CN103539355B - The glass frit compositions of gas-tight seal and preparation method, sealing method based on glass frit compositions - Google Patents

The glass frit compositions of gas-tight seal and preparation method, sealing method based on glass frit compositions Download PDF

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CN103539355B
CN103539355B CN201310514152.9A CN201310514152A CN103539355B CN 103539355 B CN103539355 B CN 103539355B CN 201310514152 A CN201310514152 A CN 201310514152A CN 103539355 B CN103539355 B CN 103539355B
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glass frit
frit compositions
glass
oxide powder
preparation
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CN103539355A (en
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张建华
李艺
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University of Shanghai for Science and Technology
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Abstract

The invention provides a kind of glass frit compositions of gas-tight seal and preparation method, sealing method based on glass frit compositions.The glass frit compositions of this gas-tight seal, comprises following component according to molar percentage: 30-60SiO 2, 10-30P 2o 5, 5-20Li 2o, 4-15ZnO, 0-15Al 2o 3, 10-20Co 2o 3, 0-3RO, wherein, R is at least one in Fe, Cr, Mg, Ti.The preparation method of described glass frit compositions, comprises the steps: sintered oxide powder, and obtains granulated glass sphere with the oxide powder shrend of melting; The granulated glass sphere obtained described in pulverizing forms the glass frit compositions of glass particle form; Wherein, described oxide powder comprises following component according to molar percentage: 30-60SiO 2, 10-30P 2o 5, 5-20Li 2o, 4-15ZnO, 0-15Al 2o 3, 10-20Co 2o 3, 0-3RO, wherein, R is at least one in Fe, Cr, Mg, Ti.Adopt the present invention can obtain the high air hermetic encapsulation of sealing intensity, and free from environmental pollution.

Description

The glass frit compositions of gas-tight seal and preparation method, sealing method based on glass frit compositions
Technical field
The present invention relates to sealing material technical field, particularly relate to a kind of glass frit compositions of gas-tight seal and preparation method, sealing method based on glass frit compositions.
Background technology
The sealing material of gas-tight seal, such as frit, be applied to as the class intermediate materials sealed substrate luminescent device sealing-in, to make inside and the ambient environment of luminescent device, avoid luminescent device be subject to the impact of surrounding environment and make degradation.
Luminescent device, such as organic electroluminescence device, obtain increasing concern and widespread use.In organic electroluminescence device, display of organic electroluminescence OLED all has potential advantage as a kind of emerging flat-panel monitor in color contrast, visual angle, response speed and energy consumption etc., and sealing material is particularly important for the performance of luminescent device.
But traditional sealing material contains the toxic substances such as Vanadium Pentoxide in FLAKES, to absorb the laser realizing base plate seals as absorption agent, and when sealing material temperature of fusion is lower, thermal expansivity raise, formed sealing-in time crackle and subside, there is the defect that sealing intensity is not high.
Summary of the invention
Based on this, there is the glass frit compositions of the gas-tight seal that higher, the free of contamination gas-tight seal of a kind of sealing intensity is provided.
In addition, there is a need to the preparation method that high, the free of contamination glass frit compositions of a kind of sealing intensity is provided.
In addition, there is a need to provide a kind of sealing intensity high, the free of contamination sealing method based on glass frit compositions.
The glass frit compositions of above-mentioned gas-tight seal and preparation method, sealing method based on glass frit compositions, by introducing Co 2o 3, with Co 2o 3nontoxic and the good absorbing effect of main additive as absorbing laser, lower thermal expansivity (CTE) is obtained while making glass frit compositions obtain lower temperature of fusion as a kind of glass, and then ensure that wettability good between glass frit compositions and substrate, apply above-mentioned glass frit compositions and sealing-in is carried out to substrate will ensure that the sealing intensity of sealing-in is high, pollution-free.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of the glass frit compositions of an embodiment;
Fig. 2 is the schema of the sealing method based on glass frit compositions of an embodiment;
Fig. 3 is the CTE of the glass frit compositions of an embodiment and the relation schematic diagram of melting temperature.
