CN103922596B - Glass frit compositions, frit paste composition, electrical element sealing method and electrical element - Google Patents
Glass frit compositions, frit paste composition, electrical element sealing method and electrical element Download PDFInfo
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Abstract
The invention discloses a kind of glass frit compositions for electrical element sealing, glass frit compositions is by mole% comprising: Bi
2o
320%-45%; SiO
210%-35%; ZnO5%-35%; CuO5%-20%; Al
2o
35%-15%; MnO
21%-15%; Fe
2o
31%-5%; BaO0.1%-5%; TiO
20.1%-5%; WO
30.1%-5%.Present invention also offers a kind of frit paste composition, electrical element sealing method and electrical element.Glass frit compositions of the present invention, frit paste composition, electrical element sealing method and electrical element; reduce glass transition temp and softening temperature; demonstrate excellent low-firing stability; be conducive to the low temperature gas-tight seal of electrical element, protection electric device and energy-conservation object can be reached.
Description
Technical field
The present invention relates to electrical element technical field of sealing technology, particularly relate to a kind of glass frit compositions, frit paste composition, electrical element sealing method and electrical element.
Background technology
Organic Light Emitting Diode (OrganicLightEmittingDiode), the electric elements such as photodiode (LED) lighting or dye sensitization solar battery (DSSC) need to seal, and make the performance and used life minimizing to improve electric elements from the moisture of outside and the impact of gas.
Wherein, Organic Light Emitting Diode is widely used in display field, is called as organic light emitting display (OrganicLightEmittingDisplay, OLED).OLED display has the advantage such as high color contrast and wide visible angle, but the electrode of OLED display and organic layer are easily and the oxygen of surrounding enviroment and moisture transmission effect and cause it aging, therefore, electrode in OLED and organic layer are needed to carry out gas-tight seal to separate with surrounding environment, thus improves the performance and used life of OLED display.
OLED adopts organic/inorganic thin-film package, can 10 be reached
-6g/m
2the ability of the obstruct steam in/sky, and existing frit is encapsulated, then need in high temperature or laser technology, adopt glass frit compositions to be sealed by upper and lower base plate, thus reach 10
-6g/m
2the ability of the obstruct steam in/sky.But the shortcoming of thin-film package is the high of whole packaging cost, and also comparatively complicated in technique.Although based on PbO, Sb
2o
3, the composition such as CdO the sealing property of frit encapsulation better, but problem is all to contain in most of frit compositions heavy metal element, easily causes problem of environmental pollution.And owing to considering the cost requirement wanting summation device of OLED material stability in post laser encapsulation, then need glass frit compositions can meet machining at low temperature technique, the hermetically sealing material therefore developing a kind of frit based on low temperature, environmental protection is particularly urgent.
At present, vanadate system packaged glass material has expensive starting materials, melts process processed and easily bubbles, the shortcoming of not resistance to pickling.The thermal expansivity (CTE) of phosphate system frit is higher, chemical stability is poor, even if add multiple filler component can not reach application target, be difficult to apply, and the package strength of vanadate system frit and phosphate system frit is not high, easily cause spallation problems in actual applications, reduce the yield of product.
Summary of the invention
In view of this, the object of the invention is to propose a kind of glass frit compositions, frit paste composition, electrical element sealing method and electrical element, low temperature gas-tight seal can be realized.
For reaching this object, a first aspect of the present invention provides a kind of glass frit compositions for electrical element sealing,
Described glass frit compositions is by mole% comprising:
A second aspect of the present invention provides a kind of frit paste composition, comprises:
Above-mentioned glass frit compositions;
Polymeric adhesive;
Organic solvent.
A third aspect of the present invention provides a kind of sealing method of electrical element, and described electrical element at least comprises the first sealing substrate and second sealing substrate of needs sealing, and described sealing method comprises:
Above-mentioned frit paste composition is arranged on the predetermined position between described first sealing substrate and described second sealing substrate needing sealing;
Heat to make its melting to described frit paste composition;
Described first sealing substrate and described second sealing substrate is sealed through overcooling.
A fourth aspect of the present invention provides a kind of electrical element adopting above-mentioned sealing method to carry out gas-tight seal to obtain.
Glass frit compositions of the present invention, frit paste composition, electrical element sealing method and electrical element; reduce glass transition temp and softening temperature; demonstrate excellent low-firing stability; be conducive to the low temperature gas-tight seal of electrical element, protection electric device and energy-conservation object can be reached.
Accompanying drawing explanation
Fig. 1 is the schema of the sealing method of electrical element of the present invention;
Fig. 2 is the schematic cross-section of OLED display panel of the present invention;
Fig. 3 is the adhesive structure schematic diagram of OLED display panel of the present invention;
Fig. 4 is the schema of the sealing method of OLED display panel of the present invention.
