd) S:Cu, Al, Zn ₂SiO ₄: Mn, As, Y ₃Al ₅O ₁₂: Ce, CeMgAl ₁₁O ₁₉: Tb, Gd ₂O ₂S:Tb, Y ₃Al ₅O ₁₂: Tb, ZnO:Zn, (Y, Gd) BO ₃: Tb, (Ba, Sr, Mg) OaAl ₂O ₃Mn etc.Cyan can be enumerated Sr ₅(PO ₄) ₃Cl:Eu, BaMgAl ₁₄O ₂₃: Eu, BaMgAl ₁₆O ₂₇: Eu, BaMg ₂Al ₁₄O ₂₄: Eu, CaMgSi ₂O ₆: Eu, Y ₂SiO ₃: Ce, BaMgAl ₁₀O ₁₇: Eu etc.

In addition, also can use the tantalic acid terres rares fluorophor of using at least a element replacement that is selected from thulium (Tm), terbium (Tb) and the europium (Eu) to be selected from least a parent formation rare earth element in yttrium (Y), gadolinium (Gd) and the lutetium (Lu).Preferred tantalic acid terres rares fluorophor is composition formula Y _1-XEu _XTaO ₄The yttrium tantalate fluorophor of the europium activation of (in the formula, X be about 0.005～0.1) expression.Red-emitting phosphors preferably uses the yttrium tantalate of europium activation, and green-emitting phosphor preferably uses tantalic acid terres rares fluorophor to be composition formula Y _1-XTb _XTaO ₄The yttrium tantalate of the terbium activation of (in the formula, X be about 0.001～0.2) expression.In addition, the cyan fluorophor preferably uses tantalic acid terres rares fluorophor to be Y _1-XTm _XTaO ₄The yttrium tantalate of the thulium activation of (in the formula, X be about 0.001～0.2) expression.

The fluorophor powder preferable particle size of using in the fluorophor paste of the present invention is the fluorophor powder of 0.2～5 μ m, more preferably 1～3 μ m.Particle diameter is during greater than 5 μ m, has fluorophor powder free settling when placing after the slurry manufacturing, the tendency that causes easily producing crawling or brightness disproportionation etc. because of the density of forming, in addition, when powder is meticulous, have fluorophor powder aggegation easily takes place, because surface activation and easily and the tendency of other composition generation chemical reactions such as adhesive etc.Particle diameter is estimated following carrying out: during pulverulence, adopt the particle size distribution meter (for example, Nikkiso Company Limited's system " Microtrac MT3300 ") of laser diffraction formula to estimate.The state of filming or burning till caudacoria is observed by transmission electron microscope (for example, Jeol Ltd.'s system " JEM-4000EX ") and is estimated.Observe in the image at transmission electron microscope, fluorophor powder can be discerned according to the different of contrast with organic principle.Therefore, the transmission electron microscope that for example can be about 10 μ m * 50 μ m by the area of section to film is observed image and is carried out image analysis and estimated.

The specific area of the fluorophor powder that uses in the fluorophor paste of the present invention is preferably 200～1200m ²/ kg, more preferably 300～1000m ²/ kg.By making specific area in this scope, can improve the dispersiveness of fluorophor powder in organic bond resin and organic solvent, obtain the fluorophor paste of coating excellence.In addition, owing to can form fine and close luminescent coating, obtain the high life so can improve luminous efficiency by dispersed raising.Specific area is less than 200m ²During/kg, have fluorophor powder free settling when placing after the luminescent coating that is difficult to form evenly and smoothly desired thickness, the slurry manufacturing, cause easily taking place tendencies such as crawling or brightness disproportionation because of forming density.On the other hand, specific area is greater than 1200m ²During/kg, has the tendency that powder is meticulous, aggegation easily takes place fluorophor powder, cause other composition generation chemical reactions such as easy and adhesive because of surface activation.Need to prove, the mensuration of specific area generally can use Lea-Nurse method, subsieve size apparatus method, Bu Laien (Blaine) method, constant voltage aeration type specific area measuring device etc. to use the method for air transmission beam method, or make the molecule or the ion of powder surface absorption known dimensions, according to the absorption method of the specific area of its quantitative determination powder.

The use level of fluorophor powder is preferably 40～60 weight % in fluorophor paste, more preferably 40～55 weight %.When the use level of fluorophor powder is lower than 40 weight %,, has the tendency that necessary wet coating thickness increases, easily produces the thickness inequality in order to obtain desired thickness.In addition, when particularly in the ditch of striped or cancellate dividing plate figure fluorophor being formed pattern, because wet coating thickness is bigger than dividing plate height, fluorophor paste flows in the ditch of adjacency, so have easy generation colour mixture or the tendency of thickness inequality occurs.On the other hand, when the use level of fluorophor powder is higher than 60 weight %, have the fluorophor powder free settling in the fluorophor paste, or the viscosity of slurry changes easily, the viscosity of slurry tendency such as easily raise.And, because adhesive, the ratio of solvent composition in the slurry reduce relatively, so the thickness inequality easily takes place when having coating, the fillibility of burning till the back fluorescent membrane significantly reduces, the easy tendency such as reduction of brightness.