Embodiment
Below in conjunction with embodiment and accompanying drawing, to glass frit compositions and the preparation method of gas-tight seal, be described in further detail based on the sealing method of glass frit compositions.
The glass frit compositions of the gas-tight seal of one embodiment, comprises following component according to molar percentage: 30-60SiO 2, 10-30P 2o 5, 5-20Li 2o, 4-15ZnO, 0-15Al 2o 3, 10-20Co 2o 3, 0-3RO, wherein, R is at least one in Fe, Cr, Mg, Ti.
The glass frit compositions of above-mentioned gas-tight seal and preparation method, sealing method based on glass frit compositions, by introducing Co 2o 3, with Co 2o 3nontoxic and the good absorbing effect of main additive as absorbing laser, lower thermal expansivity (CTE) is obtained while making glass frit compositions obtain lower temperature of fusion as a kind of glass, and then ensure that wettability good between glass frit compositions and substrate, apply above-mentioned glass frit compositions and sealing-in is carried out to substrate will ensure that the sealing intensity of sealing-in is high, pollution-free.
Traditional glass frit compositions is for making thermal expansivity far above 80 about making melting temperature maintain lesser temps, the glass frit compositions compared with low melting point temperature and relatively low thermel expansion coefficient cannot be obtained simultaneously, and above-mentioned glass frit compositions does not need to add any fire resistant infilling and can reach the low and feature that thermal expansivity is low of fusing, ensure that the material of lower thermal expansivity and substrate matches and obtain good sealing effectiveness.
Refer to Fig. 1, the preparation method of the glass frit compositions of an embodiment, comprises the following steps:
S110, sintered oxide powder, and obtain granulated glass sphere with the oxide powder shrend of melting.
In the present embodiment, oxide powder comprises following component according to molar percentage: 30-60SiO 2, 10-30P 2o 5, 5-20Li 2o, 4-15ZnO, 0-15Al 2o 3, 10-20Co 2o 3, 0-3RO, wherein, R is at least one in Fe, Cr, Mg, Ti.
Molar percentage weighs a certain amount of SiO as described above 2, P 2o 5, Li 2o, ZnO, Al 2o 3, Co 2o 3be mixed to get oxide powder with RO phase, oxide powder to be placed in High Temperature Furnaces Heating Apparatus the oxide powder that sintering obtains molten state, and the oxide powder of molten state is poured into water carries out shrend and form granulated glass sphere.
S130, pulverizes the glass frit compositions that the granulated glass sphere obtained forms glass particle form.
In the present embodiment, the average particle size distribution pulverizing the glass frit compositions of the granulated glass sphere form obtained is less than 5 microns.Can be ball milling, grinding or other suitable mode for pulverizing the mode of granulated glass sphere.
In the preparation method of the glass frit compositions of other embodiment, after above-mentioned steps S130, also comprise the step that selection by winnowing obtains the glass frit compositions conformed to default size-grade distribution.
Refer to Fig. 2, the sealing method based on glass frit compositions of an embodiment, comprises the following steps:
S210, is deposited on substrate by glass frit compositions.
In the present embodiment, glass frit compositions comprises following component according to molar percentage: 30-60SiO 2, 10-30P 2o 5, 5-20Li 2o, 4-15ZnO, 0-15Al 2o 3, 10-20Co 2o 3, 0-3RO, wherein, R is at least one in Fe, Cr, Mg, Ti.
There is provided first substrate and second substrate, make glass frit compositions be deposited on substrate by modes such as silk screen printings, this substrate is second substrate; Pre-laminating first substrate and second substrate, make the glass frit compositions being deposited on second substrate be placed between first substrate and second substrate.
S230, the substrate that presintering deposited glass frit compositions obtains prefabricated component.