Embodiment
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing.Be understandable that, specific embodiment described herein is only for explaining the present invention, but not limitation of the invention.It also should be noted that, for convenience of description, illustrate only part related to the present invention in accompanying drawing but not full content.
Embodiments provide a kind of glass frit compositions for electrical element sealing, comprising: molar percentage is the Bi of 20%-45%
2o
3; Molar percentage is the SiO of 10%-35%
2; Molar percentage is the ZnO of 5%-35%; Molar percentage is the CuO of 5%-20%; Molar percentage is the Al of 5%-15%
2o
3; Molar percentage is the MnO of 1%-15%
2; Molar percentage is the Fe of 1%-5%
2o
3; Molar percentage is the BaO of 0.1%-5%; Molar percentage is the TiO of 0.1%-5%
2; Molar percentage is the WO of 0.1%-5%
3.
When the content forming the composition of frit of the present invention is outside above-mentioned scope, can not vitreum be formed, or water tolerance is obviously deteriorated, or is unfavorable for the absorption of frit to source of radiation.Frit of the present invention does not use lead or antimony, belongs to Environment-friendlylow-temperature low-temperature sintered frit.
Glass frit compositions comprises basal component, extinction component and fluxing component and other components, is described in detail below to each component.
Substrate component: in the glass frit compositions of the embodiment of the present invention, metallic element Bi belongs to the P district of period 6 with plumbous (Pb) element, follows antimony element to be congeners again, thus comparatively similar in the chemically.Bi element contains the d track of five heavy degeneracys, belongs to multiple ligand element, can form the regular octahedron structure of 6 coordinations or the positive tetrahedron structure of four parts, therefore the oxide compound Bi of Bi
2o
3can as glass network body, it and SiO
2glass-former, in embodiments of the present invention using the basal component as frit.
Frit system of the present invention is Bi
2o
3-SiO
2binary basal component, wherein, 20-45mol%Bi
2o
3and 10-35mol%SiO
2glass network body can be formed, Bi
2o
3the mobility of glass frit compositions can be increased, again because the bond energy of Bi-O is smaller, be generally 300kj/mol, therefore, it is possible to reduce glass transition temp Tg and the softening temperature Tdsp of frit paste composition system, be conducive to low temperature sintering technology and laser package technique.
Extinction component: the Infrared receptivity of transition metal oxide to 810nm place is splendid, can make glass frit compositions melt, thus between glass substrate, form hermetically sealing dam, with protection device, in glass frit compositions of the present invention, CuO and Fe
2o
3as extinction component, for absorbing infrared light, glass frit compositions is merged.Wherein, CuO and Fe
2o
3the uptake factor of the infrared light at 810nm place is had to the specific absorbance of more than 33/mm, strong uptake factor is conducive to realizing lower technological temperature when follow-up use laser encapsulates frit.
Fluxing component: MnO
2, TiO
2and WO
3as fluxing component, for reducing the glass transition temp of glass frit compositions, and increase a certain amount of BaO and ZnO, the intensity of glass network body or link level are died down, thus reduces sintering temperature.
It should be noted that, for this multicomponent mixture of composition of the present invention, with the addition of these fluxing component, the not interpolation of simple material, and relate to the process that physics and chemistry occurs, because these components can be supplied to the ability of the frit components free oxygen forming glass network body in sintering process, make this frit network body link ability and die down, because this reducing the glass transition temp Tg of glass frit compositions.
Wherein, when in frit, the mole percent level of ZnO component is less than 5mol%, frit paste composition has comparatively high softening temperature Tdsp, and the mole percent level of ZnO component is when being greater than 5mol%, frit paste composition softening temperature Tdsp reduces, this is mainly because the ZnO component of high-content has the ability that part provides free oxygen in frit Network former, the fracture of the old key of glass network and the restructuring of new key is made to become relatively easy, thus there is the benefit of fluxing, and ZnO also contributes to the mobility improving frit, PbO can be substituted, thus realize environmental protection object.Contrary, if the mole percent level of the ZnO component in above-mentioned glass frit compositions higher than 35% time, the high-content of ZnO reduces greatly by causing the network contiguity in whole glass network former, thus make the weaken of frit, be unfavorable for obtaining the good frit of welding strength.
Wherein, when the content of the BaO component in frit is less than 0.1mol%, there is the problem that softening point temperature increases in glass frit compositions, because the barium ion of divalence, be free on outside glass network former, have very strong polarizability, the Network former link level in frit is died down, and softening temperature Tdsp reduces.Contrary, when the content of the B component aO in above-mentioned frit is higher than 5mol%, is then unfavorable for the stable of frit, sometimes devitrification occurs.