In addition, in order to make the charging property unanimity of redness, cyan, green fluorophor powder of all kinds, suppress viscosity variation etc., can be with the be covered surface of fluorophor powder of metal oxide.As metal oxide, can enumerate zinc oxide, yittrium oxide, aluminium oxide, bismuth oxide, magnesium oxide etc.

Preferably oxidation or decomposition or gasification when burning till of adhesive resin, carbide does not remain in the inorganic matter, particularly, can preferably use ethyl cellulose, methylcellulose, NC Nitroncellulose, cellulose ethanoate, cellulose propionate, cellulose butylate, hydroxylated cellulose, cellulosic resins such as methyl hydroxylated cellulose, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) isopropyl acrylate, (methyl) acrylic acid 2-ethyl-methyl ester, (methyl) acrylic acid 2-hydroxyethyl ester, the acrylic resin that polymer such as Sodium Polyacrylate or copolymer constitute, polyvinyl butyral resin, polyvinyl acetate, polyvinyl alcohol, polyethylene, silicon polymer (polymethyl siloxane for example, PSI), butadiene/styrene copolymers, polystyrene, PVP, polyamide, high molecular weight polyether, the copolymer of oxirane and expoxy propane, polyacrylamide, poly--α-first sulfone, polybutene etc.In the above-mentioned binder resin, burn till the few luminescent coating aspect of adhesive residue, back from being difficult to take place gelation reaction etc. because of the drawback aspect of adding amines and causing or from forming, preferred cellulose resinoid, particularly preferable methyl cellulose, ethyl cellulose, hydroxylated cellulose, methyl hydroxylated cellulose.In addition, when using acrylic resin, no matter whether add amines, all exist to be difficult to take place the tendency that viscosity changes, compare when using ethyl cellulose resin, have resinous polymer when burning till burnouting property deterioration, be difficult to obtain the tendency of the uniformity etc. of coating film thickness.

In addition, in the cellulosic resin, the solution viscosity when preferably using toluene/ethanol (mixing ratio 80/20) mixed solvent to make 5 weight % solution is the cellulosic resin of 0.004～0.025Pas.When solution viscosity is higher than 0.025Pas, the viscosity increased of fluorophor paste integral body, not preferred from the coating aspect.On the other hand, when solution viscosity was lower than 0.004Pas, in order to obtain the suitable viscosity as fluorophor paste, the amount of essential adhesive resin increased, and was difficult to keep the fluorophor powder necessary among the present invention and the ratio of adhesive resin.Viscosity uses Type B viscosity agent (for example, Brookfield society system, " DV-III ") to estimate.

In addition, the use level of adhesive resin preferably is 5～20 weight %, more preferably 5～15 weight % in fluorophor paste.When the use level of adhesive resin is lower than 5 weight %, the weight ratio that can not keep above-mentioned fluorophor powder and adhesive resin, and can not keep in the fluorophor paste of the present invention necessary fluorophor powder ratio, in addition, have the tendency that the viscosity of slurry becomes too high when being higher than 20 weight %.The use level of adhesive resin hour, burnouting property is good.

In addition, generally speaking,, also can obtain the decentralized stabilization effect sometimes by adding acid compound.But, when using acid compound, the characteristic on fluorophor powder surface make viscosity easily take place through the time change.For example, when exposing alkaline components, can obtain certain decentralized stabilization effect by acid compound when making slurry, but this slurry placement during a couple of days, is carried out gelation, exist viscosity and slurry just to make the different situation in back on the surface of fluorophor powder.Even in these cases, by containing amines of the present invention, also can suppress chemical reactions such as gelation, guarantee viscosity stability.As acid compound, particularly can enumerate aliphatic acid, soap, alkyl sulfate salt, alkylbenzenesulfonate, alkyl sulfo succinate and naphthalene sulfonic acids, polycarboxylic acids macromolecule etc.By making acid compound have the carbon number identical, identical carbochain kind, also can obtain burnouting property and decentralized stabilization effect with the amines that uses in the fluorophor paste of the present invention.Concrete example as above-mentioned acid compound, can enumerate positive enanthic acid, sad, pelargonic acid, n-capric acid, positive dodecoic acid, positive enanthic acid carboxylic acid sodium, n-capric acid carboxylic acid sodium, lauryl sodium sulfate, myristyl sodium sulphate, neopelex, dipropyl sodium sulfosuccinate, dibutyl sodium sulfosuccinate, propyl group sodium naphthalene sulfonate, sodium butylnaphthalenesulfonate, consider low molecular weight material such as preferred positive enanthic acid, sad, positive enanthic acid carboxylic acid sodium from the viewpoint of burnouting property.

When employing promoted the combination of gelation reaction and so on fluorophor powder and adhesive resin by acid compound, there were preferable range in the combination of acid compound and amines and both additions.The present application people found that through concentrating on studies, at above-mentioned particularly preferred amines, N-methoxy ethyl amine or 2-(methylamino) ethanol or 2-(2-amino ethoxy) ethanol, select fatty acid, fatty acid salt or polycarboxylic acids high score subclass material as acid compound, the use level of amines is during more than acid compound, suppress gelation reaction, compare during simultaneously with each compound of use, can guarantee viscosity stability for a long time.

