CN1243355C - Insulating slurry for manufacturing insulating layer of vacuum fluorescent display, and preparation method thereof - Google Patents

Insulating slurry for manufacturing insulating layer of vacuum fluorescent display, and preparation method thereof Download PDF

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Publication number
CN1243355C
CN1243355C CN 03104723 CN03104723A CN1243355C CN 1243355 C CN1243355 C CN 1243355C CN 03104723 CN03104723 CN 03104723 CN 03104723 A CN03104723 A CN 03104723A CN 1243355 C CN1243355 C CN 1243355C
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slurry
insulating barrier
fluorescent display
vacuum fluorescent
organic carrier
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CN1525493A (en
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罗世永
吕艳英
孙正海
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BOE Technology Group Co Ltd
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BOE Technology Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
    • C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
    • C03C3/074—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron containing zinc
    • C03C3/0745—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron containing zinc containing more than 50% lead oxide, by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip

Abstract

The present invention relates to an insulating slurry for manufacturing insulating layer of a vacuum fluorescent display, and the present invention also relates to a method for preparation thereof. The present invention comprises insulating vitreous power, an organic carrier and high temperature inorganic black paint. The insulating vitreous power is evenly dispersed in the organic carrier, the organic carrier is liquor formed by dissolving resin in organic solvent, and paste-shaped compositions are formed by adding the high temperature inorganic black paint. The present invention has the preparation method that evenly mixing the vitreous power and the black paint according to the variety and the occupied weight percentage of the black paint; finely grinding the obtained mixtures to the power of which the average particle diameter is less than 5 mu m, and the particle diameter of the largest particle is smaller than or equal to 10 mu m; evenly mixing the mixtures of the vitreous power and the black paint and the organic carrier in a slurry blender; finally, grinding and dispersing obtained mixing slurry on a three-roll grinder until the fineness is less than 15 mu m. By using the insulating layer manufactured by the present invention, the present invention has the advantages of favorable graphics resolution, macroscopy, no pinpricks, no microcracks, glossy black glass and high insulating electric intensity.

Description

Be used for insulation paste of vacuum fluorescent display insulating barrier making and preparation method thereof
Technical field
The present invention relates to a kind of electronic isolation slurry, the especially a kind of insulation paste of vacuum fluorescent display insulating barrier making and preparation method of this insulation paste of being used for belongs to chemical technology field.
Background technology
Vacuum fluorescent display (VFD) is a kind of self-luminous flat-panel monitor of the sixties in 20th century invention, has characteristics such as brightness height, visual angle are wide, anti-environment, is widely used in household electrical appliance, commercial appliance, automobile and industrial instrumentation instrument etc.During making, electronic circuit is printed on the plate glass, needs by silk screen printing electronic isolation pulp layer in the middle of the multilayer circuit or between circuit and the electronic device, behind sintering, form the insulating barrier between the conductive layer and conductive layer in the vacuum fluorescent display.
The related data record, Japanese patent laid-open 9-218508 proposes a kind of photosensitive glass slip material that can be used for making plasma display (PDP) next door, the compound that this patent adopts bismuth-containing or plumbous low-melting glass, photonasty organic principle and has the pyridine structure form slurry of mixing.Japanese patent laid-open 6-144871 proposes a kind of photosensitive pulp that is applicable to that the sensitization implantation is used.Japanese patent laid-open 9-295830 proposes a kind of sensitization implantation that is applicable to and makes the thermosetting frit slurry in PDP next door.Japanese patent laid-open 8-119665 proposes a kind of glass paste, is used for the dielectric thick film of PDP back substrate.U.S. Pat P4547467 proposes a kind of crown glass slurry, wherein SiO 214-26%, ZnO 34-46%, B 2O 315-25%, Al 2O 31-6%, K 2O 0-6%, Na 2O 2-10%, CaO 1-5%, Li 2O 0-2%, firing temperature are lower than 580 ℃, are used to make the insulating medium layer on the PDP metacoxal plate.These slurries that are used for PDP all are aimed at the specific glass substrate P D200 that PDP adopts and design, and can not be applicable to VFD.
