KR101252179B1 - Slurry composite for exhaust tube sealing device comprising inorganic solvent and method for manufacturing granule of the same, and method for manufacturing exhaust tube sealing device using the same - Google Patents

Abstract

PURPOSE: A slurry composition for an exhaust sealing device is provided to prevent bubble generation and sealability loss by adding SrO into a glass frit composition which includes Bi2O3, B2O3, ZnO, Al2O3, BaO, and CoO. CONSTITUTION: A slurry composition for an exhaust sealing device comprises a lead-free glass frit. The lead-free glass frit comprises 70-90 weight% of Bi2O3, 4-9 weight% of B2O3, 8-14 weight% of ZnO, 0.1-1 weight% of Al2O3, 0.1-1.5 weight% of BaO, 0.1-1 weight% of CoO, and 0.5-3 weight% of SrO. The slurry composition for the exhaust sealing device comprises 40-80 weight% of the lead-free glass frit, 30-80 weight% of an inorganic solvent, and 0.05-5 weight% of an organic binder. The inorganic solvent is water and the organic binder is polyvinyl alcohol(PVA, PVOH, PVAl). [Reference numerals] (AA) Start; (BB) No; (CC) Yes; (DD) End; (S100) Manufacturing a slurry composition containing an inorganic solvent; (S200) Spray-drying; (S300) Normal powder?; (S400) Forming a molded product; (S500) Thermal treatment; (S600) Manufacturing a sealing device;

Description

Slurry composite for exhaust tube sealing device comprising inorganic solvent and method for manufacturing granule of the same, and method for manufacturing exhaust tube sealing device using the same}

The present invention relates to a method for manufacturing an exhaust pipe sealing element used for sealing an electronic component and a flat panel display device, and in particular, in preparing a slurry composition for an exhaust pipe sealing element of a flat panel display device, and a slurry composition for an exhaust pipe sealing element including an inorganic solvent; A method for producing granules and a method for producing an exhaust pipe sealing element using the same.

As a sealing material for electronic parts and flat display devices, it has excellent chemical durability and heat resistance as compared with resin-based sealing materials, and is suitable for securing airtightness such as flat display devices, and includes a mother glass and a ceramic filler. Frit compositions that exist in a glass state after the sealing process are widely used.

The frit composition is basically low in transition point, softening point, etc. so as to enable low temperature sealing, and excellent in fluidity, high temperature stability without crystallization problem even at low temperature, and excellent in reliability, durability and chemical resistance after sealing. I ask for it as a characteristic.

Among them, the sealing glass frit used in OLEDs, organic ELs and dye-sensitized solar cells is calcined at a low temperature of 430 degrees or lower. Most glass frit compositions that can be fired at low temperatures contain 80% or more of PbO because they have a lower melting point than other glass and are very stable physically and chemically before and after firing.

Meanwhile, among the key technologies in the technical field used to seal electronic components and flat panel display devices, there is a development of a component for sealing between an exhaust pipe and a panel for injecting discharge gas or exhausting impurity gas inside the panel. At this time, since the sealing material located between the exhaust pipe and the panel must maintain airtightness after injecting and discharging the discharge gas, a glass composition similar to the sealing glass used for bonding the glass facing surfaces is used.

A representative technique for sealing between the exhaust pipe and the panel using a glass composition similar to this sealing glass is a sealing device manufactured in the form of a paste and a solid by mixing lead-free glass frit with an organic solvent and an organic binder.

However, in the case of paste, the organic binder is not sufficiently burned and there is a problem that air bubbles are generated during firing, thereby reducing the airtightness, and the paste is manually applied at the position where the exhaust hole formed in the corner of the panel and the exhaust pipe are connected. As a result, there was a problem of low productivity.

