Glass sealant as well as preparation method and application thereof

Abstract

The invention relates to the technical field of semiconductor packaging, and discloses a glass sealant and a preparation method and application thereof. The glass powder comprises the first glass powder and the second glass powder, the first glass powder and the second glass powder can be mixed for use and can also be independently used, and the softening point temperature of the first glass powder is lower than that of the second glass powder. The OLED device packaged by using the glass sealant provided by the invention not only has a good effect of isolating water vapor and air, but also has excellent anti-falling performance, and can meet the sealing requirements of miniaturized and lightweight electronic devices.

Description

Technical Field

[0001] The present application belongs to the field of semiconductor packaging technology, and specifically relates to a glass sealant and a preparation method and application thereof. Background Art

[0002] Electronic components such as organic light emitting diodes (OLEDs) and some semiconductor chips are sensitive to water vapor and air. When exposed to water vapor and air, their performance will be reduced and their lifespan will be shortened. Therefore, they need to be sealed so that they can be used under conditions of isolation from water vapor and air.

[0003] At present, glass sealants are used in the industry to seal electronic components. The sealing process is to print the glass sealant on the glass cover, dry it, pre-sinter it, and then fit it with the sealed component (for example, the glass substrate), and then perform laser welding to achieve the purpose of sealing. With the miniaturization and lightweight of electronic devices, the size of electronic components is getting smaller, the weight is getting lighter, and the thickness is getting thinner. The original glass sealant can no longer meet the needs.

[0004] Therefore, it is urgent to provide a novel glass sealant to meet the needs. Summary of the invention

[0005] In view of the above problems, the present application provides a glass sealant and a preparation method and application thereof, aiming to achieve excellent sealing through the glass sealant to achieve effective isolation of water vapor and air, as well as excellent anti-fall effect.

[0006] In a first aspect, the present application provides a glass sealant, which comprises the following components based on the total weight of the glass sealant being 100%:

[0007] Glass powder: 45%~85%;

[0008] Composite ceramic powder: 2% to 15%;

[0009] Organic carrier: 12% to 40%;

[0010] Modified sintering aid: 1%~5%;

[0011] The glass powder includes at least one of a first glass powder and a second glass powder, and the softening point temperature of the first glass powder is lower than the softening point temperature of the second glass powder.

[0012] The embodiment of the present application provides a glass sealant, which has excellent pre-sintering performance, laser welding performance and strength. Therefore, the laser sintering glass sealant can achieve good adhesion with both the glass substrate and the glass cover plate. In this way, the device encapsulated using the glass sealant provided by the embodiment of the present application not only has a good effect of isolating water vapor and air, but also has excellent anti-drop performance, which can meet the sealing needs of miniaturized and lightweight electronic devices.

[0013] In a second aspect, the present application provides a packaging structure, including a glass substrate, a glass cover plate and the above-mentioned glass sealant, wherein the glass substrate and the glass cover plate are arranged opposite to each other, and the glass substrate and the glass cover plate are sealed by the above-mentioned glass sealant to form an accommodating space.

[0014] The embodiment of the present application provides a packaging structure, which is packaged by using the above-mentioned glass sealant. It not only has a good effect of isolating water vapor and air, but also has excellent anti-drop performance. The comprehensive performance of the packaging structure is good.

[0015] In a third aspect, the present application provides a method for preparing the above-mentioned glass sealant, comprising the following steps:

[0016] The glass powder, the composite ceramic powder, the organic carrier and the modified sintering aid are uniformly mixed, ground and filtered to obtain the glass sealant.

[0017] The embodiment of the present application provides a method for preparing a glass sealant, which can prepare a laser-sintered glass sealant with excellent pre-sintering performance, laser welding performance and high strength. Therefore, when the laser-sintered glass sealant is used for device packaging, it not only has a good effect of isolating water vapor and air, but also has excellent anti-drop performance, which can meet the sealing needs of miniaturized and lightweight electronic devices, and the preparation method of the glass sealant is simple and easy to implement.