Meanwhile, the Al in above-mentioned frit
2o
3content when being less than 5mol%, the water resistance of glass frit compositions will reduce, and affects the effect of gas-tight seal.Al in above-mentioned frit
2o
3component when being greater than 15mol%, will reduce the content of Network former in frit, glass-former will become unstable.Therefore in order to the Al of this scope
2o
3ensure the water tolerance of glass composition.
Preferably, for the glass frit compositions of electrical element sealing, comprise: molar percentage is the Bi of 30%-40%
2o
3; Molar percentage is the SiO of 15%-30%
2; Molar percentage is the ZnO of 5%-25%; Molar percentage is the CuO of 5%-20%; Molar percentage is the Al of 5%-15%
2o
3; Molar percentage is the MnO of 1%-15%
2; Molar percentage is the Fe of 1%-5%
2o
3; Molar percentage is the BaO of 0.1%-5%; Molar percentage is the TiO of 0.1%-5%
2; Molar percentage is the WO of 0.1%-5%
3.
In this preferable range, the glass transition temperature of glass frit compositions is between the scope of 350 DEG C-400 DEG C.Those skilled in the art can know, heat decomposition temperature due to the binding agent in frit paste is between 250 DEG C-350 DEG C, gas meeting in presintering that the thermolysis of high temperature molecular binder is formed cause the detrimentally affect on pattern to glass frit compositions, and the preferred embodiments of the present invention scope avoids this detrimentally affect.
Glass frit compositions due to the embodiment of the present invention has used Bi
2o
3its thermal expansivity (Coefficientofthermalexpansion, CTE) coefficient can be larger, be unfavorable for that glass frit compositions is mated with the CTE of glass substrate, match to make the thermal expansivity of glass frit compositions and glass substrate, therefore need to increase the filler component reducing thermal expansivity, improve the hot expansibility of glass frit compositions, thus durable hermetically sealing dam is provided and prevents from breaking.
Alternatively, the CTE of glass frit compositions controls 50 × 10
-7/ DEG C-80 × 10
-7/ DEG C scope in.Further, glass frit compositions also comprises the filler reducing thermal expansivity further.Alternatively, described filler is selected from beta-eucryptite, β-triphane, LiAlSiO
4, pyrophosphate salt, a kind of in cyanines green stone or at least two kinds mixture.Wherein, filler is the 0-30% of the weight of glass frit compositions, if namely glass frit compositions is 100 weight parts, filler is 0-30 weight part.
Need to further illustrate, except the composition of glass composition, the size of composition dynamics is also very important, and the particle of the glass frit compositions of the present invention containing mentioned component is preferably the size of 0.1 μm-20 μm.The size of the particle of glass frit compositions is in above-mentioned scope, can machining at low temperature, be applicable to the gas-tight seal of heat labile element, and laser can be used to process, the leakage efficiency of electrical element can be improved, improve the fine ratio of product of electric elements.
Glass transition temp Tg of the present invention is in the scope of 300-400 DEG C; its softening temperature (softeningtemperature) Tdsp is in the scope of 300-400 DEG C; reduce the processing temperature of glass frit compositions in seal process; be conducive to the low temperature seal technique of electrical element; protection OLED and energy-conservation object can be reached; demonstrate excellent low-firing stability; and by adding the filler reducing thermal expansivity, the thermal expansivity of glass frit compositions can control 50 × 10
-7/ DEG C-80 × 10
-7/ DEG C scope in, the thermal expansivity of glass frit compositions and glass substrate can be made to match.
In order to seal electrical element, present invention also offers a kind of frit paste composition, it comprises: above-mentioned glass frit compositions; Polymeric adhesive and organic solvent.
Preferably, frit paste composition contains: the glass frit compositions of 65-90 weight part; The polymeric adhesive of 0.1-5 weight part and the organic solvent of 5-30 weight part.
Wherein, high polymer binder can use usually commercially available high polymer binder.Alternatively, described high polymer binder is selected from acrylic resin (AC), ethyl cellulose (EC), or the mixture of zinc-containing solid catalyst a kind of or at least two kinds.
Wherein, organic solvent uses organic solvent that can be compatible with the high polymer binder that uses in frit paste composition of the present invention.Alternatively, described organic solvent is selected from acetate of butyl carbitol (BCA), terpinol (TPN), dibutyl phthalate (DBP), or 2,2,4-trimethylammonium-1.3 pentanediol mono isobutyrate, or the mixture of a kind of in triglyme or at least two kinds.
In order to realize the better cooperation of high polymer binder and organic solvent, preferably, being combined as of described high polymer binder and described organic solvent: the combination of ethyl cellulose (EC) and acetate of butyl carbitol (BCA), acrylic resin (AC) and 2,2, the combination of 4-trimethylammonium-1.3 pentanediol mono isobutyrate (Texanol ester alcohol), or the combination of zinc-containing solid catalyst and triglyme.