Japanese patent laid-open 7-25568 proposes to be used for the PbO-SiO of PDP and VFD dielectric layer 2Be frit slurry, its frit consists of PbO-SiO 2-Al 2O 3-TiO 2-BaO-CeO 2-La 2O 3System, its coefficient of expansion is about 8.5 * 10 -61/ ℃.Its sintering temperature is 580-620 ℃.Close with the present invention, but its coefficient of expansion is bigger, can not mate with the ordinary plate glass substrate, and contain the rare earth oxide of compositions such as Ce and La, cost height in its glass composition.
High voltage withstanding glass dust among the Japanese patent laid-open 11-246236 is formed with the present invention similar.But its ZnO content is higher, and the organic carrier part is not quite clear.Japanese patent laid-open 10-338544 has reported a kind of crystal type insulation paste at 850-900 ℃ of sintering.Japanese patent laid-open 11-209147 has reported that weight ratio is PbO 65%, B 2O 35%, SiO 225%, the glass paste of CaO 5%, but its organic carrier part is not quite clear.These slurries are mainly used in and make insulating barrier in the multilayer ceramic capacitor.
In existing insulation paste patent, majority is the special sizing agent of using at PDP, and the insulation paste close with patent of the present invention is mainly used in multilayer ceramic capacitor.The coefficient of expansion and ordinary plate glass coupling behind the VFD requirement insulation paste sintering have the electrical strength height under the prerequisite of insulating barrier thin (40-60 μ m) behind the sintering, and leakage current is little, and mechanical strength and chemical stability are good.Require the rheological property of slurry can satisfy the silk screen printing requirement simultaneously, flowability after glass softens when the flowability of printing disposed slurry and sintering is suitable, it is excessive or stop up and reserve micro-through-hole that mobile very good meeting causes reserving on the insulating barrier clear size of opening degree that diminishes, and flowability is too poor then to be easy to form behind the sintering critical defect such as fine pin hole.Do not find to be exclusively used in insulation paste patent and other bibliographical information of VFD at present as yet.
Summary of the invention
The objective of the invention is to provide a kind of insulation paste that the vacuum fluorescent display insulating barrier makes and preparation method thereof that is used at the deficiency of prior art, insulating barrier in the making vacuum fluorescent display between conductive layer and conductive layer has the advantages that processing performance is good, dielectric strength is high.
For this reason, the invention provides following technical scheme and realize above-mentioned purpose:
A kind of insulation paste that is used for the making of vacuum fluorescent display insulating barrier, its insulation paste mainly is made up of nature of glass powder, inorganic pigment and organic carrier three parts.This insulating glass matter powder is dispersed in the organic carrier, organic carrier is for to be dissolved in the solution that organic solvent forms by resin, and add the inorganic mineral black of high temperature, form a kind of paste composition, the coefficient of expansion of the insulating barrier that the 40-60 μ m that forms behind the insulation paste sintering of use is thick is (7.2 ± 0.3) * 10 -61/ ℃.Wherein the resin in the organic carrier is ethyl cellulose or nitrocellulose, and organic solvent is terpinol, diethylene glycol butyl ether, diethylene glycol ether, diethylene glycol monobutyl ether acetate, diethyl phthalate, butyl carbinol, glycerol, N-N-methyl-2-2-pyrrolidone N-or its mixture; The mass percent that resin occupies airborne body gross mass is 3-10%.
Insulating glass matter powder is formed and percentage by weight mainly comprises: PbO 50-75%, B 2O 30-20%, SiO 25-30%, Al 2O 30.5-10%, ZnO 0.5-5%, CaO 0.5-5%, each oxide aggregate are 100%.Simultaneously, can also add or not add Bi 2O 3, TiO 2, ZrO 2, BaO, MgO, SnO 2One of or any frit commonly used of composition combination wherein.
As levelling agent and/or the defoamer and/or the anti-settling agent of auxiliary agent, auxiliary agent is 5% weight portion of organic carrier in the organic carrier solution, and in the mixed aid of these materials, the weight portion of each composition is 0-2%.