Organic solvent is according to the final viscosity that obtains in the fluorophor paste, or the drying condition of fluorophor paste coated film is suitably selected, particularly can use diethylene glycol single-butyl ether acetic acid esters, ethylene glycol monobutyl ether ethanol, the diethylene glycol single-butyl ether, the triethylene glycol single-butyl ether, glycol monomethyl-2-ethylhexyl ether, diethylene glycol list-2-ethylhexyl ether, 2,2,4-trimethyl-1, the 3-pentanediol mono isobutyrate, 2,2,4-trimethyl-1, the 3-pentanediol diisobutyrate, 2-ethyl-1, the 3-hexylene glycol, methyl ethyl ketone diox, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, terpineol, benzyl alcohol, oxolane, gamma-butyrolacton, propylene carbonate, ethyl lactate, N-methyl pyrrolidone etc. or contain the ORGANIC SOLVENT MIXTURES of more than one above-claimed cpds.Organic solvent is preferably the good solvent of adhesive therefor resin.The dissolubility of the adhesive resin of the volatility of organic solvent and use is mainly considered in the selection of organic solvent.If organic solvent is low to the dissolubility of adhesive resin, even solid state component than identical, also exists the viscosity of coating fluid to raise the tendency that coating characteristics worsens.

In addition, owing to the compatibility of the organic solvent that has hydroxyl in the above-mentioned organic solvent and hydroxyl in the amines or alkoxyl is big, so the easier stably dispersing effect that presents is preferred.And, since dry, burn till in organic solvent wave when loosing easy and amines together wave diffusing, so also can obtain the effect that helps amines to burnout.As the concrete example of organic solvent, can enumerate alcohol compound, isobutanol, isopropyl alcohol, terpineol, benzyl alcohol in the particularly preferred above-mentioned organic solvent with hydroxyl.

The use level of organic solvent is preferably 35～65 weight % in fluorophor paste, more preferably 40～60 weight %.When the use level of organic solvent was lower than 35 weight %, the viscosity with fluorophor paste was too high, the bad bad tendency of flatness that causes coated face of homogenizing.On the other hand, the use level of organic solvent is during greater than 65 weight %, and the sedimentation of dispersed particle is accelerated, and the composition that produces fluorophor paste is difficult to stabilisation, needs problems such as lot of energy and time when dry.

Fluorophor paste of the present invention also can (for example further add antioxidant, defoamer, thickener, plasticizer as required, dibutyl phthalate, dioctyl phthalate, polyethylene glycol etc.) etc., the addition of above-mentioned organic principle is preferably below 3 weight %.Mentioned component disperses residual when burning till sometimes, causes the colourity of light-emitting phosphor to change or deterioration in brightness.

Add photonasty compositions such as photo-sensitive monomer, photonasty oligomer, photosensitive polymer in the fluorophor paste of the present invention, or additive components such as Photoepolymerizationinitiater initiater, sensitizer, antioxidant, ultra-violet absorber, polymerization inhibitor, also can be used as photosensitive fluorophor paste and use.

Fluorophor paste of the present invention cooperates various compositions to be after the composition of regulation, mixes equably by mixing dispersal devices such as 3 rollers mill or mixing rolls and disperses to make.

The present invention also relates to contain and use above-mentioned fluorophor paste to be coated on the manufacturing method of display device of the operation on the substrate.Can enumerate a example as the manufacture method of the plasma scope of display of the present invention.

At first, the manufacture method of the front panel of article on plasma volumetric display is set forth.As substrate, can use soda-lime glass or plasma scope heat resistant glass " PP8 " (NEG society system), " PD200 " (Asahi Glass society system).The size of glass substrate does not have special qualification, can used thickness be the substrate of 1～5mm.

At first, sputter indium-tin-oxide (ITO) on glass substrate forms pattern by photoetching process.Then, process black electrode black electrode slurry.The main component of black electrode slurry is organic bond, black pigment, electroconductive powder and the photonasty composition when being used for photoetching process.As black pigment, preferably use metal oxide.As metal oxide, have titanium black or, the composite oxides of the oxide of copper, iron, manganese or above-mentioned substance, cobalt/cobalt oxide etc., from mix the preferred cobalt/cobalt oxide in few aspect that fades when burning till with glass.As electroconductive powder, can enumerate metal dust or metal oxide powder.Do not have special restriction as metal dust, can use as the normally used gold, silver of electrode material, copper, nickel etc.This black electrode is because resistivity is bigger, so form bus electrode in order to make the little electrode of resistivity, electrode slurry (for example, with silver being the slurry of main component) that can printing conductive is high on the printing surface of black electrode slurry.Then, the bus electrode pattern is made in single exposure/development.In order positively to guarantee conductivity, can be before development the high electrode slurry of printing conductive once more, once develop after the exposure again.Burn till after forming the bus electrode pattern.Afterwards, in order to improve contrast, be preferably formed blackstreak or black matix.Black electrode slurry after burning till and burn till after the thickness of conductive paste respectively preferred in the scope of 1～5 μ m.In addition, the live width after burning till is preferably 20～100 μ m.