In the present embodiment, carry out presintering in 400 DEG C to the substrate that deposited glass frit compositions, wherein, the atmosphere of presintering can be any one in rare gas element, reducing gas or low oxygen atmosphere environment.This low oxygen atmosphere environment is oxygenous lower than 5%, will be oxidized to prevent the transition of oxide compound in glass frit compositions.
Compared with traditional glass frit compositions, because traditional glass frit compositions needs to carry out presintering under the environment of 450 DEG C, and glass frit compositions as above only needs can complete presintering process at 400 DEG C, avoid the pyrolytic damage that too high temperature causes.
S250, forms the hermetic between substrate by source of radiation sealing-in prefabricated component.
In the present embodiment, this source of radiation can be any one in laser, infrared rays and microwave.By radiation source heats glass frit compositions, glass frit compositions is melted and forms strip of paper used for sealing, to be connected by two substrates, namely first substrate is connected on second substrate.
Another embodiment based in the sealing method of glass frit compositions, glass frit compositions mixes with organic binder bond, and before above-mentioned S230, the method also comprises:
To deposited the base plate heating to 300 DEG C-350 DEG C of glass frit compositions, and stop Preset Time, burnout organic binder bond.
In the present embodiment, in the process that the substrate that deposited glass frit compositions is heated, stop Preset Time when Heating temperature rises to 300 DEG C-350 DEG C, burnout to make organic binder bond total number in presintering process.
The glass frit compositions of above-mentioned gas-tight seal and preparation method, sealing method based on glass frit compositions, by glass frit compositions absorbing radiation source to reach the effect of local heating in substrate, can be used for the air hermetic encapsulation realized in thin-film device or organic luminescent device, to be ensured the performance of thin-film device or organic luminescent device by stronger stopping property.
Be described below in conjunction with specific embodiment.
Embodiment 1
Preparation glass frit compositions, it comprises following component according to molar percentage: 30SiO 2, 30P 2o 5, 10Li 2o, 6ZnO, 7Al 2o 3, 15Co 2o 3, 1.5TiO 2and 0.5Fe 2o 3.
SiO is weighed according to as above molar percentage 2, P 2o 5, Li 2o, ZnO, Al 2o 3, Co 2o 3, TiO 2and Fe 2o 3, and be mixed to get oxide powder, be placed in sintering in High Temperature Furnaces Heating Apparatus and obtain the oxide powder of molten state, and the oxide powder of molten state is poured into water carries out shrend and obtain granulated glass sphere;
The granulated glass sphere that pulverizing obtains to obtain the glass frit compositions that average particle size distribution is less than the glass particle form of 5 microns, and selects the particle of required each size-grade distribution by selection by winnowing.
The melting temperature of this glass frit compositions prepared is 450 DEG C, and thermal expansivity is 87.5.
Embodiment 2
Preparation glass frit compositions, it comprises following component according to molar percentage: 45SiO 2, 20P 2o 5, 5Li 2o, 8ZnO, 2Al 2o 3and 20Co 2o 3.
SiO is weighed according to as above molar percentage 2, P 2o 5, Li 2o, ZnO, Al 2o 3and Co 2o 3, and be mixed to get oxide powder, be placed in sintering in High Temperature Furnaces Heating Apparatus and obtain the oxide powder of molten state, and the oxide powder of molten state is poured into water carries out shrend and obtain granulated glass sphere;
The granulated glass sphere that pulverizing obtains to obtain the glass frit compositions that average particle size distribution is less than the glass particle form of 5 microns, and selects the particle of required each size-grade distribution by selection by winnowing.
The melting temperature of this glass frit compositions prepared is 487 DEG C, and thermal expansivity is 77.6.
Embodiment 3
Preparation glass frit compositions, it comprises following component according to molar percentage: 60SiO 2, 10P 2o 5, 15Li 2o, 5ZnO and 100Co 2o 3.
