KR101220443B1 - Crystallizable glass for sealing, crystallizable glass composition for sealing comprising the same, crystallizable glass paste, and oled panel - Google Patents

Abstract

PURPOSE: A crystallized glass for welding, a crystallized glass composition for welding including the same, crystallized glass paste for welding, and an organic light-emitting diode panel are provided to enhance light absorbance, and to bond at low temperature. CONSTITUTION: A crystallized glass for welding comprises 35-65 mol% of V2O5, 0.1-35 mol% of P2O5, 0.1-25 mol% of SrO, 0.1-30 mol% of a mixture including Fe2O3 and Sb2O3, 0.1-25 mol% of metal oxide, 0.1-20 mol% of alkaline earth oxide, and 0.1-20 mol% of transition metal oxide. The metal oxide is selected from Al2O3, SiO2, B2O3, SnO, TeO2, Bi2O2, and Tl2O. The alkaline earth oxide is selected from MgO, CaO, BaO and ZnO. The transition metal oxide is selected from ZrO2, TiO2, MnO, NiO, CuO, SeO, and Nd2O3. The crystallized glass for welding includes Tl2O, CuO, and Nd2O3.

Description

Crystallizable glass for sealing, Crystallizable glass composition for sealing forming the same, Crystallizable glass paste, and OLED panel

The present invention relates to a low melting point crystallized glass for bonding, a low melting point crystallized glass composition for bonding comprising the same, a low melting point crystallized glass paste for bonding, and an organic light emitting diode panel, and more particularly, fluorescent material without substantially containing lead A low melting point crystallized glass for bonding, which may be used for bonding or sealing an opening or a junction of an electronic product such as a display panel, an organic light emitting diode panel, a plasma display panel, a semiconductor package, and the like, and a low melting point crystallized glass composition for bonding comprising the same A low melting point crystallized glass paste for bonding comprising a low melting point crystallized glass composition for bonding, and an organic light emitting diode panel manufactured using the low melting point crystallized glass paste for bonding.

In general, a sealing glass material is used for sealing various electronic products that use the inside as a high vacuum, and for sealing an electronic component package for preventing the intrusion of corrosive gas or moisture and ensuring operational stability. The glass material for sealing processing is made of powder of low melting point glass, and the powder is pasted into an organic binder solution and applied to the sealed part of the object to be sealed, and then fired in an electric furnace or the like to volatilize the vehicle component to melt the glass powder. It is to form a glass continuous layer.

Conventionally, as such a glass material for sealing processing, PbO-B ₂ O _{3 type} lead glass powder is widely used. In other words, lead glass can be sealed at low processing temperature and wide temperature range by PbO's low melting point and high meltability, and because of its low thermal expansion, excellent adhesion, adhesiveness, chemical stability, etc. There is an advantage that strength and durability can be obtained. However, since lead is a toxic substance, there is a problem in terms of labor safety and hygiene in the manufacturing process of lead glass. When lead electronic components or electrical appliances used for sealing reach the end of their life, they are disposed of as acid rain or the like when disposed of as it is. Elution may lead to soil contamination or groundwater contamination, and due to strict environmental regulations in recent years, disposal is not possible due to landfilling.

In line with this, research on inorganic adhesives containing no lead has been actively conducted. Korean Patent Publication No. 10-2008-0037889 discloses a low melting point glass composition for sealing OLED based on Bi ₂ O ₃ . However, the mechanical and chemical properties do not meet the requirements for sealing the electronic component package, and there is a problem of causing a problem of moisture absorption between the substrate and the substrate, thereby degrading the characteristics of the product. In addition, there is a method of bonding the substrate and the substrate to form an adhesive layer by curing the inorganic filler and epoxy with ultraviolet light, such an adhesive is generally excellent in physical strength, but the raw material is very expensive and oxygen and moisture into the substrate There is a problem that does not block the spread. In order to solve this problem, a desiccant is used, which is difficult to thin due to the use of the desiccant, and has a disadvantage in that a complicated process is required.

Derived to solve the conventional problems of the present invention, the object of the present invention is excellent light absorption, low energy and low-melting crystallization for adhesion capable of high-strength adhesion at low temperature, excellent physical and chemical properties An organic light emitting diode panel manufactured using glass, a low melting point crystallized glass composition for bonding comprising the same, a low melting point crystallized glass paste for bonding comprising the low melting point crystallized glass composition for bonding, and the low melting point crystallized glass paste for bonding In providing.