Preferably, the viscosity of described frit paste composition is 500-100000cps.Further alternatively, the viscosity of described frit paste composition is 2000-80000cps.When the present composition has the viscosity in above-mentioned scope, can be coated with by silk screen print method, operating efficiency can be improved further.
The viscosity of frit paste composition has impact to a certain extent for the yield of its gas-tight seal on the first glass substrate and the second glass substrate.When the viscosity of frit paste composition is lower than 500cps, frit paste composition, in silk screen printing process, extremely easily penetrates half tone and cannot reach the ideal thickness of frit.When the viscosity of frit paste composition is higher than 100000cps, caking agent just directly adheres on half tone, and returning in black technique in printing, sometimes can cause the plug-hole phenomenon of silk-screen half tone.Meanwhile, when the viscosity of frit paste composition is higher than 100000cps, the surface topography of frit on the first glass substrate also can be uneven, and the drop of high lower is very big, has a great impact the yield of follow-up gas-tight seal.Therefore, the viscosity of frit paste composition is preferably 500-100000cps, the viscosity more preferably 2000-80000cps of described frit paste composition.
Glass frit compositions paste composition of the present invention except the advantage with glass composition, and effectively can control the viscosity of frit paste, is convenient to the fixing attachment of frit paste composition, is conducive to follow-up pre-sintering process.
Fig. 1 is the schema of the sealing method of electrical element of the present invention, as shown in Figure 1, present invention also offers a kind of sealing method of electrical element, described electrical element at least comprises the first sealing substrate and second sealing substrate of needs sealing, and described sealing method comprises:
S110, above-mentioned frit paste composition is arranged on the predetermined position between described first sealing substrate and described second sealing substrate needing sealing.
Wherein, the method that can be coated with by screen painting or some glue carries out the setting of frit paste composition, glass paste composition is coated on the first sealing substrate or on the second sealing substrate, also can on the first sealing substrate and the second sealing substrate equal coated glass material paste composition, then the first sealing substrate and the second sealing substrate are fitted, thus glass paste composition is arranged on the predetermined position between the first sealing substrate and the second sealing substrate.
Generally for fixing glass paste composition, need to carry out presintering to it.In order to enable, frit paste composition and described first sealing substrate plate are fixing to be adhered to, presintering is carried out after the coating carrying out frit paste, wherein, about about 300 DEG C of the temperature of presintering, when carrying out presintering, can be fixedly attached on described first sealing substrate by frit paste composition, wherein high polymer binder and organic solvent can vapor away.
S120, heat to make its melting to described frit paste composition.
Wherein, laser can be utilized to heat described frit paste composition, described laser is preferably infrared light, by heating frit paste composition to make its melting to sinter, thus the first hermetic sealing substrate and the second hermetic sealing substrate is bondd securely.Its mid-infrared light, is preferably the infrared light at 810nm place.
It should be noted that the object of presintering is fixed attachment to frit paste composition, usually at about 300 DEG C, and the object of sintering is fixed to carry out sealing glass frit compositions melting, and sintering temperature reaches about 500 DEG C usually.
S130, seal described first sealing substrate and described second sealing substrate through overcooling.
After bonding, through overcooling, the first hermetic sealing substrate and the second hermetic sealing substrate engage by frit paste composition, thus achieve the gas-tight seal of electrical element.
Fig. 2 is the schematic cross-section of OLED display panel of the present invention; Fig. 3 is the adhesive structure schematic diagram of OLED display panel of the present invention.In the preferred embodiment of the present invention, if described electrical element is organic electroluminescence display panel (OLED), as depicted in figs. 1 and 2, described first sealing substrate is first glass substrate 11 being formed with organic light-emitting units 14 above of described organic electroluminescence display panel, described second sealing substrate is the second glass substrate 12 of described organic electroluminescence display panel, and the tack coat 13 formed by described frit paste composition when sealing carries out hermetic seal to it.
Hermetic seal to be carried out to the first glass substrate 11 of OLED display panel and the second glass substrate 12, first on the first glass substrate 12 by known method evaporation organic light-emitting units 14, then following sealing method seals.Fig. 4 is the schema of the sealing method of OLED display panel of the present invention, and as shown in Figure 4, the sealing method of OLED display panel of the present invention comprises following steps:
S210, described frit paste composition is arranged on the default bonding part of described first glass substrate 11.
Wherein, the method that can be coated with by screen painting or some glue carries out the setting of frit paste composition, frit paste composition is coated in the default bonding part of the first glass substrate, is usually coated in the surrounding of the first glass substrate.In order to enable frit paste composition and described first glass substrate mortise, presintering is carried out after the coating carrying out frit paste, wherein, about about 300 DEG C of the temperature of presintering, when carrying out presintering, can be fixedly attached on described first glass substrate by frit paste composition, wherein high polymer binder and organic solvent can vapor away.
S220, described second glass substrate 12 to be fitted with described first glass substrate 11 contraposition.