In addition, an organic solvent such as toluene, acetate, alcohol, or the like is used to prepare a slurry composition for a sealing device. However, in the case of the organic solvent described above, there is a risk of fire and explosion because there is a serious danger to the human body in handling, and there is a ignition point. In addition, since the generation of CO ₂ by the organic solvent increases during the calcination, environmental pollution may be raised.

On the other hand, conventionally, when spray drying for producing a granule of the slurry composition does not have a complete spherical or relatively small particles are discharged powder, these powders are poor in flowability and formability, so the problem that is not manufactured into granules and discarded there was.

Therefore, the present invention has been made to solve the above problems, to prevent the occurrence of internal bubbles and deterioration of airtightness in the sealing of the panel and exhaust pipe, and to prepare a slurry composition for producing granules, Reducing the harmfulness and eliminating environmental problems and recycling the powder that has problems in forming during spray drying of the slurry composition in an efficient manner, having an optimal lead-free composition that can easily manufacture and apply the sealing element while reducing the production cost It is an object of the present invention to provide a method for producing a slurry composition for a sealing element of a flat panel display device.

Features of the slurry composition for exhaust pipe sealing device comprising an inorganic solvent according to the present invention for achieving the above object is Bi ₂ O ₃ 70 to 90% by weight, B ₂ O ₃ 4 to 9% by weight, ZnO 8 to 14 It comprises a lead-free glass frit comprising 0.1% to 1% by weight of Al ₂ O ₃ , 0.1 to 1.5% by weight of BaO, 0.1 to 1% by weight of CoO, and 0.5 to 3% by weight of SrO.

Preferably, the slurry composition for the exhaust pipe sealing device is characterized in that it comprises 40 to 80% by weight of lead-free glass frit, 30 to 80% by weight of inorganic solvent, and 0.05 to 5% by weight of organic binder.

Preferably, water is used as the inorganic solvent, and polyvinyl alcohol including PVA, PVOH, and PVAI is used as the organic binder.

Characteristic of the method for producing a granule of the slurry composition for exhaust pipe sealing device comprising an inorganic solvent according to the present invention for achieving the above object (A) to prepare a slurry composition for exhaust pipe sealing device comprising an inorganic solvent through the above process. And (B) spray-drying the prepared slurry composition for a sealing element to form granules.

Preferably, the step (A) comprises the steps of (A1) impeller stirring or ball milling the inorganic solvent and the organic binder to prepare a vehicle as a mixture, and (A2) adding a lead-free glass frit to the vehicle. It is characterized in that it comprises a step of producing a slurry by mixing again with an impeller or ball milling.

Preferably the step (A1) is characterized in that the impeller (impeller) stirring for 2 to 4 hours at 200 to 400rpm, or ball milling for 1 to 3 hours at 100 to 300rpm.

Preferably, the step (B) accumulates a predetermined amount after collecting abnormal granules having a relatively small particle size and spherical shape among the granules formed during spray drying, and storing the accumulated abnormal granules in the manufactured vehicle. It is characterized in that it further comprises the step of adding to further prepare a slurry.

Preferably the step (B) is characterized in that proceeds to a condition of 7000 to 11000rpm during spray drying.

Features of the method for producing an exhaust pipe sealing device using the slurry composition for exhaust pipe sealing device comprising an inorganic solvent according to the present invention for achieving the above object (a) for the exhaust pipe sealing device comprising an inorganic solvent through the above process Forming the granules produced by the granule manufacturing method of the slurry composition to form a sealing device molded body, and (b) completing the sealing device through the heat treatment process of the formed molded body.

Preferably step (b) is characterized in that the heat treatment of the molded body for 10 to 70 minutes at a temperature of 300 to 500 ℃.

Preferably step (a) is characterized in that to form a molded body by pressing at a pressure of 16.0 to 20.0kgf / cm ^{2 with} a designed mold.

As described above, the slurry composition for the exhaust pipe sealing device including the inorganic solvent according to the present invention, the granule manufacturing method thereof, and the method of manufacturing the exhaust pipe sealing device using the same have the following effects.