In order to solve the above object, the present invention is V ₂ O ₅ 40-65 mol%, P ₂ O ₅ 5-20 mol%, Fe ₂ O ₃ 3-12 mol% and Sb ₂ O ₃ 1-16 mol% Provided is a low melting point crystallized glass for bonding comprising as a main component.

In order to solve the above object, the present invention also provides a low melting point crystallized glass composition for adhesion comprising 70 to 95% by volume of the low melting point crystallized glass and 5 to 30% by volume of the refractory ceramic filler.

In order to solve the above object, the present invention also comprises a low melting point crystallized glass composition 60 to 90% by weight and a vehicle solution 10 to 40% by weight, the vehicle solution is a low melting point for adhesion, characterized in that consisting of a resin and a solvent Provide a crystallized glass paste.

In order to solve the above object, the present invention also provides a panel with an organic light emitting diode interposed between two substrates, at least one of the two substrates is transparent, the two substrates are low melting point crystallized glass for adhesion of claim 7 Provided is an organic light emitting diode panel which is bonded by a paste.

The low melting point crystallized glass for adhesion of the present invention and the low melting point crystallized glass composition for bonding comprising the same are capable of firing a glass substrate or a heterogeneous substrate in a preliminary firing region of 300 to 500 ° C., and reacting and firing at a specific wavelength band. It can be used for hermetic adhesion of semiconductor electric devices and the like, which is superior in quality to conventional PbO-containing crystallized glass compositions, and does not contain lead components, thereby making it possible to realize light and short reduction of semiconductor electric devices. In addition, it is environmentally friendly, which can reduce the cost of processing the environment. In addition, the adhesive material of the present invention can be bonded at low power when the light absorption firing, it is excellent in moisture resistance, it is possible to obtain an effect that can significantly increase the life of the semiconductor electrical device.

1 is a schematic cross-sectional view of an organic light emitting diode panel to which the low melting point crystallized glass paste for adhesion of the present invention is applied as a sealing material.

Hereinafter, the present invention will be described in detail.

One aspect of the present invention relates to a low melting point crystallized glass, the low melting point crystallized glass according to an embodiment of the present invention is V ₂ O ₅ 40 ~ 65 mol%, P ₂ O ₅ 5 ~ 20 mol%, Fe ₂ O ₃ 3 to 12 mol% and Sb ₂ O ₃ 1 to 16 mol% as main components. In addition, the low melting point crystallized glass according to an embodiment of the present invention is preferably SrO, Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , SnO, MgO, BaO, ZnO, TiO ₂ , MnO, NiO, CuO, SeO ₂ , and Nd ₂ O ₃ One or more accessory ingredients selected from the group consisting of residual amounts. In addition, the low melting point crystallized glass according to an embodiment of the present invention is more preferably Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , SnO, ZnO, TiO ₂ , MnO, NiO, CuO, SeO ₂ , and Nd ₂ One or more metal oxides selected from the group consisting of O ₃ and one or more alkaline earth metal oxides selected from the group consisting of SrO, MgO, and BaO are included in the remaining amount. In addition, the low melting point crystallized glass according to an embodiment of the present invention is most preferably one or more selected from the group consisting of Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , SnO, SeO ₂ , and Nd ₂ O ₃ Metal oxide and at least one alkaline earth metal oxide selected from the group consisting of SrO, MgO, and BaO and at least one transition metal oxide selected from the group consisting of ZnO, TiO ₂ , MnO, NiO, and CuO do.

Another aspect of the present invention relates to a low melting point crystallized glass composition for bonding, wherein the low melting point crystallized glass composition for bonding according to an embodiment of the present invention is 70 to 95% by volume of the low melting point crystallized glass and 5 to 30 refractory ceramic fillers. Volume%. At this time, if the refractory ceramic filler is a low thermal expansion ceramic component, the type is not particularly limited, for example, zircon, cordierite, aluminum titanate, alumina, mullite, silica (crystal, α-quartz, quartz glass, cristobalite, tree) Dimite, fused silica, etc.), tin oxide ceramics, β-eucryptite, β-spodumene, zirconium phosphate ceramics and β-quartz solid solutions, and the like, and preferably Pyrex, silica, cordierite And at least one member selected from the group consisting of aluminum titanate, mullite, eutectite, zirconium tungsten oxide and mullite.