For improving dispersiveness, in organic carrier, add the powder dispersant of hyper-dispersant, the mass percent that dispersant occupies airborne body gross mass is 0.5-6%; The concrete composition of dispersant can be the mixture of the block copolymer hyper-dispersant of oxirane expoxy propane or this hyper-dispersant and hydrogenation castor oil, soybean lecithin.
In above-mentioned organic carrier, can also further add and occupy airborne body weight percentage the tetraethoxysilane that is 1-6%; Its objective is by the silicon alkoxide network that half hydrolysis or complete hydrolysis form partial cross-linking in air, can improve the printed pattern resolution of slurry, and when the slurry sintering, resolve into SiO 2Nano powder can improve the sintering character of slurry and the insulation property of insulating barrier.
On the other hand, to be preferably Co-Fe-Cr-Ni be that Co-Fe-Cr-Mn is the inorganic mineral black of high temperature for painted mineral black.
The present invention also comprises a kind of as the application of above-mentioned slurry in vacuum fluorescent display.
The present invention also comprises a kind of preparation method of as above-mentioned slurry, specifically comprises following preparation process:
At first, kind and shared percentage by weight according to mineral black evenly mix nature of glass powder and mineral black;
Secondly, the said mixture that obtains is finely ground to the powder average grain diameter less than 5 μ m, the largest particles particle diameter is not more than 10 μ m;
Then, in the slurry mixer, the mixture and the organic carrier of glass dust mineral black evenly mixed;
At last, the mixed slurry that obtains is ground on three-roll grinder be dispersed to fineness less than 15 μ m.
According to technical scheme of the present invention as can be known: insulation paste of the present invention is used for making the insulating barrier between vacuum fluorescent display conductive layer and conductive layer.Have the advantages that processing performance is good, dielectric strength is high.
In above-mentioned prescription, introduce ZnO, when having improved the slurry sintering to the wetability of glass substrate; By introducing Al 2O 3The insulation electrical intensity and the chemical stability of insulating barrier have been improved; Temperature-viscosity variation characteristic after glass softens when having changed the slurry sintering by introducing CaO, the insulating barrier that makes making is no pin-hole defect both, be unlikely to because of the reservation micro-through-hole on the mobile excessive obstruction insulating barrier of glass after softening again or make the preformed hole change in size excessive, promptly the slurry graphics resolution is good.
Organic carrier among the present invention is the volatilization of completing combustion below 400 ℃ in the slurry sintering process, and the organic component residual quantity is little; Glass dust and pigment can evenly disperse in organic carrier, and it is not stratified that slurry can be stablized within a certain period of time, and viscosity changes little; This organic carrier is also given slurry rheological characteristic preferably, has satisfied and has made the requirement of vacuum fluorescent display to the slurry rheological characteristic, makes the rheological property of slurry can satisfy that silk screen printing requires and suitable, i.e. the printed pattern good resolution of slurry.The composition of organic carrier has guaranteed that the powder fineness of dispersion of product insulation paste of the present invention is less than 15 μ m.
The block copolymer of the hyper-dispersant oxirane expoxy propane among the present invention, form the adsorbing anchoring group of anchoring at inorganic powder surface, make inorganic particulate form the sufficiently long polymer solvent chain of stabilisation by steric effect, form affinity interaction with organic carrier, the net ability of crossing when having guaranteed the fineness of dispersion of slurry and silk screen printing.Micron and the even dispersion of submicro inorganic powder in organic carrier have been guaranteed; The hyper-dispersant that adds keeps the state and the flocculation of particle is suppressed by reducing interparticle collision efficient of being separated by of dispersed particle physically, this has increased stability of slurry, reduced the fineness of dispersion of inorganic particle in organic carrier, simultaneously can reduce drying time, improve the rate of heat addition, the shortening heat processing time, increase bonding or the like between sinter layer and substrate.
Add hyper-dispersant and suppressed the reunion of submicron powder in the slurry, thereby improved the uniformity of slurry, improved rheological property and thixotropic property, make size performance satisfy the technological requirement of silk screen printing and vacuum fluorescent display making.