First, in the sealing of the panel and the exhaust pipe to prevent the occurrence of internal bubbles and deterioration of airtightness can be improved reliability and durability after sealing.

Second, in preparing the slurry composition for the exhaust pipe sealing device, through the slurry composition for the exhaust pipe sealing device including an inorganic solvent, it is possible to solve the harmful effects on the human body and environmental problems in the handling of the solvent.

Third, it is possible to reduce the production cost by recycling the powder having a problem in forming the spray drying of the slurry composition in an efficient manner.

1 is a process flowchart for manufacturing a sealing element of a flat panel display device according to an exemplary embodiment of the present invention.
FIG. 2 is a flowchart illustrating a process of manufacturing a slurry composition for a sealing device including an inorganic solvent in FIG. 1.
3 to 7 are graphs for comparing thermal characteristics generated during a manufacturing process of a sealing element of a flat panel display device with a comparative example.

Other objects, features and advantages of the present invention will become apparent from the detailed description of the embodiments with reference to the accompanying drawings.

Referring to the accompanying drawings, a preferred embodiment of the slurry composition for the exhaust pipe sealing device comprising the inorganic solvent according to the present invention, a method for producing granules thereof, and a method for producing an exhaust pipe sealing device using the same are as follows. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. It is provided to let you know. Therefore, the embodiments described in the present specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention and are not intended to represent all of the technical ideas of the present invention. Therefore, various equivalents It should be understood that water and variations may be present.

1 is a process flowchart for manufacturing a sealing element of a flat panel display device according to an exemplary embodiment of the present invention.

Referring to Figure 1, first to prepare a slurry composition for a sealing element containing an inorganic solvent (S100).

At this time, the process of producing a slurry composition for a sealing element comprising the inorganic solvent will be described in more detail with reference to FIG.

First, an inorganic solvent and an organic binder are impeller stirred or ball milled to prepare a vehicle, which is a mixed agent (S110). At this time, the impeller (impeller) for 2 hours to 4 hours at 200 to 400 rpm, or ball milling for 1 to 3 hours at 100 to 300 rpm is preferable. Water is used as the inorganic solvent, and polyvinyl alcohol (PVA, PVOH, PVAI) is used as the organic binder.

This is because polyvinyl alcohol (PVA, PVOH, PVAI) easily soluble in water because the organic binder is sufficiently dissolved in the inorganic solvent to satisfy the appropriate viscosity, so that it is easy to take out granules having favorable fluidity and moldability in the next step of spray drying. ) As an organic binder.

Subsequently, the lead-free glass frit is added to the vehicle in which melting is completed, and then mixed by impeller or ball milling to prepare a slurry (S120). Mixing the lead-free glass frit with the inorganic solvent and the organic binder raw material is intended to facilitate the manufacture of a sealing device using granules prepared by spray drying to form a slurry having fluidity.

The composition of the slurry thus prepared is 70 to 90 wt% of Bi ₂ O ₃ , 4 to 9 wt% of B ₂ O ₃ , 8 to 14 wt% of ZnO, 0.1 to 1 wt% of Al ₂ O ₃ , and 0.1 to 1.5 wt% of BaO. 40 to 80 wt% of lead-free glass frit containing 0.1 to 1 wt% of CoO, 0.5 to 3 wt% of SrO, 10 to 15 wt% of cordierite, 30 to 80 wt% of inorganic solvent and organic binder 0.05 to 5 wt%.

Here, SrO lowers the thermal properties of the lead-free glass and provides a function of improving chemical stability. The content of SrO is preferably 0.5 to 3% by weight, and less than 0.5% by weight of SrO affects thermal properties such as softening point and thermal expansion coefficient. If not more than 3% by weight, the glass becomes unstable, resulting in a decrease in durability and adhesive strength.