Another aspect of the present invention relates to a low melting point crystallized glass paste for adhesion, wherein the low melting point crystallized glass paste for adhesion according to an embodiment of the present invention is 60 to 90% by weight of the low-melting point crystallized glass composition and the vehicle solution 10 ~ 40 weight percent. At this time, the vehicle solution is composed of a resin and a solvent, for example, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, into a solvent such as terpineol, butyl carbitol acetate, ethyl carbitol acetate, Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acryl by dissolving propyl cellulose, nitrocellulose or the like or into a solvent such as methyl ethyl ketone, terpineol, butyl carbitol acetate, ethyl carbitol acetate It can be prepared by dissolving an acrylic resin such as late and 2-hydroxyethyl methacrylate.

Another aspect of the invention relates to an organic light emitting diode panel. 1 is a schematic cross-sectional view of an organic light emitting diode panel to which the low melting point crystallized glass paste for adhesion of the present invention is applied as a sealing material. As shown in FIG. 1, an organic light emitting diode panel according to the present invention is a panel in which an organic light emitting diode is interposed between two substrates, at least one of the two substrates is transparent, and the two substrates are the low adhesive materials described above. It is characterized by adhering by melting point crystallized glass paste.

Hereinafter, the low melting point crystallized glass for bonding, the low melting point crystallized glass composition for bonding, and the low melting point crystallized glass paste for bonding according to another example of the present invention will be described.

The low melting point crystallized glass for adhesion according to another embodiment of the present invention contains substantially no lead, 35 to 65 mol% of V ₂ O _5, 0.1 to 35 mol% of P ₂ O ₅ , 0.1 to 25 mol% of SrO, and Fe _2. 0.1 to 30 mol% of O ₃ + Sb ₂ O ₃ as the main component, and the metal oxides Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , SnO, TeO ₂ , Bi ₂ O ₂ , Tl ₂ O 0.1-25 mol%, alkaline earth oxides MgO, CaO, BaO, ZnO 0.1-20 mol%, transition metal oxides ZrO ₂ , TiO ₂ , MnO, NiO, CuO, SeO, Nd ₂ O ₃ 0.1-20 mol% selectively It contains. In addition, the low melting point crystallized glass containing 0.1 to 15 mol% Fe ₂ O ₃ , TiO ₂ as an internal crystallization aid is characterized in that the alkali metal oxide content is less than 0.1 mol%. In addition, the low melting point crystallized glass of the present invention satisfies the relationship of TiO ₂ / Fe ₂ O ₃ ratio of 0.01 to 0.5, and / or (CuO + Fe ₂ O 3) / V ₂ O ₅ = 0.01 to 0.3 on a molar ratio basis.

In addition, the low melting point crystallized glass composition for adhesion according to another embodiment of the present invention includes the low melting point crystallized glass for adhesion described above and a refractory ceramic filler having low thermal expansion (NTE) characteristics. At this time, the refractory ceramic filler is composed of any one or more of Pyrex, cordierite, eukrypite, mullite, zirconium tungsten oxide. In addition, the low melting point crystallized glass composition for adhesion according to another embodiment of the present invention includes 50 to 95% by volume of the low melting point crystallized glass and 0.1 to 40% by volume of the refractory ceramic filler. The low melting point crystallized glass composition for adhesion according to another example of the present invention may be bonded at an adhesion temperature or less without crystallization even when pre-fired.

In addition, the low melting point crystallized glass paste for adhesion according to another embodiment of the present invention is obtained by mixing the low melting point crystallized glass composition and the vehicle solution, wherein the low melting point crystallized glass composition content is 50 to 85% by weight, the vehicle The solution content is 0.1-30% by weight. The low melting point crystallized glass paste for adhesion according to another embodiment of the present invention is made of a composition containing vanadium crystallized glass, and there is no possibility of causing environmental problems due to the lead component. In addition, the low melting point crystallized glass paste for bonding according to another embodiment of the present invention has a wide selectable temperature range and does not crystallize even when prebaked at 350 to 550 ° C., and has excellent light absorption ability. The low melting point crystallized glass composition or the low melting point crystallized glass paste of the present invention has excellent light absorption ability and can be used for adhesion using a laser light source or the like.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only for clearly illustrating the present invention, and do not limit the protection scope of the present invention.