Then, use the transparent dielectric slurry to form transparency dielectric layer.Main component in the transparent dielectric slurry is organic bond, organic solvent, glass, also can add suitable additives such as plasticizer.The formation method of transparency dielectric layer does not have special restriction, for example can followingly make, promptly be coated with method, rolling method, metal pattern rubbing method, scraper rubbing method, spin-coating method etc. by silk screen printing, rod, after comprehensive coating or part are coated with the transparent dielectric slurry on electrode formation substrate, adopt any means such as ventilated drying oven, heating plate, infrared drying stove, vacuumize to carry out drying, form thick film.In addition, also the transparent dielectric slurry can be made raw cook, it is layered in electrode form on the substrate.Preferred thickness is 0.01～0.03mm.

Then, in firing furnace, burn till.Burn till atmosphere or temperature according to the kind of slurry or substrate and difference can be burnt till in air or under the atmosphere such as nitrogen, hydrogen.As firing furnace, can use batch-type firing furnace or roller conveyance formula continuous type firing furnace.Firing temperature is the temperature of the abundant unsticking mixture of used resin.Under 430～650 ℃, burn till when usually, using acrylic resin.Firing temperature is crossed when low, and resinous principle is easily residual, and glass substrate deforms and ruptures when too high.

And then, form diaphragm.Preferably use MgO, MgGd as diaphragm ₂O ₄, BaGd ₂O4, Sr _0.6Ca _0.4Gd ₂O ₄, Ba _0.6Sr _0.4Gd ₂O ₄, SiO ₂, TiO ₂, Al ₂O ₃, at least a in the above-mentioned low softening point glass, preferred especially MgO.The manufacture method of diaphragm can be used technique known such as electron beam evaporation plating or ion plating method.

Next, the manufacture method of the rear board of plasma scope is described.Glass substrate is identical with front panel, can use soda-lime glass, " PD200 ", " PP8 ".Pass through metals such as silver or aluminium, chromium, nickel on the glass substrate, form addressing striated electrode pattern.As the formation method, can use following method, promptly by silk screen printing to being that the metal paste of main component carries out the pattern method of printing with above-mentioned metal dust and organic bond, or after the photonasty metal paste of coating usability photosensitiveness organic principle as organic bond, adopt photomask to carry out pattern exposure, remove part not by the developing procedure dissolving, and then heat the photosensitive paste method that forms electrode pattern of burning till down at 350～600 ℃ usually.Can also use etching method, i.e. painting erosion resistant agent after evaporation chromium or the aluminium on glass substrate is removed part not by etching resist being carried out the pattern exposure back of developing.And, dielectric layer preferably is set on addressing electrode.By dielectric layer is set, can improves discharge stability or suppress to be formed on the collapsing or peel off of dividing plate on dielectric layer upper strata.In addition, as the method that forms dielectric layer, have being that the dielectric slurry of main component carries out silk screen printing or adopts slit metal pattern rubbing method etc. to print or the method that is coated with etc. with inorganic constituents such as glass powder or high melting point glass powder and organic bond comprehensively.

Then, the method that forms dividing plate by photoetching process is described.The dividing plate pattern does not have special restriction, but is preferably clathrate, Wa Fuer (Waffle) shape etc.At first, be formed with the dividing plate slurry that coating is made of photosensitive paste of the present invention on dielectric substrate.Coating process can adopt rod to be coated with methods such as method, rolling method, slit metal pattern rubbing method, scraper rubbing method, silk screen printing.Coating thickness depends on the shrinkage of burning till generation of the height and the slurry of desired dividing plate.Coating thickness can be adjusted by coating number of times, the mesh of silk screen, the viscosity of slurry etc.Among the present invention, preferably being coated with and making dried coating thickness is more than the 150 μ m.By making thickness is more than the 150 μ m, can obtain sufficient discharge space, enlarges the coating scope of fluorophor, improves the brightness of plasma scope.

Behind the dividing plate slurry drying of coating, expose.The general method of as photoetching process commonly used, exposing that adopts of exposure by photomask.In addition, also can not use photomask, adopt the method for directly describing with laser etc.As exposure device, can use stepping exposure machine, proximity printing machine etc.The active light source that use this moment for example can be enumerated near ultraviolet ray, ultraviolet ray, electron ray, X ray, laser etc.Wherein most preferably ultraviolet ray as its light source, for example can be used low pressure mercury lamp, high-pressure mercury lamp, ultrahigh pressure mercury lamp, halogen lamp, bactericidal lamp etc.Wherein, preferred ultrahigh pressure mercury lamp.Conditions of exposure is according to coating thickness and difference, and using power output usually is 1～100mW/cm ²Ultrahigh pressure mercury lamp exposure 0.01～30 minute.

After the exposure, utilize exposed portion and non-exposed portion that the poor solubility of developer solution is developed, adopt infusion process or spin-coating method, spread coating etc. usually.Can use the organic solvent that can dissolve the organic principle in the photosensitive paste as developer solution, when having compound in the photosensitive paste, can use alkaline aqueous solution to develop with acidic-groups such as carboxyls.Can use NaOH, sodium carbonate, potassium hydroxide aqueous solution etc. as alkaline aqueous solution, use the scheme of the organic base aqueous solution when burning till, easily to remove alkaline components, so preferred.