Wherein, the first glass substrate 12 and the second glass substrate 11 that are provided with frit paste composition are carried out accurate contraposition, thus is fitted in the predetermined position of the frit blends of the first glass substrate and the second glass substrate.
S230, have an X-rayed described second glass substrate 12 by described laser 15, heat to make its melting to described frit paste composition.
Wherein, laser 15 can be utilized to heat described frit paste composition, described laser is preferably infrared light, to the position irradiating laser being provided with frit paste composition, carry out heating to make the melting of frit paste composition, first glass substrate 11 and the second glass substrate 12 are bonded, thus gas-tight seal is carried out to organic luminous panel.Due to the glass transition temp of frit paste composition of the present invention and softening temperature lower, and uptake factor is higher, especially very good to ultrared absorption, is conducive to using laser to carry out heat fusion, improves working (machining) efficiency and save production cost.
S240, seal described first glass substrate 11 and described second glass substrate 12 through overcooling.
After bonding, through overcooling, the first glass substrate 11 and the second glass substrate 12 engage to form hermetically sealing dam between by frit paste composition, thus achieve the gas-tight seal of electrical element.
In addition, present invention also offers a kind of electrical element adopting above-mentioned sealing method to carry out gas-tight seal to obtain.Alternatively, described electrical element comprises organic electroluminescence display panel, photodiode (LED) lighting or dye sensitization solar battery (DSSC), sensor or other optics, by using the glass frit compositions being conducive to machining at low temperature, its disadvantageous effect for electrical element can be alleviated, significantly improve the sealing effectiveness to moisture and gas, promote its work-ing life.
In order to understand the present invention further, under list preferred embodiment, preferred embodiment is below just in order to illustrate the present invention, and embodiments of the invention are not limited to following embodiment.
Manufacture the glass frit compositions of embodiment 1-6 and comparative example 1 according to the composition of following table 1, the unit in lower list 1 is molecular fraction.
Embodiment one
Table 1
In table 1 above, comparative example 1 does not form frit, cannot carry out the sealing of electrical element, in embodiment 1-6, can manufacture the frit of 0.1 μm-20 μm.
The frit blends of above-described embodiment 1-5 is utilized to manufacture frit paste composition, frit blends in above-described embodiment 1-5, high polymer binder and the organic solvent weight part according to table 2 is weighed, and mix, kind and the Different Weight ratio of polymeric adhesive and solvent can be regulated as required, the different viscosity of frit paste composition can be obtained, carry out operation with the silk screen printing process of applicable screen painting or some glue coating process.Further, frit paste composition is upside down in further the batch mixing that three-roller carries out once or several times, more preferably silk-screen effect can be reached.
The frit O of comparative example 1 is carried out being mixed to get comparative example 2 according to the type of the weight part in table 2 and high polymer binder and organic binder bond, carried out being mixed to get comparative example 3 and embodiment 7-13 according to the type of weight part corresponding in mark 2 and high polymer binder and organic binder bond by embodiment 1-5, wherein embodiment 7-13 is the frit paste composition realizing the technology of the present invention effect.
As can be seen from comparative example 3 and embodiment 7-9, the viscosity of embodiment 7-9 is in the scope of 500-100000cps, and embodiment 9 viscosity is 8000cps, control further in the scope of 2000-80000cps, and the viscosity of comparative example 3 is at 14Kcps, viscosity is higher, is unfavorable for silk screen printing.The present invention by controlling the weight part of glass frit compositions, high polymer binder and organic binder bond is: 65-90 parts by weight of glass feed composition; The polymeric adhesive of 0.1-5 weight part; The organic solvent of 5-30 weight part, and then control viscosity is in the silk screen printing process of applicable screen painting or the scope of some glue coating process.
Table 2
Between the glass of two panels same thickness, weld body to the frit paste composition processing that above-described embodiment 9-13 and comparative example 3 manufacture to form one below, can become OLED test piece, then be determined as follows OLED test piece, its result as shown in Figure 3.
1, glass transition temp (Tg)
Utilize DTA device (DTG-60HShimatz), heat up with the speed of 10 DEG C/min, measure glass transition temp.
2, softening temperature (Tdsp)
Utilize DTA device, heat up with the speed of 10 DEG C/min, measure softening temperature.
3, thermal expansivity (CTE (× 10
-7))
Utilize TMA device, heat up with the speed of 5 DEG C/min, measure thermal expansivity.
4, water tolerance
The OLED test piece of sealing is soaked 24 hours in the pure water of 70 DEG C, measures its weight, be designated as " √ " when the gradient of emphasis is less than 0.5%, when the gradient of emphasis is less than 0.5%, be designated as "×".
5, intensity (N)
By peeling off (Peeling) strength test instrument, the OLED test piece of sealing is measured.