1. Adhesive Low melting point  Preparation of Crystallized Glass and Its Characterization Test

To mix the raw materials in the mixing ratio of Table 1, put it in an electric furnace, and melted by heating at about 1200 ℃ for 1 hour, and then quenched dry using a cooling roller to prepare a low melting point crystallized glass. Thereafter, the low melting point crystallized glass was coarsely ground with a disk mill, and then finely ground with a dry mill to obtain a low melting point crystallized glass powder for adhesion having a particle size of 1 to 3 µm. The glass transition point, softening point and coefficient of thermal expansion of the low melting point glass powders obtained in Examples 1 to 10 and Comparative Example 1 were measured by a differential thermal analyzer (DTA) and a thermal mechanical analyzer (TMA). The results are shown in Table 2.

Raw material Raw material content (mol%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 1 PbO - - - - - - - - - - 62.0 V ₂ O ₅ 40.0 51.1 57.2 48.5 64.7 62.6 54.1 57.3 60.1 61.1 - P ₂ O ₅ 12.3 18.1 18.5 31.6 5.4 14.1 11.8 20.8 12.7 15.6 14.0 SrO 17.1 2.5 6.1 - - - 1.6 - - - - Fe ₂ O ₃ 4.8 6.3 6.3 3.1 3.5 8.7 11.8 10.0 9.0 5.7 12.0 Sb ₂ O ₃ 2.4 4.0 7.3 3.3 1.1 6.1 15.9 6.2 6.6 4.3 12.0 Al ₂ O ₃ - - 1.3 - - - - - - - - SiO ₂ 1.1 - - 1.0 3.6 - - - - 8.0 - B ₂ O ₃ - 1.2 1.5 - 12.9 - - - 1.0 - - SnO - 5.4 - - - - - - - - - MgO 2.4 1.2 - - 2.6 - - - - - - BaO 5.7 - - 2.3 3.4 - 0.4 3.3 - - - ZnO 11.5 9.0 - 8.8 1.8 - 3.4 - 2.7 - - TiO ₂ 1.6 - 1.8 - - 7.3 - 1.9 - - - MnO - - - - 1.0 - - - 6.3 - - NiO - - - - - 1.2 - - - 5.3 - CuO - 1.2 - 0.4 - - 1.0 0.5 - - - SeO ₂ 1.1 - - - - - - - 1.6 - - Nd ₂ O ₃ - - - 1.0 - - - - - - - Linear Expansion Coefficient (× 10 ^-7 / ℃) 114 113 71 87 84 84 84 89 82 89 70

Test Items Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 1 Glass transition point (℃) 355 340 337 333 332 311 338 316 335 325 325 Softening point (℃) 376 360 362 352 352 330 362 338 356 348 475 Thermal expansion coefficient (× 10 ^-7 / ℃) 114 113 85 87 84 64 84 89 82 89 70

2. Adhesive Low melting point  Preparation of Crystallized Glass Compositions and Their Characterization Tests

Raw materials were mixed at the blending ratios of Table 3 to prepare a low melting point crystallized glass composition for adhesion. Specifically, in Examples 11 to 19, the low melting point crystallized glass powder obtained in Example 3 and the refractory ceramic filler were mixed to prepare a low melting point crystallized glass composition for adhesion. On the other hand, in Comparative Example 2, the low melting point glass powder obtained in Comparative Example 1 and the refractory ceramic filler were mixed to prepare a low melting point crystallized glass composition for adhesion. In addition, its softening point, thermal expansion coefficient, crystallization upon prefiring, gelation, plastic density, power sensitivity, moisture resistance, and bonding characteristics were measured, and the results are shown in Table 4.