Embodiment
Insulation paste of the present invention mainly comprises nature of glass powder, inorganic pigment and organic carrier three parts composition.Wherein organic carrier is the resin solubilizer,
Nature of glass powder is: with PbO, the B of technical grade 2O 3, SiO 2, Al 2O 3, ZnO, CaCO 3By the component design weighing, evenly be mixed and made into batch, fusing clarification in about 1350 ℃ is dried after the melt shrend in platinum crucible Deng raw material, and it is standby to cross 100 mesh sieves after the coarse crushing.
Preferred insulating glass system is PbO-B 2O 3-SiO 2Introduce the firing temperature that PbO reduces slurry; B 2O 3And SiO 2Be glass former, improve simultaneously insulating barrier behind the sintering thermal stability and and sintering process in the temperature-viscosity characteristics of glass after softening; Introduce Al 2O 3Improve the chemical stability and the insulation electrical intensity of insulating barrier; Introduce ZnO and improve the wetability of the softening back of glass, introduce CaO and regulate PbO-B glass substrate 2O 3-SiO 2Temperature-viscosity characteristics after system glass is softening.The thermal coefficient of expansion of insulating barrier meets the requirements of under the prerequisite PbO, B after guaranteeing sintering simultaneously 2O 3, SiO 2, Al 2O 3Relative amount can fluctuate within the specific limits, simultaneously can also add or not add Bi 2O 3, TiO 2, ZrO 2, BaO, MgO, SnO 2Etc. frit commonly used.Be finely ground to the powder average grain diameter less than 5 μ m, the largest particles particle diameter is not more than 10 μ m.
When in nature of glass powder, introducing ZnO and improving the slurry sintering to the wetability of glass substrate; Introduce Al 2O 3Improve the insulation electrical intensity and the chemical stability of insulating barrier; Temperature-viscosity variation characteristic after glass softens when introducing CaO adjusting slurry sintering, the insulating barrier that makes making is no pin-hole defect both, is unlikely to because of the reservation micro-through-hole on the mobile excessive obstruction insulating barrier of glass after softening again or makes the preformed hole change in size excessive.
Organic carrier is a kind of mixture, promptly is made up of such as optional ingredients such as anti-settling agent, levelling agent, defoamers the resinae polymer that plays thickening power, solvent and other.Organic carrier among the present invention requires to satisfy following the requirement:
The volatilization of completing combustion below 400 ℃ in the slurry sintering process, the organic component residual quantity is little.
Glass dust and pigment can evenly disperse in organic carrier, and it is not stratified that slurry can be stablized within a certain period of time, and viscosity changes little.
Give slurry rheological characteristic preferably, satisfy and make the requirement of vacuum fluorescent display the slurry rheological characteristic.Require the rheological property of slurry can satisfy the silk screen printing requirement, the flowability of printing disposed slurry is suitable, mobile very good meeting causes reserving on the insulating barrier clear size of opening and diminishes or stop up, flowability is too poor then to be easy to form critical defect such as fine pin hole, i.e. the printed pattern good resolution of slurry behind sintering.
The resinae polymer can be ethyl cellulose, acrylic polymer, nitrocellulose, hydroxyethylcellulose among the present invention.Organic solvent both can be single terpinol, diethylene glycol butyl ether, diethylene glycol ether, diethylene glycol monobutyl ether acetate, diethyl phthalate, butyl carbinol, glycerol, N-N-methyl-2-2-pyrrolidone N-etc., also can be their mixture.Wherein to occupy the mass percent of airborne body gross mass be 3-10% to resin.Add the mixture of the block copolymer of hyper-dispersant oxirane expoxy propane or itself and common dispersants simultaneously, the mass percent that dispersant occupies airborne body gross mass is 0.5-6%.Can add in the organic carrier or do not add auxiliary agents such as levelling agent, defoamer, anti-settling agent.