6, stability is fired
Glass frit powder be filled in metal grinding tool, after extrusion forming, be warmed up to 600 DEG C with the speed of 10 DEG C/min, firing rear observation has nodeless mesh.Wherein, " outstanding " representative does not have crystallization and glossiness is very good; " well " representative does not have crystallization and glossiness is good; " poor " representative there occurs crystallization and lackluster degree.
Table 3
| Tdsp | Softening temperature | CTE | Water tolerance | Intensity | Fire stable |
| (℃) | (℃) | (×10 -7) | (N) | Property | ||
| Comparative example 2 | 350 | 365 | 80 | × | 73 | Poor |
| Comparative example 4 | 358 | 360 | 81 | × | 72 | Poor |
| Ratio example 5 | 359 | 362 | 80 | × | 72 | Poor |
| Embodiment 9 | 320 | 350 | 75 | √ | 80 | Outstanding |
| Embodiment 10 | 340 | 360 | 75 | √ | 78 | Well |
| Embodiment 11 | 330 | 358 | 75 | √ | 79 | Well |
| Embodiment 12 | 328 | 356 | 76 | √ | 76 | Well |
| Embodiment 13 | 338 | 359 | 76 | √ | 77 | Well |
In order to prove technique effect of the present invention further, adopt comparative example 4 and comparative example 5 to contrast, wherein, the glass frit compositions (vanadate system frit) in ratio example 4 is by weight percentage: V
2o
460%; P
2o
520%; Sb
2o
320%, frit paste composition is: 75 parts by weight of glass feed compositions, 3 weight part ethyl cellulose, 20 weight part BCA.Glass frit compositions (phosphate system frit) in comparative example 5 is by mole% being P
2o
540%; SnO
435%; ZnO25%, frit paste composition is: 75 parts by weight of glass feed compositions, 3 weight part ethyl cellulose, 20 weight part BCA.
As can be seen from Table 3, the embodiment of the present invention 9 compare the glass transition temp of embodiment 10-13 and softening temperature lower, thus can find out that the formula of the embodiment 9 (the frit C that embodiment 3 is filled a prescription) that embodiment 9 adopts is relatively optimum.And the glass transition temp of embodiment 9-13 all controls in the scope of 320-340 DEG C, softening temperature all controls in the scope of 350-370 DEG C, the glass transition temperature of embodiment 9-13 compares comparative example 2 and comparative example 4 reduces 18-28 DEG C, the softening temperature of embodiment 9-13 compares comparative example 2 and comparative example 4 reduces 1-15 DEG C, and thermal expansivity is about 75 DEG C, can mate with glass substrate better.The water tolerance of embodiment 9-13 is also more excellent relative to ratio 2-4, and embodiment 9 (the frit C that embodiment 3 is filled a prescription) compares embodiment 10-13, and to fire stability better, reach " outstanding " grade, there is no crystallization and glossiness is very good, and the stability of firing of embodiment 10-13 also reaches " well " grade, there is no crystallization and glossiness is good, and comparative example 2 and 4 to fire stability all poor, there occurs crystallization and lackluster degree.
What is more important, the intensity that inventive embodiments 9 compares embodiment 10-13 is higher, thus can find out, the formula of the embodiment 3 (the frit C that embodiment 3 is filled a prescription) that embodiment 9 adopts is relatively optimum, and comparative example 9-13 is relative to comparative example 2-4, and intensity improves 3-8N, that is the cohesive strength of glass frit compositions scope of the present invention is higher, and also improves cohesive strength relative to vanadate system frit and phosphate system frit.
Glass transition temp Tg of the present invention is in the scope of 300-400 DEG C; its softening temperature (softeningtemperature) Tdsp is in the scope of 300-400 DEG C; reduce the processing temperature of glass frit compositions in seal process; demonstrate excellent low-firing stability; be conducive to the low temperature seal technique of electrical element; protection OLED and energy-conservation object can be reached; and by adding the filler reducing thermal expansivity, the thermal expansivity of glass frit compositions can control 50 × 10
-7/ DEG C-80 × 10
-7/ DEG C scope in, the thermal expansivity of glass frit compositions and glass substrate can be made to match.
Frit paste composition of the present invention is adopted to seal electrical element, excellent to the sealing effectiveness of steam and oxygen, reduce glass transition temp and softening temperature, be conducive to the low temperature seal technique of low-temperature sintering and laser package.And, frit paste composition of the present invention relative to vanadate system glass composition and phosphate system glass frit compositions intensity higher, overcoming both holds flaky problem in actual use, improves the yield of product.In addition, frit paste composition of the present invention not only overcomes the shortcoming of vanadate system frit, melt process processed be not easy bubble, resistance to pickling; And the coefficient of expansion of relative phosphate system frit is lower, chemical stability is higher, can obtain actual applying.