Raw material Raw material content (% by volume) Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Comparative Example 2 Glass 100 90 90 90 90 75 75 75 75 70 Mullite - 10 - - - 25 - - - - Eucryptite - - 10 - - - 25 - - - Zirconium Tungsten Oxide - - - 10 - - - 25 - Pyrex - - - - 10 - - 25 - Cordierite - - - - - - - 30

Test Items Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Comparative Example 2 Softening point (℃) 363 365 364 365 366 370 371 371 373 356 Thermal expansion coefficient (× 10 ^-7 / ℃) 71 65 70 59 58 65 69 58 53 68 Crystallization at prefiring (450 ℃, 30 minutes) Crystallized at the surface Crystallized Internally Crystallized Internally Crystallized Internally Crystallized at the surface Crystallized Internally Crystallized Internally Crystallized Internally Crystallized Internally No crystallization Gelation Good Good usually usually Good Good Good Good usually usually Plastic density Good Good Good usually Good Good Good Good usually usually Power Sensitivity (W at 6ms) 15 to 30 15 to 30 15 to 30 15 to 30 15 to 30 15 to 30 15 to 30 15 to 30 20-23 20-23 Moisture resistance usually Good Good usually Good Good Good Good Good Good Bonding characteristics 3.75 3.41 3.45 3.97 3.36 3.63 3.42 3.54 3.07 3.07

3. Adhesive Low melting point  Preparation of Crystallized Glass Paste

Examples 20-28:

70 parts by weight of the low melting point crystallized glass composition for bonding prepared in Examples 11 to 19 and 30 parts by weight of the vehicle solution prepared at the blending ratio (based on the weight%) of Table 5 were mixed, roll milled and degassed to obtain Melting point crystallized glass pastes were prepared. Thereafter, a low-melting-point crystallized glass paste for adhesion was coated on the alkali-free transparent glass substrate using a screen printing method to a thickness of about 4 to 60 μm, and dried by applying heat of about 120 to 180 ° C.

Comparative Example 3:

70 parts by weight of the low melting point crystallized glass composition for adhesion prepared in Comparative Example 2 and 30 parts by weight of the vehicle solution prepared at the blending ratio (based on the weight percent) of Table 5, followed by roll milling and degassing to bond low melting point crystallized glass paste Was prepared. Thereafter, a low-melting-point crystallized glass paste for adhesion was coated on the alkali-free transparent glass substrate using a screen printing method to a thickness of about 4 to 60 μm, and dried by applying heat of about 120 to 180 ° C.

division Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Comparative Example 3 Low Melting Crystallized Glass Composition Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Comparative Example 2 Vehicle

solution Suzy Ethyl cellulose 15 15 10 5 Nitrocellulose 15 10 5 Acrylic resin 20 15 10 solvent Isoamyl acetate One One One One One One One One One One α-terpineol 5 5 4 3 5 4 3 50 40 30 Butyl Carbitol Acetate 79 79 85 91 79 85 91 29 44 59

4. Review the results

The prepared low melting point crystallized glass composition is preferably blended with an ethyl cellulose-based vehicle solution and a mixing ratio of about 7: 3% by weight as shown in Table 5, but the ethyl cellulose-based vehicle solution contains a volatile component. You may mix | blend and adjust suitably within the compounding ratio range of 5: 5-9.5: 0.5 according to the viscosity of the low melting-point crystallized glass paste. In addition, the ethyl cellulose-based vehicle solution may be used alone or appropriately mixed with BCA (Butyl Carbinol Acetate), DBP (Debutyl Phthalate), etc., in addition to alpha-terpineol. The dried low melting point crystallized glass paste was fired in a nitrogen atmosphere and at a temperature of about 450 ° C. to prepare nine sample samples, and a glass composition including a conventional PbO component as a comparative sample was prepared under the same conditions as in the embodiment of the present invention. 1 type was prepared and it was made into the comparison object. The low melting point crystallized glass composition may use a method such as a dispensing method or an offset method in addition to the screen printing method. Softening point (Ts), coefficient of thermal expansion, gelation, moisture resistance, presence or absence of internal crystallization, bonding properties, and the like were measured using the respective samples prepared as described above.