The block copolymer that has added hyper-dispersant oxirane expoxy propane among the present invention has guaranteed micron and the even dispersion of submicro inorganic powder in organic carrier.The size average grain particle diameter of glass and inorganic pigment is less than 5 μ m in the slurry, and the individual particle maximum particle diameter is no more than 10 μ m.The surface energy height of general glass and inorganic mineral black, poor with the organic carrier affinity that surface energy is low, and lead glass density is big, if dispersant kind and consumption are improper, then slurry is easy to layering or inorganic particle and is easy to reunite and lost efficacy for second particle causes slurry.Add hyper-dispersant, form the adsorbing anchoring group of anchoring at inorganic powder surface, make inorganic particulate form the sufficiently long polymer solvent chain of stabilisation, form affinity interaction, the net ability of crossing when having guaranteed the fineness of dispersion of slurry and silk screen printing with organic carrier by steric effect.The hyper-dispersant that adds keeps the state and the flocculation of particle is suppressed by reducing interparticle collision efficient of being separated by of dispersed particle physically, this has increased stability of slurry, simultaneously can reduce drying time, improves the rate of heat addition, the shortening heat processing time, increase bonding or the like between sinter layer and substrate.
As the surfactant of hyper-dispersant, aliphatic amine, β-N-alkylamino propionic acid of block copolymer, the ethyoxyl of sodium salt, the oxirane expoxy propane of the octyl phenol of ethyoxyl sulfateization etc. are arranged.The mixture of the block copolymer of optimization ethylene oxide expoxy propane of the present invention or itself and common dispersants hydrogenation castor oil and soybean lecithin.
The organic carrier composition has guaranteed that the powder fineness of dispersion of product insulation paste of the present invention is less than 15 μ m.
The silicon alkoxide that the present invention adds in organic carrier and occupies airborne body weight percentage is 1-6%.Its objective is that silicon alkoxide half hydrolysis or complete hydrolysis in air form the network of partial cross-linking, improve the printed pattern resolution of slurry; And when the slurry sintering, resolve into SiO 2Nano powder improves the sintering character of slurry and the insulation property of insulating barrier.The silicon alkoxide that uses is tetraethoxysilane.In like manner, also can optionally add other metallo-organic compounds such as titanium alkoxide Ti (OC 4H 9) 4, butyl borate B (OC 4H 9) 3, Al (OCH 3) 3, Zr (OC 3H 7) 4Deng, when the slurry sintering, decomposite corresponding nano-oxide.
Colouring agent in the insulation paste of the present invention can use all inorganic mineral blacks in principle.Preferred Co-Fe-Cr-Ni is that Co-Fe-Cr-Mn is the inorganic mineral black of high temperature.It is standby that commercial mineral black is crossed 100 mesh sieves.
Prepare above-mentioned slurry, can be specifically according to the kind difference of mineral black, the shared percentage by weight difference of mineral black (being generally 5-18%).After nature of glass powder and mineral black evenly mixed by preset proportion, be finely ground to the powder average grain diameter less than 5 μ m, the largest particles particle diameter is not more than 10 μ m; Mixture and organic carrier with the glass dust mineral black in the slurry mixer evenly mix, and wherein to account for the percetage by weight of slurry total amount be 8-25% to organic carrier, grind on three-roll grinder then and are dispersed to fineness less than 15 μ m.
Below be application example in conjunction with concrete prescription, preparation process and use slurry:
Embodiment 1
Glass formula is PbO 55%, B 2O 315.5%, SiO 220%, Al 2O 33.5%, ZnO 4.0%, and CaO 2.0%.
After each oxide is prepared into glass dust by preceding method, adds percentage by weight and be after 12% Co-Fe-Cr-Ni is mineral black, be finely ground to the powder average grain diameter less than 5 μ m, the largest particles particle diameter is not more than 10 μ m.
Organic carrier is filled a prescription by weight percentage and is: ethyl cellulose 7%, and terpinol 84%, hyper-dispersant 2%, rilanit special 2%, tetraethoxysilane 2%, auxiliary agent 3% mixes.
Mix after above-mentioned powder and organic carrier be respectively 80%, 20% batching by weight percentage, rolling is dispersed to fineness and is finished product less than 15 μ m on three-roll grinder then.
The slurry of preparation is pressed the vacuum fluorescent display manufacturing condition with method for printing screen make insulating barrier on ordinary plate glass, sintering temperature is 600 ℃, and sintering time is 10 minutes.