The hermetically sealing of embodiment 14:OLED display panel:
Embodiment 14 uses frit to be fixed on the predetermined bonding position of the first glass substrate by screen printing process or some glue coating process for OLED display panel, laser source is utilized to take heated frit paste, first glass substrate is welded on the second described glass substrate and also forms gas-tight seal dam betwixt, thus realize gas-tight seal.
Below by detailed method for hermetically sealing of setting forth OLED element with half tone silk screen printing process and laser radiation heating technique.It is to be understood that the frit paste composition of setting forth in the embodiment of the present invention and air hermetic packing technique, be not limited to half tone silk-screen or laser radiation heating.The sealing means of OLED display panel is as follows:
(1) preparation of frit paste composition
By according in embodiment 9 frit paste composition uniform stirring batch mixing, to reach silk-screen condition, usually first frit paste composition is carried out stirring more than at least 1 hour before silk-screen, scraper can be adopted to stir, or be positioned over the upper rotation number hour of roller machine (roller).
(2) silk screen printing process
By frit paste composition good for batch mixing, be applied in the upper surface of the half tone of silk-screen board, regulate the corresponding scraper of silk-screen board or the angle of inclination of returning blade, the height of silk-screen half tone and the first glass substrate upper surface, and the pressure and other parameters pressing down half tone of returning blade or scraper, silk-screen is in the predetermined position of the first glass substrate upper surface, and wherein the first glass substrate upper surface orientates the one side of silk printing glass material paste composition as.
(3) sintering process
Frit paste composition on above-mentioned first glass substrate predetermined position is carried out presintering.
First, at a lower temperature by complete for the organic solvent drying in frit paste composition.
Then, frit paste composition complete for drying is carried out carbonization treatment technique.Generally speaking, the polymeric adhesive in carbonization treatment processing requirement frit paste composition as far as possible all within 300 DEG C smooth oxygenolysis become gas.Specifically, in the present invention frit paste composition to the selection of polymeric adhesive based on the glass transition temp of frit blends higher than the complete decomposition temperature of polymeric adhesive, and the viscosity of polymeric adhesive will meet silk screen printing process requirement.
Finally, the frit paste composition after carbonization treatment is carried out sintering processes.
(4) air hermetic glass capsulation
The first glass substrate after sintering and the second glass substrate carry out air hermetic glass capsulation.
First, the upper surface of the second glass substrate of thin film transistor (thinfilmtransistor, TFT) technique will be prepared, carry out vacuum thermal evaporation art breading, form OLED unit, the upper surface of the second described glass substrate is defined as the one side of carrying out TFT technique.
Then, the upper surface of the upper surface of the second described glass substrate and the first described glass substrate is carried out exactitude position, is fitted in the predetermined position of the frit blends on the first glass substrate upper surface and the second glass substrate upper surface.
Finally, titanium-doped sapphire (Ti: sapphire) laser (λ=810nm) is passed into its upper surface by the lower surface of the first glass substrate, frit paste mixture on its upper surface being heated, sealing forming hermetically sealing dam between the upper surface and the upper surface of the second glass substrate of the first glass substrate.
These are only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (18)
1., for a glass frit compositions for electrical element sealing, described glass frit compositions is by mole% comprising:
2. glass frit compositions according to claim 1, described glass frit compositions is by mole% comprising:
3. glass frit compositions according to claim 1 and 2, is characterized in that, described glass frit compositions also comprises the filler reducing thermal expansivity further.
4. glass frit compositions according to claim 3, is characterized in that, described filler is selected from beta-eucryptite, β-triphane, LiAlSiO
4, pyrophosphate salt, a kind of in cyanines green stone or at least two kinds mixture.
5. a frit paste composition, is characterized in that, it comprises:
Glass frit compositions according to any one of claim 1-4;
Polymeric adhesive;
Organic solvent.
6. frit paste composition according to claim 5, it is characterized in that, said composition contains:
Glass frit compositions according to any one of the claim 1-4 of 65-90 weight part;
The polymeric adhesive of 0.1-5 weight part;
The organic solvent of 5-30 weight part.
7. the frit paste composition according to claim 5 or 6, it is characterized in that, described high polymer binder is selected from the mixture of a kind of of acrylic resin (AC), ethyl cellulose (EC) or zinc-containing solid catalyst or at least two kinds.
8. the frit paste composition according to claim 5 or 6, it is characterized in that, described organic solvent is selected from acetate of butyl carbitol (BCA), terpinol (TPN), dibutyl phthalate (DBP), 2, the mixture of a kind of in 2,4-trimethylammonium-1.3 pentanediol mono isobutyrate or triglyme or at least two kinds.
9. the frit paste composition according to claim 5 or 6, it is characterized in that, being combined as of described high polymer binder and described organic solvent: the combination of ethyl cellulose (EC) and acetate of butyl carbitol (BCA), acrylic resin (AC) and 2, the combination of 2,4-trimethylammonium-1.3 pentanediol mono isobutyrate or the combination of zinc-containing solid catalyst and triglyme.