Then, the prepared slurry composition for the sealing element is spray dried (S200) to form granules (S300). Here, spherical granules may be obtained when the spray drying proceeds under conditions of 7000 to 11000 rpm.

However, since the particle size of the granules formed during spray drying is not uniform, some of the relatively small particle size and spherical abnormal granules are generated, and the powder is collected in a separate container through a filtration device of the spray dryer, The abnormal granules generated here are inferior in fluidity and formability, and are caught in molds during the production of molded bodies of the powders, causing wear and damage of the molds. In order to solve this problem, the abnormal granules are accumulated in a predetermined amount after collection, and when the appropriate amount is reached, an additional addition to the vehicle prepared in step S100 is performed to prepare a slurry composition. And again carry out the spray drying process performed in step S200. As such, the abnormal powder generated in the spray drying phase is difficult to collect, and then manufactured and reused as a slurry composition (S300). Through this method, by reusing the abnormal granules, there is an advantage that can reduce the production cost.

Next, by molding the granules prepared in the spray drying process to form a sealing element molded body (S400). At this time, the mold is designed in consideration of the appropriate pressure transfer pressure is pressed at a pressure of 16.0 to 20.0kgf / cm ² to form a molded body.

And it is completed as a sealing element through the heat treatment process (S500) of the formed body (S600). At this time, the appropriate heat treatment temperature of the molded body is preferably heat-treated for 10 to 70 minutes at 300 to 500 ℃.

On the other hand, the factor that has the greatest influence on the thermal properties and the sealing strength of the sealing element manufacturing method described above is the composition of the glass frit added to the vehicle is completed dissolution to prepare a slurry in step S120 shown in FIG. . Therefore, the glass frit composition and the slurry composition using the same will be described below with the results according to the examples and comparative examples.

1st Example

70 to 90 wt% Bi ₂ O ₃ , 4 to 9 wt% B ₂ O ₃ , 8 to 14 wt% ZnO, 0.1 to 1 wt% Al ₂ O ₃ , 0.1 to 1.5 wt% BaO, 0.1 to 1 wt% CoO After adding 0.5% by weight of SrO to the lead-free glass frit, including, and kneading with 10 to 15% by weight of cordierite to adjust the coefficient of thermal expansion, 1.5g was added to a cemented carbide 8mm diameter, 10kg / The pellets formed through the heat treatment process after forming at a pressure of cm ² were flattened on the upper and lower parts by SiC paper, and thermal characteristics were measured using a TMA device. The measurement results of the composition added with SrO are shown in FIG. 3. .

Further, for comparison with the first embodiment, 70 to 90% by weight of Bi ₂ O ₃ without SrO in the first comparative example, 4 to 9% by weight of B ₂ O ₃ , 8 to 14% by weight of ZnO, Al ₂ O ₃ 0.1 to 1 wt%, BaO 0.1 to 1.5 wt%, CoO 0.1 to non-associated one to the coefficient of thermal expansion adjusted to the glass frit kneading the cordierite (cordierite) 10 to 15% by weight of the back, including the 1% by weight of the In the same manner as in Example 1, thermal properties were measured using a TMA apparatus after pellet formation, heat treatment, and planarization. Thus, the measurement result of the composition which does not add SrO is shown in FIG.

Table 1 below shows the compositions included in the lead-free glass frit in the first and first comparative examples. For reference, the unit is weight percent.

Bi ₂ O ₃ B ₂ O ₃ ZnO Al ₂ O ₃ BaO CoO SrO First Embodiment 79.3 7 10.9 0.8 1.2 0.3 0.5 First Comparative Example 79.7 7 11 0.8 1.2 0.3 -

3 and 4, the transition point (T _g ) of the lead-free glass frit without SrO is 357.22 ° C, the strain point (T _dsp ) is 368.35 ° C, and the coefficient of thermal expansion (CTE) is It was measured 75.82 × 10 ⁻⁷ / ° C. The transition point (T _g ) of the lead-free glass frit to which SrO was added was 350.81 ° C., the strain point (T _dsp ) was 363.86 ° C., and the coefficient of thermal expansion (CTE) was measured to be 75.76 × 10 ⁻⁷ / ° C.