The crystallized glass transition point was recorded by measuring the temperature at which the transition (time to start the mass transfer) occurs while heating the glass to a temperature of 600 ℃ at a temperature increase rate of 10 ℃ / min, the crystallized glass softening point is the crystallization The glass was prepared in a block shape and polished to a size of 3 mm x 3 mm x 19 mm, and then the temperature at which softening (time from the solid phase to the liquid phase) occurred while the temperature was raised to 600 ° C. at a temperature rising rate of 10 ° C./min was measured and recorded. The presence or absence of crystallization is recorded by visually inspecting whether or not crystallization occurs at a temperature of 700 ° C. in the process of measuring the transition point, and the water resistance is measured by distilled water at 30 ° C. after polishing the sample sample to a size of 4 mm × 4 mm. After immersion for 24 hours, color change of fresh water solution and inductively coupled plasma (ICP) component analysis were observed. The coefficient of thermal expansion (TEC) is made of molten crystallized glass in the form of a block, polished to a size of 3 mm × 3 mm × 15 mm, and then the specimen is expanded between 30 and 250 ° C. while raising the temperature to 300 ° C. at a temperature rising rate of 10 ° C./min. The degree was measured.

As can be seen from the experimental results of Table 1 and Table 2, the crystallized glass transition point and softening point decrease with addition of V ₂ O ₅ , and the dielectric constant and coefficient of thermal expansion are increased, and Fe ₂ O ₃ is increased. , P ₂ O ₅ It can be seen that the transition point and softening point of the crystallized glass increases as the content increases, unlike in general crystallized glass. In addition, the lower the SiO ₂ and Al ₂ O ₃ content, the lower the moisture resistance, and if the content is 10 mol% or more, the firing density after firing is lowered.

The low melting point crystallized glass composition of the present invention satisfies the relationship of TiO ₂ / Fe ₂ O ₃ ratio of 0.01 to 0.5 and (CuO + Fe ₂ O ₃ ) / V ₂ O ₅ = 0.01 to 0.3 on a molar ratio basis.

In addition, BaO, ZnO, P ₂ O ₅ Partial replacement of the component from the B ₂ O ₃ component reduces the coefficient of thermal expansion at similar firing temperatures when properly mixed and used.

And when a part of the main components of the low melting point crystallized glass composition is added to replace the MgO, SrO, ZrO ₂ , TiO ₂ has the effect as an internal crystallization aid that can control the high temperature flowability.

In addition, Fe ₂ O ₃ , CuO, SeO, V ₂ O ₅ , Sb ₂ O ₃ , Nd ₂ O ₃ are the main components or additives to increase the absorbance by affecting the color development and absorbance of the mother glass through a redox reaction Do it.

The viscosity of the low melting point crystallized glass paste for bonding is suitably adjusted to meet the appropriate viscosity for the device coated on the material and adjusted according to the ratio between the resin and the solvent and the ratio between the vehicle solution and the low melting point glass composition for bonding. Can be. Known additives such as antifoaming agents and dispersants may be added to the low melting point crystallized glass paste for adhesion in connection with the crystallized glass paste. In addition, a known method using a rotary mixer provided with a stirring pin, a roll mill, a ball mill, or the like, may be used for producing the crystallized glass paste for adhesion.

Al ₂ O ₃ / V ₂ O ₅ of the low melting crystallized glass has a molar ratio of 1.3 / 55.2, that is, 0.024, and (Fe ₂ O ₃ + CuO) / V ₂ O ₅ is (6.3 + 0.8) /55.2, that is, 0.129 Has a molar ratio of.

A low melting point crystallized glass composition for adhesion is prepared by adding 26% by volume of mullite and 2% by volume of cryptite as a refractory ceramic filler to 72% by volume of low melting crystallized glass. The low melting point crystallized glass composition for adhesion is measured for the glass transition point, softening point by a differential thermal analyzer (DTA) to reveal that the glass transition point is 337 ° C and the load softening point is 362 ° C.

A low melting point crystallized glass paste for bonding is prepared by mixing a vehicle solution and a low melting point crystallized glass composition for bonding as described below. The low melting point crystallized glass paste for adhesion is obtained by adding a vehicle solution to the low melting point crystallized glass composition for adhesion at a mass ratio of 86 to 14 and mixing with a roll mill. The viscosity of the obtained low melting point crystallized glass paste for adhesion is measured by a B-type viscometer (HDBVII + from Brookfield Engineering Laboratories Inc.) to reveal that the viscosity is 20 to 60 Pa · s.