As organic base, can use general amines.Particularly can enumerate tetramethylammonium hydroxide, benzyltrimethyl ammonium hydroxide, monoethanolamine, diethanol amine etc.

The concentration of alkaline aqueous solution is generally 0.05～5 quality %, more preferably 0.1～1 quality %.Alkali concn is crossed and is difficult to remove soluble fraction when low, pattern is peeled off or corrodes, so not preferred.In addition, consider that from the operational administrative aspect preferably the development temperature when developing is to carry out under 20～50 ℃.

In addition, dividing plate can be by constituting more than 2 layers.By being the structure more than 2 layers, can on three-dimensional, enlarge the formation scope of partition shape.When for example being 2 layers of structure, the coating ground floor exposes for behind the striated, and the coating second layer exposes to the striated that becomes vertical direction with ground floor, develops, and can form the dividing plate with uneven curb shape structure thus.Then, in firing furnace, under 520～620 ℃ temperature, keep burning till in 10～60 minutes, form dividing plate.

On the dividing plate that is formed as described above, form above-mentioned fluorophor paste pattern.The formation method of fluorophor paste pattern does not have special restriction, for example, can enumerate silk screen print method, from nozzle the ejection fluorophor paste method, form photonasty method of patterning etc. by photoetching process at photonasty resist or fluorophor paste, wherein from nozzle the method, silk screen print method of ejection fluorophor paste owing to can obtain PDP easy, at low cost, so preferably.After forming the fluorophor paste pattern, carry out drying, burn till, form luminescent coating in the side and the bottom of dividing plate.The thickness of fluorophor does not have special restriction, and the center between the adjacent separator pattern is 10～30 μ m with the thickness of dielectric layer surface as zero time, more preferably is 15～25 μ m.Carry out the drying of fluorophor paste for desolventizing or cured resin composition (thermal polymerization by the unsaturated double-bond composition produces heat cross-linking etc.), temperature, time are set according to the boiling point of solvent or the curing temperature of resinous principle etc., are that 80～200 ℃, drying time are to carry out drying under 10～30 minutes the condition in temperature usually preferably.In addition, mainly in order to remove organic principles such as adhesive resin or amines and burn till, characteristic according to the inorganic constituentss such as thermal endurance of organic principle characteristics such as the easy fluidization property of organic principle or easy firing or fluorophor powder is set, usually be 400～550 ℃ in temperature preferably, the time is to burn till under 10～30 minutes the condition.Dry, burn till all and can carry out by the multistage heating mode.When particularly firing temperature is multisection type, be easy to avoid that organic principle burns on the fluorophor surface, the problems such as characteristics of luminescence variation of luminescent coating.From guaranteeing the aspects such as uniformity of luminescent coating thickness, do not cool off after the preferred drying and burn till continuously.

Then, seal above-mentioned rear board and front panel after, limit heating is in the space that 2 plate base compartments form, carry out after the vacuum exhaust on the limit, seals after enclosing the discharge gas that is made of He, Ne, Xe etc.From discharge voltage and brightness two aspects, preferred Xe is the Xe-Ne mist of 5～15 volume %.In order to increase ultraviolet formation efficiency, can further Xe be increased to about 30 volume %.

At last, drive circuit is installed, is carried out etching, make plasma scope thus.

[embodiment]

Next, provide embodiments of the invention and describe, but the present invention is not limited to following embodiment, the concentration among the embodiment (%) is weight %.

Embodiment 1～19

Use following material preparation fluorophor paste.

(A) fluorophor powder

(A-1) cyan fluorophor powder: BaMgAl ₁₀O ₁₇: Eu (hereinafter referred to as BAM), average grain diameter is 2.4 μ m

(A-2) red-emitting phosphors powder: (Y, Gd) BO ₃: Eu (hereinafter referred to as YGB), average grain diameter is 2.3 μ m

(A-3) green-emitting phosphor powder: Zn ₂SiO ₄: Mn (hereinafter referred to as ZSM), average grain diameter is 2.5 μ m

It is (A-4a) surface-coated that average thickness is arranged is the ZSM of the zinc oxide film of 0.2 μ m

It is (A-4b) surface-coated that average thickness is arranged is the ZSM of the yttrium oxide layer of 0.2 μ m

Need to prove, the method of the surface-coated metal oxide of fluorophor in reaching (A-4b) as (A-4a), in the aqueous solution of the chloride of the metal oxide (zinc oxide or yittrium oxide) of needs linings, nitrate etc., add the ZSM powder, after fully stirring drying, under 400 ℃～600 ℃, burn till and form.The thickness of tunicle can be adjusted by the concentration of chloride or nitrate.