SiO is weighed according to as above molar percentage 2, P 2o 5, Li 2o, ZnO and Co 2o 3, and be mixed to get oxide powder, be placed in sintering in High Temperature Furnaces Heating Apparatus and obtain the oxide powder of molten state, and the oxide powder of molten state is poured into water carries out shrend and obtain granulated glass sphere;
The granulated glass sphere that pulverizing obtains to obtain the glass frit compositions that average particle size distribution is less than the glass particle form of 5 microns, and selects the particle of required each size-grade distribution by selection by winnowing.
The melting temperature of this glass frit compositions prepared is 510 DEG C, and thermal expansivity is 75.5.
Embodiment 4
Preparation glass frit compositions, it comprises following component according to molar percentage: 36SiO 2, 23P 2o 5, 20Li 2o, 4ZnO, 2Al 2o 3, 13.5Co 2o 3and 0.5Fe 2o 3.
SiO is weighed according to as above molar percentage 2, P 2o 5, Li 2o, ZnO, Al 2o 3, Co 2o 3and Fe 2o 3, and be mixed to get oxide powder, be placed in sintering in High Temperature Furnaces Heating Apparatus and obtain the oxide powder of molten state, and the oxide powder of molten state is poured into water carries out shrend and obtain granulated glass sphere;
The granulated glass sphere that pulverizing obtains to obtain the glass frit compositions that average particle size distribution is less than the glass particle form of 5 microns, and selects the particle of required each size-grade distribution by selection by winnowing.
The melting temperature of this glass frit compositions prepared is 463 DEG C, and thermal expansivity is 76.7.
Embodiment 5
Preparation glass frit compositions, it comprises following component according to molar percentage: 30SiO 2, 21P 2o 5, 5Li 2o, 15ZnO, 15Al 2o 3and 14Co 2o 3.
SiO is weighed according to as above molar percentage 2, P 2o 5, Li 2o, ZnO, Al 2o 3and Co 2o 3, and be mixed to get oxide powder, be placed in sintering in High Temperature Furnaces Heating Apparatus and obtain the oxide powder of molten state, and the oxide powder of molten state is poured into water carries out shrend and obtain granulated glass sphere;
The granulated glass sphere that pulverizing obtains to obtain the glass frit compositions that average particle size distribution is less than the glass particle form of 5 microns, and selects the particle of required each size-grade distribution by selection by winnowing.
The melting temperature of this glass frit compositions prepared is 502 DEG C, and thermal expansivity is 79.1.
Embodiment 6
Preparation glass frit compositions, it comprises following component according to molar percentage: 40SiO 2, 20P 2o 5, 11Li 2o, 12ZnO, 2Al 2o 3, 13Co 2o 3, 1.5TiO 2and 0.5Fe 2o 3.
SiO is weighed according to as above molar percentage 2, P 2o 5, Li 2o, ZnO, Al 2o 3, Co 2o 3, TiO 2and Fe 2o 3, and be mixed to get oxide powder, be placed in sintering in High Temperature Furnaces Heating Apparatus and obtain the oxide powder of molten state, and the oxide powder of molten state is poured into water carries out shrend and obtain granulated glass sphere;
The granulated glass sphere that pulverizing obtains to obtain the glass frit compositions that average particle size distribution is less than the glass particle form of 5 microns, and selects the particle of required each size-grade distribution by selection by winnowing.
The melting temperature of this glass frit compositions prepared is 484 DEG C, and thermal expansivity is 79.3.
Embodiment 7
Preparation glass frit compositions, it comprises following component according to molar percentage: 42SiO 2, 23P 2o 5, 5Li 2o, 10ZnO, 2Al 2o 3, 14Co 2o 3, 1CrO and 3MgO.
SiO is weighed according to as above molar percentage 2, P 2o 5, Li 2o, ZnO, Al 2o 3, Co 2o 3, CrO and MgO, and be mixed to get oxide powder, be placed in sintering in High Temperature Furnaces Heating Apparatus and obtain the oxide powder of molten state, and the oxide powder of molten state is poured into water carries out shrend and obtain granulated glass sphere;
The granulated glass sphere that pulverizing obtains to obtain the glass frit compositions that average particle size distribution is less than the glass particle form of 5 microns, and selects the particle of required each size-grade distribution by selection by winnowing.