Embodiment 2
Glass formula is PbO 64%, SiO 227%, Al 2O 34.0%, ZnO 3.0%, and CaO 2.0%.
After each oxide is prepared into glass dust by preceding method, adds percentage by weight and be after 18% Co-Fe-Cr-Mn is mineral black, be finely ground to the powder average grain diameter less than 5 μ m, the largest particles particle diameter is not more than 10 μ m.
Organic carrier is filled a prescription by weight percentage and is: nitrocellulose 15%, and terpinol 50%, diethylene glycol butyl ether 22%, dibutyl phthalate 5%, the block copolymer 5% of hyper-dispersant oxirane expoxy propane, tetraethoxysilane 3% mixes.
Mix after powder and organic carrier be respectively 85%, 15% batching by weight percentage, rolling is dispersed to fineness and is finished product less than 15 μ m on three-roll grinder then.
The slurry of preparation is pressed the vacuum fluorescent display manufacturing condition with method for printing screen make insulating barrier on ordinary plate glass, sintering temperature is 580 ℃, and sintering time is 15 minutes.
Embodiment 3
Glass formula is PbO 63%, B 2O 35%, SiO 220%, Al 2O 34.0%, ZnO 2.0%, and CaO 1.0%, Bi 2O 31.0%, ZrO 22%, MgO 2%.
After each oxide is prepared into glass dust by preceding method, adds percentage by weight and be after 8% Co-Fe-Cr-Ni is mineral black, be finely ground to the powder average grain diameter less than 5 μ m, the largest particles particle diameter is not more than 10 μ m.
Organic carrier is filled a prescription by weight percentage and is: polyacrylic resin 4%, ethyl cellulose 5%, diethylene glycol monobutyl ether acetate 25%, diethyl phthalate 30%, butyl acetate 25%, the block copolymer 5% of hyper-dispersant oxirane expoxy propane, tetraethoxysilane 1%, auxiliary agent 5% mixes.
Mix after powder and organic carrier be respectively 83%, 17% batching by weight percentage, rolling is dispersed to fineness and is finished product less than 15 μ m on three-roll grinder then.
The slurry of preparation is pressed the vacuum fluorescent display manufacturing condition with method for printing screen make insulating barrier on ordinary plate glass, sintering temperature is 590 ℃, and sintering time is 13 minutes.
Embodiment 4
Glass formula is PbO 66%, B 2O 32%, SiO 220%, Al 2O 38.0%, BaO 1%, and ZnO 1.0%, and CaO 0.5%, TiO 21.5%.
After each oxide is prepared into glass dust by preceding method, adds percentage by weight and be after 14% Co-Fe-Cr-Mn is mineral black, be finely ground to the powder average grain diameter less than 5 μ m, the largest particles particle diameter is not more than 10 μ m.
Organic carrier is filled a prescription by weight percentage and is: hydroxyethylcellulose 7%, terpinol 30%, diethylene glycol monobutyl ether acetate 25%, dibutyl phthalate 30%, the block copolymer 2% of hyper-dispersant oxirane expoxy propane, hydrogen flower castor oil 2%, soybean lecithin 2%, tetraethoxysilane 2% mixes.
Mix after powder and organic carrier be respectively 85%, 15% batching by weight percentage, rolling is dispersed to fineness and is finished product less than 15 μ m on three-roll grinder then.
The slurry of preparation is pressed the vacuum fluorescent display manufacturing condition with method for printing screen make insulating barrier on ordinary plate glass, sintering temperature is 590 ℃, and sintering time is 12 minutes.
Embodiment 5
Glass formula is PbO 55%, B 2O 313%, SiO 215%, Al 2O 36.0%, ZnO 5.0%, and CaO 3.0%, Bi 2O 33%.
After each oxide is prepared into glass dust by preceding method, adds percentage by weight and be after 15% Co-Fe-Cr-Ni is mineral black, be finely ground to the powder average grain diameter less than 5 μ m, the largest particles particle diameter is not more than 10 μ m.