Table 2 below shows measurement results according to the first example and the first comparative example.

CTE (10 ^-7 / ℃) Transition point (℃) Strain point (℃) First Embodiment 75.76 350.81 363.86 First Comparative Example 75.82 357.22 368.35

Comparing the above, it was found that when SrO is added to the existing lead-free glass frit composition, the transition point and strain point are lower than those of the non-added glass. In this case, the high temperature flowability at the firing temperature is improved, and the glass frit to which SrO is added according to the present invention is shown to have an excellent sealing effect.

Second Example

After mixing 30 to 80 wt% of inorganic solvent water and 0.05 to 5 wt% of PVA in the lead-free glass frit and cordierite mixture of the first embodiment, the slurry composition as described above After the manufacturing method was carried out by spray drying, the extracted normal granules were pelletized, heat treated and planarized in the same manner as in the first embodiment, and thermal properties were measured using a TMA equipment. It is shown.

In addition, for comparison with the second embodiment, in the second comparative example, the lead-free glass frit and cordierite kneaded mixture of the first embodiment were replaced with an organic solvent alcohol instead of water, which is an inorganic solvent. After mixing 30 to 80% by weight and 0.05 to 5% by weight of organic binder ethyl cellulose, pellets, heat treatment, and planarization were carried out in the same manner as in the second embodiment, after the solid granules were removed by the same method as in the second embodiment. Through the operation, the thermal properties were measured using the TMA equipment, and the results are shown in FIG. 6.

Table 3 below shows the compositions contained in the normal granules taken from the second example and the second comparative example. For reference, the unit is weight percent.

Lead Free Glass Frit (First Embodiment) Organic Solvents (Alcohol) Inorganic solvent (water) Organic binder Ethyl cellulose P.V.A First Embodiment 37 - 60 - 3 First Comparative Example 37 60 - 3 -

5 and 6, the transition point (T _g ) of the normal granules using the inorganic solvent is 350.22 ° C., the strain point (T _dsp ) is 362.26 ° C., and the coefficient of thermal expansion (CTE) is 75.16 × 10. Measured at ^-7 / ° C. The transition point (T _g ) of the normal granules using the organic solvent was 350.80 ° C., the strain point (T _dsp ) was 363.50 ° C., and the coefficient of thermal expansion (CTE) was measured to be 75.73 × 10 ⁻⁷ / ° C.

Table 4 below shows measurement results according to the second example and the second comparative example.

CTE (10 ^-7 / ℃) Transition point (℃) Strain point (℃) Second Embodiment 75.16 350.22 362.26 2nd comparative example 75.73 350.8 363.5

Comparing the above, it was shown that the granules using the inorganic solvent are similar in thermal properties to the granules using the organic solvent. In this case, the slurry composition using the inorganic solvent, the sealing composition and the sealing effect using the organic solvent Not only is it equivalent, it can be expected to reduce the handling hazards and explosion hazards and reduce costs in mass production.

Third Example

In the third embodiment, in step S300 of FIG. 1, the physical properties were measured when the abnormal powder generated in the spray drying phase was difficult to collect and reused as a slurry composition. This is to confirm whether the problem of deterioration of the properties of the slurry composition caused by reuse.

After mixing 30 to 80 wt% of inorganic solvent water and 0.05 to 5 wt% of PVA in the lead-free glass frit and cordierite mixture of the first embodiment, the slurry composition as described above After the manufacturing method was carried out by spray drying, and subjected to the above-described reuse method in the step S300 of FIG. 1 using the collected abnormal powder, the thermal properties of the extracted normal granules were measured, and the results are shown in FIG. It is shown.

Table 5 below shows the compositions contained in the normal granules taken out in the third example. For reference, the unit is weight percent.