The melting temperature of this glass frit compositions prepared is 472 DEG C, and thermal expansivity is 81.
Refer to Fig. 3, Figure 3 shows that the melting temperature of glass frit compositions prepared by embodiment 1 ~ embodiment 7 and the test result of thermal expansivity (CTE).As can be seen from Figure 3 the melting temperature of glass frit compositions prepared of embodiment 1 ~ embodiment 7 and thermal expansivity all lower, effectively can reduce the erosion to thin-film device or organic luminescent device such as such as outside aqueous vapor in surrounding environment, thus improve performance and the life-span of thin-film device or organic luminescent device.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (6)

1. a glass frit compositions for gas-tight seal, is characterized in that, comprises following component: 36SiO according to molar percentage 2, 23P 2o 5, 20Li 2o, 4ZnO, 2Al 2o 3, 13.5Co 2o 3, 0.5Fe 2o 3.
2. a preparation method for glass frit compositions, is characterized in that, comprises the steps:
Sintered oxide powder, and obtain granulated glass sphere with the oxide powder shrend of melting;
The granulated glass sphere obtained described in pulverizing forms the glass frit compositions of glass particle form;
Wherein, described oxide powder comprises following component according to molar percentage: 36SiO 2, 23P 2o 5, 20Li 2o, 4ZnO, 2Al 2o 3, 13.5Co 2o 3, 0.5Fe 2o 3.
3. the preparation method of glass frit compositions according to claim 2, is characterized in that, the average particle size distribution of the glass frit compositions of the glass particle form that described pulverizing obtains is less than 5 microns.
4. the preparation method of glass frit compositions according to claim 2, is characterized in that, after the granulated glass sphere obtained described in described pulverizing forms the step of the glass frit compositions of glass particle form, described method also comprises:
Selection by winnowing obtains the step of the glass frit compositions conformed to default size-grade distribution.
5. based on a sealing method for glass frit compositions, it is characterized in that, comprise the steps:
Glass frit compositions is deposited on substrate;
The substrate that deposited glass frit compositions described in presintering obtains prefabricated component;
The hermetic between described substrate is formed by prefabricated component described in source of radiation sealing-in;
Described glass frit compositions comprises following component according to molar percentage: 36SiO 2, 23P 2o 5, 20Li 2o, 4ZnO, 2Al 2o 3, 13.5Co 2o 3, 0.5Fe 2o 3.
6. the sealing method based on glass frit compositions according to claim 5, it is characterized in that, described glass frit compositions mixes with organic binder bond, and before the substrate that deposited glass frit compositions described in described presintering obtains the step of prefabricated component, described method also comprises:
By the described base plate heating to 300 that deposited glass frit compositions DEG C-350 DEG C, and stop Preset Time, burnout described organic binder bond.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101454860A (en) * 2005-12-06 2009-06-10 康宁股份有限公司 Glass package that is hermetically sealed with a frit and method of fabrication
CN101475312A (en) * 2009-02-05 2009-07-08 东华大学 Copper seal powdered glass, as well as preparation and application thereof
CN102276150A (en) * 2011-06-02 2011-12-14 重庆仪表材料研究所 High-temperature and high-pressure resistant glass material for sealing and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140261975A1 (en) * 2011-11-02 2014-09-18 Ferro Corporation Microwave Sealing Of Inorganic Substrates Using Low Melting Glass Systems

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101454860A (en) * 2005-12-06 2009-06-10 康宁股份有限公司 Glass package that is hermetically sealed with a frit and method of fabrication
CN101475312A (en) * 2009-02-05 2009-07-08 东华大学 Copper seal powdered glass, as well as preparation and application thereof
CN102276150A (en) * 2011-06-02 2011-12-14 重庆仪表材料研究所 High-temperature and high-pressure resistant glass material for sealing and preparation method thereof

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