The adhesion temperature is measured as follows. Al ₂ O ₃ / V ₂ O ₅ of the aforementioned low melting point crystallized glass has a molar ratio of 0.024 to 0.050, and (Fe ₂ O ₃ + CuO) / V ₂ O ₅ has a molar ratio of 0.010 to 0.129. When the low melting point crystallized glass composition for bonding with the mixed low melting point crystallized glass and the refractory ceramic filler is fired at a preliminary firing temperature of 300 to 450 ° C., deposition of crystals is not observed in any crystallized glass. And since the low melting point crystallized glass has a softening point of 330-376 degreeC, even the low melting point crystallized glass composition for adhesion | attachment obtained by mixing with a refractory ceramic filler can fully flow at 420 degrees C or less.

5 to 15% nitrocellulose as a resin, 3 to 5% terpineol as solvent, 79 to 91% butyl carbitol acetate and 1% iso, heating at 80 ° C. for 2 hours according to the blending ratio of Table 5 Low melting point crystallized glass paste for adhesion prepared by stirring amyl acetate, 10-20% methyl methacrylate as resin, 30-50% terpineol as solvent, and 29 ~ by heating at 80 ° C for 2 hours. The low melting point crystallized glass paste for adhesion prepared by stirring 59% butyl carbitol acetate and 1% isoamyl acetate was added in a mass ratio of 70 to 30 for the low melting point crystallized glass composition and vehicle solution, respectively. Mixed by roll mill to obtain. The viscosity of the paste measured by the B-type viscometer is in the range of 20 to 60 Pa · s.

It was found by measuring by a thermomechanical analyzer (TMA) that the low melting point crystallized glass composition for adhesion had a coefficient of thermal expansion of 55 to 75 × 10 ⁻⁷ / ° C.

Although the present invention has been described through the above embodiments as described above, the present invention is not necessarily limited thereto, and various modifications can be made without departing from the scope and spirit of the present invention. In addition, many modifications may be made to adapt a particular situation and material to the teachings of the invention without departing from the essential scope thereof. Therefore, the protection scope of the present invention should be construed as including all embodiments falling within the scope of the claims appended to the present invention.

Claims (10)

V ₂ O ₅ 35-65 mol%,
P ₂ O ₅ 0.1-35 mol%,
SrO 0.1-25 mol%,
0.1-30 mol% of a mixture of Fe ₂ O ₃ and Sb ₂ O ₃ ,
0.1-25 mol% of at least one metal oxide selected from the group consisting of Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , SnO, TeO ₂ , Bi ₂ O ₂ , and Tl ₂ O,
0.1-20 mol% of at least one alkaline earth oxide selected from the group consisting of MgO, CaO, BaO, and ZnO, and
0.1-20 mol% of one or more transition metal oxides selected from the group consisting of ZrO ₂ , TiO ₂ , MnO, NiO, CuO, SeO, and Nd ₂ O ₃ ,
Tl ₂ O and CuO and Nd ₂ O ₃ , and the molar ratio TiO ₂ / Fe ₂ O ₃ ratio meets the relationship of 0.01 to 0.5, and (CuO + Fe ₂ O 3) / V ₂ O ₅ = 0.01 to 0.3 Crystallized glass for adhesion, characterized in that. delete delete delete A crystallized glass composition for adhesion comprising 70 to 95% by volume of the crystallized glass of claim 1 and 5 to 30% by volume of the refractory ceramic filler.
6. The refractory ceramic filler according to claim 5, wherein the refractory ceramic filler is composed of at least one selected from the group consisting of Pyrex, silica, cordierite, aluminum titanate, mullite, euclitite, zirconium tungsten oxide and mullite. Crystallized glass composition for adhesion | attachment.
60 to 90% by weight of the low-melting-point crystallized glass composition of claim 5 and 10 to 40% by weight of the vehicle solution, wherein the vehicle solution comprises a resin and a solvent.
A low-melting-point crystallized glass composition of claim 6 and 10 to 40% by weight of the vehicle solution, wherein the vehicle solution is a crystallized glass paste for adhesion, characterized in that consisting of a resin and a solvent.
A panel in which an organic light emitting diode is interposed between two substrates,
At least one of the two substrates is transparent,
The two substrates are bonded by the crystalline glass paste for adhesion of claim 7 characterized in that the organic light emitting diode panel.
A panel in which an organic light emitting diode is interposed between two substrates,
At least one of the two substrates is transparent,
The two substrates are bonded by the crystalline glass paste for adhesion of claim 8, characterized in that the organic light emitting diode panel.

Images