(B) dispersant

Amines with amino and hydroxyl and/or alkoxyl

(B-1) 2-(methylamino) ethanol, molecular weight: 75,156 ℃ of boiling points

(B-2) 2-methoxyethyl amine, molecular weight: 88,90 ℃ of boiling points

(B-3) N-ethyl-2-methoxyl group-ethamine, molecular weight: 103,116 ℃ of boiling points

(B-4) triethanolamine, molecular weight: 149,335 ℃ of boiling points

(B-5) three [2-(2-methoxy ethoxy) ethyl] amine, molecular weight: 323,330 ℃ of boiling points

Acid compound

(B-6) positive enanthic acid, molecular weight: 130,223 ℃ of boiling points

The amines of no hydroxyl or alkoxyl

(B-7) N-normal-butyl ethamine, molecular weight: 101,110 ℃ of boiling points

Carboxylic acid amine salt

(B-8) ammonium acetate, molecular weight: 77,112 ℃ of fusing points (boiling point is not clear)

(C) adhesive resin

(C-1) ethyl cellulose resin (ethyoxyl containing ratio 50%)

(D) organic solvent

(D-1) weight ratio of terpineol and ethylene glycol monobutyl ether acetic acid esters is 30/70 mixed solution

Fluorophor powder, dispersant, adhesive resin, each composition of organic solvent are pressed the mixed shown in the table 1, carry out mixingly again with ceramic 3 rollers mills, obtain fluorophor paste.Each composition and the use level of the fluorophor paste of gained are as shown in table 1.

(E) photosensitive silver slurry

Use the following slurry of forming

Silver particles (average grain diameter 1.5 μ m, specific area 0.80m ²/ g): 150 weight portions

The acrylic copolymer resin (acid number 30mgKOH/g, hydroxyl value 410mgKOH/g, weight average molecular weight 12000) that constitutes by 10 quality % acrylic acid, 50 quality % methyl methacrylates, 40 quality % glycerine mono acrylic esters: 12 weight portions

Trimethylolpropane triacrylate (Nippon Kayaku K. K's system, " TPA330 ", 3 functional groups): 6 weight portions

2-benzyl-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1:3 weight portion

Gamma-butyrolacton: 18 weight portions

(F) dielectric slurry

Use the following slurry of forming

Vitrification point is that 475 ℃, softening point are 515 ℃ bismuth class glass: 40 weight portions

Ethyl cellulose resin (ethyoxyl containing ratio 50%): 5 weight portions

Terpineol: 40 weight portions

(G) photosensitive glass paste

Use the following slurry of forming

Vitrification point is that 491 ℃, softening point are 528 ℃ glass powder: 24 weight portions

Vitrification point is 652 ℃ a powder filler: 6 weight portions

The acrylic copolymer resin (acid number 30mgKOH/g, hydroxyl value 410mgKOH/g, weight average molecular weight 12000) that constitutes by 10 quality % acrylic acid, 50 quality % methyl methacrylates, 40 quality % glycerine mono acrylic esters: 7 weight portions

Trimethylolpropane triacrylate (Nippon Kayaku K. K's system, " TPA330 ", 3 functional groups): 3 weight portions

2-benzyl-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1:1.5 weight portion

Urethanes UA-3348PE:(Xin Zhong village chemistry system) 1.5 weight portions

[table 1]

Figure DEST_PATH_G071C6815420070929D000011

Next,, estimate viscosity stability, thickness precision among the embodiment 1～19, and the colourity of fluorophor changes and the relative brightness of fluorophor by following assay method.

1, viscosity stability

Viscosity (η when measuring slurry respectively under the following conditions and just having made ₀) and be the viscosity (η after 20 days under 22～25 ℃ of sealings in temperature ₂₀), be the viscosity rate of change D=(η of benchmark with the viscosity when just making ₂₀-η ₀)/η ₀* 100 (%) are as the index of viscosity stability.

In viscosimetric analysis, viscosimeter uses Brookfield viscometer (Blookefield system, model DV-III), and rotor is SC4-14, and container is 25 ℃ of a small amount of sample adapter (small adapter) (specimen cup 3cc), mensuration temperature, sliding speed 1.2[s ^-1], be 5 minutes from beginning to be measured to the time of reading till the viscosity number.Need to prove that D is preferred more near 0 more, as long as item there is not the problem in the practicality in-2%≤D≤8%, as long as be the scope of 0%≤D≤5%, then viscosity stability is excellent especially, following coating can not take place in 20 days yet worsens even place, so be good.

2, thickness precision

Make rear board according to method as follows.

Use the rear board of glass substrate (Asahi Glass Co., Ltd's system " PD-200 ") formation AC (interchange) the type plasm display panel of 340 * 260 * 2.8mm size.On substrate, use photosensitive silver slurry (E) by photoetching process, forming pitch 140 μ m, live width 60 μ m, burning till back thickness is that the striated electrode of 4 μ m is as writing electrode., burn till under 550 ℃ behind coating dielectric slurry (F) on the substrate by silk screen print method, forming thickness is the dielectric layer of 10 μ m.

And then, use above-mentioned photosensitive glass paste (G) to adopt photoetching process after forming pattern on the dielectric layer, under 570 ℃, burnt till 15 minutes, form the striated dividing plate pattern of pitch 140 μ m, live width 20 μ m, high 100 μ m.On the dividing plate that forms as mentioned above, the fluorophor paste of forming shown in the silk screen printing table 1 in the ditch between the dividing plate pattern.Fluorophor paste is to make the slurry that preserved 10 days the back at slurry under 22～25 ℃ of temperature, air-proof condition.Silk screen uses the silk screen of being furnished with the striated patterns of openings of #200 mesh, pitch 140 μ m, wide 50 μ m.Print.Afterwards, carry out drying (150 ℃, 30 minutes), burn till (500 ℃, 30 minutes), form luminescent coating in the side and the bottom of dividing plate.Coating speed when adjusting silk screen printing, the average film thickness that makes the fluorescent membrane after burning till is 15 ± 0.5 μ m.Cut off glass substrate, expose cross section with the glass substrate vertical direction, by (Hitachi Co., Ltd's system S2400) is observed the cross section, estimates the fluorophor thickness (thickness of phosphor layer of the central portion between adjacent separator) that forms in the bottom of dividing plate inter-drain with scanning electron microscope.