10. frit paste composition according to claim 5, is characterized in that, the viscosity of described frit paste composition is 500-100000cps.
11. frit paste compositions according to claim 10, is characterized in that, the viscosity of described frit paste composition is 2000-80000cps.
The sealing method of 12. 1 kinds of electrical elements, described electrical element at least comprises the first sealing substrate and second sealing substrate of needs sealing, and described sealing method comprises:
Frit paste composition according to any one of the claims 5-11 is arranged on the predetermined position between described first sealing substrate and described second sealing substrate needing sealing;
Heat to make its melting to described frit paste composition;
Described first sealing substrate and described second sealing substrate is sealed through overcooling.
The sealing method of 13. electrical elements according to claim 12, is characterized in that, described in add thermal utilization laser described frit paste composition heated.
The sealing method of 14. electrical elements according to claim 13, it is characterized in that, described electrical element is organic electroluminescence display panel, described first sealing substrate is the first glass substrate of described organic electroluminescence display panel, described second sealing substrate is formed with the second glass substrate of organic light-emitting units above being, the sealing method of described organic electroluminescence display panel is:
Described frit paste composition is arranged on the default bonding part of described first glass substrate;
Described second glass substrate and described first glass substrate contraposition are fitted;
By described second glass substrate of described laser perspective, heat to make its melting to described frit paste composition;
Described first glass substrate and described second glass substrate is sealed through overcooling.
The sealing method of 15. electrical elements according to claim 14, is characterized in that, described laser is infrared light.
The sealing method of 16. electrical elements according to any one of claim 12-15, is characterized in that, is carried out the setting of frit paste composition by the method for screen painting or the coating of some glue.
17. 1 kinds of electrical elements adopting sealing method any one of the claims 12-16 to carry out gas-tight seal to obtain.
18. electrical elements according to claim 17, is characterized in that, described electrical element comprises organic electroluminescence display panel, photodiode (LED) lighting or dye sensitization solar battery (DSSC).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107275516A (en) * | 2017-06-21 | 2017-10-20 | 苏州卡睿知光电科技有限公司 | A kind of glass capsulation material for photoelectric device, paste and preparation method thereof |
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| CN105957977B (en) * | 2016-05-13 | 2019-02-05 | 京东方科技集团股份有限公司 | A kind of encapsulating material, encapsulation cover plate, agglomerating plant, sintering method and display device |
| CN106007548A (en) * | 2016-06-28 | 2016-10-12 | 蚌埠市方阵商品混凝土有限公司 | Heat insulation concrete |
| CN107162426A (en) * | 2017-06-21 | 2017-09-15 | 苏州卡睿知光电科技有限公司 | A kind of glass capsulation material, sealing material paste and preparation method thereof |
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| CN1122509A (en) * | 1994-08-01 | 1996-05-15 | 纳幕尔杜邦公司 | Cadmium-free and lead-free thick film conductor composition |
| CN1653009A (en) * | 2002-05-15 | 2005-08-10 | 费罗公司 | Electronic device having lead and cadmium free electronic overglaze applied thereto |
| CN103214185A (en) * | 2013-04-25 | 2013-07-24 | 上海大学 | Glass composition sealing material for photoelectric device laser package and preparation method of glass composition sealing material |
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| CN1122509A (en) * | 1994-08-01 | 1996-05-15 | 纳幕尔杜邦公司 | Cadmium-free and lead-free thick film conductor composition |
| CN1653009A (en) * | 2002-05-15 | 2005-08-10 | 费罗公司 | Electronic device having lead and cadmium free electronic overglaze applied thereto |
| CN103214185A (en) * | 2013-04-25 | 2013-07-24 | 上海大学 | Glass composition sealing material for photoelectric device laser package and preparation method of glass composition sealing material |
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| CN107275516A (en) * | 2017-06-21 | 2017-10-20 | 苏州卡睿知光电科技有限公司 | A kind of glass capsulation material for photoelectric device, paste and preparation method thereof |
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Effective date of registration: 20211027 Address after: No.8, liufangyuan Henglu, Donghu New Technology Development Zone, Wuhan City, Hubei Province Patentee after: WUHAN TIANMA MICRO-ELECTRONICS Co.,Ltd. Patentee after: Wuhan Tianma Microelectronics Co.,Ltd. Shanghai Branch Patentee after: Tianma Micro-Electronics Co.,Ltd. Address before: Room 509, building 1, No. 6111, Longdong Avenue, Pudong New Area, Shanghai, 200120 Patentee before: SHANGHAI TIANMA AM-OLED Co.,Ltd. Patentee before: Tianma Micro-Electronics Co.,Ltd. |