Abnormal powder Organic Solvents (Alcohol) Inorganic solvent (water) Organic binder P.V.A Third Embodiment 37 - 60 3

Referring to FIG. 7, the measurement result shows that the transition point T _g is 351.86 ° C., the strain point T _dsp is 365.51 ° C., and the coefficient of thermal expansion (CTE) is 76.56 × 10 ⁻⁷ / ° C.

Table 6 below shows measurement results according to the third and second embodiments.

CTE (10 ^-7 / ℃) Transition point (℃) Strain point (℃) Third Embodiment 76.56 351.86 365.51 Second Embodiment 75.16 350.22 362.26

Comparing the above description, in this case it can be seen that the thermal granularity of the second embodiment in which spray drying is performed once using an inorganic solvent is similar to the normal granules. Cost savings can be expected.

Although the technical spirit of the present invention described above has been described in detail in a preferred embodiment, it should be noted that the above-described embodiment is for the purpose of description and not of limitation. In addition, those skilled in the art will understand that various embodiments are possible within the scope of the technical idea of the present invention. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

Claims (9)

70 to 90 wt% Bi ₂ O ₃ , 4 to 9 wt% B ₂ O ₃ , 8 to 14 wt% ZnO, 0.1 to 1 wt% Al ₂ O ₃ , 0.1 to 1.5 wt% BaO, 0.1 to 1 wt% CoO Including;
SrO composition comprising a lead-free glass frit containing 0.5 to 3% by weight Slurry composition for exhaust pipe sealing device. According to claim 1, wherein the slurry composition for exhaust pipe sealing device
A slurry composition for an exhaust pipe sealing element, comprising 40 to 80 wt% lead-free glass frit, 30 to 80 wt% inorganic solvent, and 0.05 to 5 wt% organic binder. The method of claim 2,
Slurry composition for exhaust pipe sealing device, characterized in that using water (water) as the inorganic solvent, and using a polyvinyl alcohol containing PVA, PVOH, PVAI as an organic binder. (A) preparing a slurry composition for exhaust pipe sealing element of any one of claims 1 to 3,
(B) a method for producing granules of the slurry composition for exhaust pipe sealing element, comprising spray drying the prepared slurry composition for sealing element into granules. The method of claim 4, wherein step (A)
(A1) impregnating the inorganic solvent and the organic binder at 200 to 400 rpm for 2 hours to 4 hours, or ball milling at 100 to 300 rpm for 1 hour to 3 hours to prepare a vehicle as a mixture; ,
(A2) The method for producing granules of the slurry composition for exhaust pipe sealing element, comprising the step of adding a lead-free glass frit to the vehicle, followed by mixing by impeller or ball milling again to prepare a slurry. The method of claim 5, wherein
Accumulating a certain amount after collecting abnormal granules having a relatively small particle size and not having a spherical shape among the granules formed during spray drying in step (B);
The method for producing granules of the slurry composition for an exhaust pipe sealing device, characterized in that it further comprises the step of adding the accumulated abnormal granules to the prepared vehicle (vehicle) to form a slurry. (a) molding the granules produced by the method for producing granules of the slurry composition for exhaust pipe sealing element described in claim 4 to form a sealing element molded body,
(B) exhaust pipe sealing device using the slurry composition for exhaust pipe sealing device comprising the step of completing the sealing element through the heat treatment process of the formed molded body. The method of claim 7, wherein
The step (b) is exhaust pipe sealing device using the slurry composition for exhaust pipe sealing device characterized in that the heat treatment of the molded body at a temperature of 300 to 500 ℃ 10 to 70 minutes. The method of claim 7, wherein
The step (a) is exhaust pipe sealing element using the slurry composition for exhaust pipe sealing element, characterized in that to form a molded body by pressing at a pressure of 16.0 to 20.0kgf / cm ^{2 with} a designed mold.

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