And then, in same rear board, select 20 to measure the fluorophor thickness at random, according to the discrete amplitude of thickness, estimate the precision of thickness as described below.

The maximum of the fluorophor thickness at A:20 place and the difference of minimum value are below the 0.8 μ m

The maximum of the fluorophor thickness at B:20 place and the difference of minimum value are greater than 0.8 μ m and be below the 1.2 μ m

The maximum of the fluorophor thickness at C:20 place and the difference of minimum value are greater than 1.2 μ m and be below the 1.5 μ m

The maximum of the fluorophor thickness at D:20 place and the difference of minimum value are greater than 1.5 μ m

During the bad dispersibility of the fluorophor powder in the fluorophor paste, the thickness deterioration in accuracy.In addition, the use level of fluorophor powder is used for becoming big in the coating film thickness (wet coating thickness) of burning till the necessary thickness of back acquisition after a little while, so the easy variation of thickness precision.

In order to make PDP have uniform display characteristic, the difference that must make maximum and minimum value is below the 1.2 μ m.

3, the colourity of fluorophor variation, relative brightness

Adopting silk screen print method to form average film thickness at (Asahi Glass Co., Ltd's system " PD-200 ") on the glass substrate of 340 * 260 * 2.8mm size in area 200mm * 200mm is the fluorophor paste film of 15 ± 0.5 μ m, carry out drying (150 ℃, 30 minutes) afterwards, burn till (500 ℃, 30 minutes), form luminescent coating.It is 5cm * 5cm that the glass substrate that gained is had a fluorophor cuts into area, be arranged in the vacuum chamber, be set to nitrogen atmosphere in the system and with the vacuum ultraviolet of Excimer lamp (USHIO Electric Co., Ltd system, UER20H-146V) as excitation source illumination wavelength 147nm, use spectrophotometer (Otsuka Electronics Co., Ltd. system, MCPD2000) and brightness instrument (the system LS-100 of Minolta Co., Ltd.) measure colourity, the brightness of the light that luminescent coating sends.Nitrogen atmosphere is by will being decompressed to 9Pa with vacuum pump in the vacuum chamber, be blown into nitrogen afterwards under the pressure of 98.4kPa and realize.Excitation light irradiation is to shine from the last side direction luminescent coating of fluorescent membrane with tilt 15 ° angle of the thickness vertical direction of luminescent coating.The luminous colourity of luminescent coating, brightness detect the luminous of the face vertical upper side shine luminescent coating by take into account the brightness instrument with spectrophotometric, estimate.In addition, when determination object is untreated fluorophor powder, be carved with dark 1mm, area is 30mm

The stainless steel clamps of ditch in powder filler, carry out mensuration same as described above, estimate colourity, brightness.

Colourity, brightness by the fluorescent membrane that will be coated with, burn till are compared with untreated fluorophor powder, estimate the slurry processing, burn till the influence to the characteristics of luminescence.The colourity of fluorophor changes following the evaluation.

The x of A: colourity x, y and untreated fluorophor powder, the variation that y compares are all in ± 0.020

The x of any among B: colourity x, the y and untreated fluorophor powder, the variation that y compares are greater than ± 0.020

In addition, as benchmark, estimate the relative brightness of the fluorescent membrane after burning till with the brightness of untreated fluorophor powder.If relative brightness is more than 95.0%, then the slurry processing is little to the influence of brightness, and is good.

List viscosity variation, colourity variation, thickness precision and relative brightness in the table 2 respectively.

[table 2]

Figure DEST_PATH_G071C6815420070929D000041

Comparative example 1

Except that using N-normal-butyl ethamine (B-7), adopt the method preparation fluorophor paste identical, by the method evaluation rerum natura identical with embodiment 1 with embodiment 3 as the dispersant.The use level of each composition in the fluorophor paste and measurement result are shown in table 3 and table 4.

Comparative example 2

Except that dispersant and organic solvent are the use level shown in the table 2, adopt the method preparation fluorophor paste identical, by the method evaluation rerum natura identical with embodiment 1 with comparative example 1.The use level of each composition in the fluorophor paste and measurement result are shown in table 3 and table 4.

Comparative example 3

Mismatch dispersant, the fluorophor paste of use level shown in the preparation table 2 is estimated rerum natura by the method identical with embodiment 1.The use level of each composition in the fluorophor paste and measurement result are shown in table 3 and table 4.

Comparative example 4

Except that using three [2-(2-methoxy ethoxy) ethyl] amine (B-5), adopt the method preparation fluorophor paste identical, by the method evaluation rerum natura identical with embodiment 1 with embodiment 4 as the dispersant.The use level of each composition in the fluorophor paste and measurement result are shown in table 3 and table 4.