Organic carrier is filled a prescription by weight percentage and is: polymethacrylates 5%, terpinol 10%, diethylene glycol ether 40%, diethylene glycol monobutyl ether acetate 25% dibutyl phthalate 10%, the block copolymer 6% of hyper-dispersant oxirane expoxy propane, tetraethoxysilane 4% mixes.
Mix after powder and organic carrier be respectively 81%, 19% batching by weight percentage, rolling is dispersed to fineness and is finished product less than 15 μ m on three-roll grinder then.
The slurry of preparation is pressed the vacuum fluorescent display manufacturing condition with method for printing screen make insulating barrier on ordinary plate glass, sintering temperature is 595 ℃, and sintering time is 10 minutes.
Embodiment 6
Glass formula is PbO 65%, B 2O 33%, SiO 225%, Al 2O 31.0%, ZnO 3.5%, and CaO 0.5%, SnO 22%.After each oxide is prepared into glass dust by preceding method, adds percentage by weight and be after 12% Co-Fe-Cr-Mn is mineral black, be finely ground to the powder average grain diameter less than 5 μ m, the largest particles particle diameter is not more than 10 μ m.
Organic carrier is filled a prescription by weight percentage and is: ethyl cellulose 5%, N-N-methyl-2-2-pyrrolidone N-4%, diethyl carbitol 60%, diethyl carbitol acetate 20%, the block copolymer 5% of dispersant oxirane expoxy propane, tetraethoxysilane 2%, auxiliary agent 4% mixes.
Mix after powder and organic carrier be respectively 84%, 16% batching by weight percentage, rolling is dispersed to fineness and is finished product less than 15 μ m on three-roll grinder then.
The slurry of preparation is pressed the vacuum fluorescent display manufacturing condition with method for printing screen make insulating barrier on ordinary plate glass, sintering temperature is 600 ℃, and sintering time is 10 minutes.
Good, the macroscopical free of pinholes of insulating barrier graphics resolution, micro-crack, black glass gloss, insulation electrical intensity height by the various embodiments described above making.

Claims (15)

1, a kind of insulation paste that is used for the making of vacuum fluorescent display insulating barrier, it comprises insulating glass matter powder, organic carrier and the inorganic mineral black of high temperature, this insulating glass matter powder comprises PbO, SiO at least 2, Al 2O 3, ZnO and CaO are dispersed in this insulating glass matter powder in the organic carrier, and organic carrier is for to be dissolved in the solution that organic solvent forms by resin, and the inorganic mineral black of interpolation high temperature, forms paste composition.
2, the insulation paste that is used for the making of vacuum fluorescent display insulating barrier as claimed in claim 1, wherein, insulating glass matter powder is formed and percentage by weight comprises at least: PbO 50-75%, B 2O 30-20%, SiO 25-30%, Al 2O 30.5-10%, ZnO 0.5-5%, CaO 0.5-5%, each oxide aggregate are 100%.
3, the insulation paste that is used for the making of vacuum fluorescent display insulating barrier as claimed in claim 2 wherein, also adds Bi in the insulating glass matter powder 2O 3, TiO 2, ZrO 2, BaO, MgO, SnO 2One of or the wherein arbitrarily combination of composition, and each oxide weight total amount is 100%.
4, as claim 1 or the 2 or 3 described insulation pastes that are used for the making of vacuum fluorescent display insulating barrier, wherein, insulating glass matter powder is finely ground to the powder average grain diameter less than 5 μ m, and the largest particles particle diameter is not more than 10 μ m.
5, the insulation paste that is used for the making of vacuum fluorescent display insulating barrier as claimed in claim 1, wherein, the percetage by weight that organic carrier accounts for the slurry total amount is 8-25%, comprises resin, dispersant and organic solvent at least; Wherein, the mass percent that resin occupies airborne body gross mass is 3-10%, and the mass percent that dispersant occupies airborne body gross mass is 0.5-6%.
6, the insulation oar material that is used for the making of vacuum fluorescent display insulating barrier as claimed in claim 5, wherein, resin is that ethyl cellulose or nitrated fine heap are plain.
7, the insulation paste that is used for the making of vacuum fluorescent display insulating barrier as claimed in claim 5, wherein, dispersant is aliphatic amine, the β-N-alkylamino propionic acid of sodium salt, the ethyoxyl of the octyl phenol of ethyoxyl sulfateization, the block copolymer of oxirane expoxy propane, or the mixture of this copolymer and rilanit special, soybean lecithin.
8, the insulation paste that is used for the making of vacuum fluorescent display insulating barrier as claimed in claim 5, this organic solvent is a kind of or its mixture in terpinol, diethylene glycol butyl ether, diethylene glycol ether, diethylene glycol monobutyl ether acetate, diethyl phthalate, butyl carbinol, glycerol, the N-N-methyl-2-2-pyrrolidone N-.
9, as claim 1 or 5 or 6 or the 7 or 8 described insulation pastes that are used for the making of vacuum fluorescent display insulating barrier, wherein, also further be added with levelling agent and/or defoamer and/or anti-settling agent as auxiliary agent in the organic carrier, auxiliary agent is 5% weight portion of organic carrier.
10, the insulation slurry section that is used for the making of vacuum fluorescent display insulating barrier as claimed in claim 9, wherein, in the mixed aid of levelling agent or defoamer or anti-settling agent, the weight portion of each auxiliary agent is 0-2%.
11, as claim 1 or 5 or 6 or the 7 or 8 described insulation pastes that are used for the making of vacuum fluorescent display insulating barrier, wherein, also further be added with tetraethoxysilane or titanium alkoxide Ti (OC in the organic carrier 4H 9) 4Or butyl borate B (OC 4H 9) 3Or Al (OCH 3) 3Or Zr (OC 3H 7) 4, wherein to occupy airborne body weight percentage be 1-6% to metallo-organic compound; And be used for when air half hydrolysis or complete hydrolysis, forming the network of partial cross-linking, improve the printed pattern resolution of slurry, and when the slurry sintering, resolve into the nano powder of corresponding oxide, improve the sintering character of slurry and the insulation property of insulating barrier.
12, the insulation paste that is used for the making of vacuum fluorescent display insulating barrier as claimed in claim 1, wherein, mineral black is that Co-Fe-Cr-Ni system or Co-Fe-Cr-Mn are the inorganic mineral black of high temperature.
13, the insulation paste of being confused as claim 1 that is used for the making of vacuum fluorescent display insulating barrier, wherein, the coefficient of expansion of the insulating barrier that the 40-60 μ m that forms behind the insulation oar material sintering of use is thick is (7.2 ± 0.3) * 10 -61/ ℃.
14, a kind of as described slurry of above-mentioned arbitrary claim is printed on the application on the vacuum fluorescent display glassy layer.
15, a kind of method for preparing the described arbitrary insulation paste of claim 1-13, at first, kind and shared percentage by weight according to mineral black evenly mix nature of glass powder and mineral black; Secondly, the nature of glass powder of acquisition and the mixture of mineral black are finely ground to the powder average grain diameter less than 5 μ m, the largest particles particle diameter is not worked energetically 10 μ m; Then, in the slurry mixer, the mixture and the organic carrier of glass dust mineral black evenly mixed; At last, the mixed slurry that obtains is ground on three-roll grinder be dispersed to fineness less than 15 μ m.
CN 03104723 2003-02-27 2003-02-27 Insulating slurry for manufacturing insulating layer of vacuum fluorescent display, and preparation method thereof Expired - Lifetime CN1243355C (en)

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CN101794639B (en) * 2010-03-16 2011-10-05 彩虹集团公司 Environment-friendly glass frit and preparation method thereof
CN102347093A (en) * 2011-07-19 2012-02-08 彩虹集团公司 Inorganic adhesive for silicon-based solar cell front silver paste and preparation method thereof
CN106686767A (en) * 2015-11-05 2017-05-17 中山市乾元高科电子有限公司 Processing technology of micro-crystal glass heater
CN115132402B (en) * 2022-06-30 2023-11-28 上海匠聚新材料有限公司 Glass paste for chip resistor and preparation method thereof
CN114933414B (en) * 2022-07-25 2022-11-08 西安宏星电子浆料科技股份有限公司 Temperature sensitivity resistant LTCC insulating medium slurry

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