Comparative example 5

Except that using ammonium acetate (B-8), adopt the method evaluation rerum natura identical with embodiment 1 as the dispersant.The use level of each composition in the fluorophor paste and measurement result are shown in table 3 and table 4.

Comparative example 6

Except that using ammonium acetate (B-8), adopt the method evaluation rerum natura identical with embodiment 5 as the dispersant.The use level of each composition in the fluorophor paste and measurement result are shown in table 3 and table 4.

Comparative example 7

Except that using triethanolamine (B-4), adopt the method evaluation rerum natura identical with embodiment 3 as the dispersant.The use level of each composition in the fluorophor paste and measurement result are shown in table 3 and table 4.

[table 3]

Figure DEST_PATH_G071C6815420070929D000061

[table 4]

Figure DEST_PATH_G071C6815420070929D000062

Among the embodiment 1～5, the dispersant use level is that the viscosity variation of the embodiment 3 of 1.0 weight portions and the embodiment 4 that the dispersant use level is 3.0 weight portions is little, coating is also good.Embodiment 5 is because addition is bigger, so the relative brightness of fluorophor reduces to a certain extent.The use level of dispersant is among the embodiment 6,7 of 1.0 weight portions and the kind that changes dispersant, embodiment 6 obtains the result that is more or less the same with embodiment 1, embodiment 7 is owing to using the big dispersant of molecular weight, so the viscosity rate of change increases and the relative brightness of fluorophor reduces.

Embodiment 8～13 is the fluorophor paste that the composition kind is identical, the use level of fluorophor powder is different, wherein, the fluorophor powder sedimentation does not take place in the slurry of the cooperation ratio of embodiment 9 and embodiment 13, burnouting when burning till is also good, and viscosity changes little, also can obtain good result aspect coating.

Among embodiment 14 and the embodiment 15, not only contain 2-(methylamino) ethanol (B-1) but also contain positive enanthic acid (B-6) as dispersant.As implied above, by coexistence acid in fluorophor paste, can make viscosity stability and goodization of thickness precision.

For embodiment 1～15, use cyan fluorophor powder (Ba, Eu) MgAl ₁₀O ₁₇(A-1) preparation fluorophor paste, when using red-emitting phosphors powder (embodiment 16) and green-emitting phosphor powder (embodiment 19), and use fluorophor powder surface-coated have average thickness be the zinc oxide film of 0.2 μ m ZSM, be coated with the embodiment 17,18 o'clock of ZSM that average thickness is the yttrium oxide layer of 0.2 μ m, can obtain dispersion stabilization and coating stability.When particularly using the powder of lining zinc oxide film, yttrium oxide layer, suppress the effective of viscosity variation.

On the other hand, use N-Methylethyl amine that amines do not have hydroxyl or an alkoxyl as the comparative example 1,2 of dispersant and do not conform to the viscosity stability of comparative example 3 of dispersant and the thickness precision all than embodiment difference.

Comparative example 4 is because the use molecular weight is the amines more than 300, so suppress the weak effect that viscosity changes.In addition, because of the colourity that residues in the fluorophor that causes in the film after burning till changes, brightness is reduced in outside the scope of permission.

Comparative example 5 is owing to use the carboxylic acid amine salt compound, so suppress the weak effect that viscosity changes, the thickness precision also reduces to a certain extent.In the comparative example 6, though owing to the addition that increases the carboxylic acid amine salt compound has obtained dispersion effect, colourity changes, brightness changes outside the scope that allows.

In addition, comparative example 7 is owing to the triethanolamine that uses as tertiary amine, so it is insufficient to suppress the effect of viscosity variation.

Claims

1. a fluorophor paste is characterized in that, the molecular weight that described fluorophor paste contains fluorophor powder, adhesive resin, have hydroxyl and/or an alkoxyl is primary amine, and the organic solvent below 300.

2. fluorophor paste as claimed in claim 1, wherein, the boiling point of described amines is 80～350 ℃.

3. fluorophor paste as claimed in claim 1, wherein, the use level of described amines in fluorophor paste is 0.2～5 weight %.

4. fluorophor paste as claimed in claim 2, wherein, the use level of described amines in fluorophor paste is 0.2～5 weight %.

5. as each described fluorophor paste in the claim 1～4, wherein, the use level of described fluorophor powder in fluorophor paste is 40～60 weight %, and the use level of described adhesive resin in fluorophor paste is 5～20 weight %.

6. as each described fluorophor paste in the claim 1～4, wherein, described organic solvent has hydroxyl.

7. fluorophor paste as claimed in claim 5, wherein, described organic solvent has hydroxyl.

8. as each described fluorophor paste in the claim 1～4, wherein, also contain acid compound.

9. fluorophor paste as claimed in claim 5 wherein, also contains acid compound.

10. fluorophor paste as claimed in claim 6 wherein, also contains acid compound.

11. fluorophor paste as claimed in claim 7 wherein, also contains acid compound.

Be coated with each described fluorophor paste in the claim 1～11 on the substrate 12. the manufacture method of a display, described manufacture method are included in, burn till, form the operation of luminescent coating thus.