[0018] In a fourth aspect, the present application provides a packaging method of a packaging structure, comprising the following steps:

[0019] The glass sealant is applied on the glass cover plate to form a sealing pattern, and then dried and pre-sintered in sequence to form a dense sealing pattern attached to the glass cover plate;

[0020] After the side of the glass cover plate with the dense sealing pattern is bonded to the side of the glass substrate, the glass sealant is irradiated with laser until it melts to obtain a packaging structure.

[0021] The embodiment of the present application provides a packaging method for a packaging structure, which not only has a good effect of isolating water vapor and air, but also has excellent anti-drop performance, can meet the sealing needs of miniaturized and lightweight electronic devices, and the packaging method of the packaging structure is simple and easy to implement.

[0022] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Various other advantages and benefits will become apparent to those of ordinary skill in the art by reading the detailed description of the optional embodiments below. The accompanying drawings are only used for the purpose of illustrating the optional embodiments and are not to be considered as limiting the present application. Moreover, the same reference numerals are used throughout the drawings to represent the same components. In the drawings:

[0024] Figure 1 A schematic diagram of a packaging structure of an OLED device provided in an embodiment of the present application;

[0025] Figure 2 A process flow chart of preparing a glass sealant provided in an embodiment of the present application;

[0026] Figure 3 A process flow chart of a preparation process of an OLED device provided in an embodiment of the present application;

[0027] Figure 4 This is a microstructure diagram of the glass sealant after laser sintering provided in Example 1 of the present application;

[0028] Figure 5 This is a microstructure diagram of the glass glue after laser sintering provided in Comparative Example 1;

[0029] Figure 6 A microstructure diagram of a glass substrate-glass sealant-glass cover plate subjected to a 4.2 g steel ball drop resistance test provided in Example 1 of the present application;

[0030] Figure 7 A photo of a 4.2g steel ball drop resistance test sample provided in Example 1 of the present application;

[0031] Figure 8 A microstructure diagram of a glass substrate-glass sealant-glass cover plate subjected to a 10.0 g steel ball drop resistance test provided in Example 1 of the present application;

[0032] Fig. 9 This is a photo of the 10.0g steel ball drop test sample provided in Example 1 of the present application. DETAILED DESCRIPTION

[0033] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0034] In this application, the term "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0035] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b or c", or "at least one of a, b and c", can all represent: a, b, c, ab (i.e. a and b), ac, bc or abc, where a, b, c can be single or multiple, respectively.

[0036] It should be understood that in the various embodiments of the present application, the size of the serial number of each process does not mean the order of execution, some or all of the steps can be executed in parallel or sequentially, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0037] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.

[0038] The weight of the relevant components mentioned in the embodiment description of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the embodiment description of the present application, it is within the scope disclosed in the embodiment description of the present application. Specifically, the mass in the embodiment description of the present application can be a well-known mass unit such as μg, mg, g, kg, etc.

[0039] The terms "first", "second", etc. are used only for descriptive purposes to distinguish objects such as substances from each other, and should not be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. For example, without departing from the scope of the embodiments of the present application, the first XX may also be referred to as the second XX, and similarly, the second XX may also be referred to as the first XX. Thus, a feature defined as "first", "second", etc. may explicitly or implicitly include one or more of the features.

[0040] In a first aspect, an embodiment of the present application provides a glass sealant, which includes the following components based on 100% weight of the glass sealant: glass powder: 45% to 85%; composite ceramic powder: 2% to 15%; organic carrier: 12% to 40%; modified sintering aid: 1% to 5%.

[0041] The glass powder includes a first glass powder and a second glass powder. The first glass powder and the second glass powder can be mixed and used or used alone.

[0042] In actual applications, the glass sealant provided in the embodiments of the present application can be used to package glass plates and glass plates, glass plates and ceramic plates, ceramic plates and ceramic plates, glass plates and silicon wafers, ceramic plates and silicon wafers, etc. There is no specific limitation on the usage scenarios of the glass sealant here, and it is subject to actual application.

[0043] When the glass sealant is used to encapsulate the glass plates, illustratively, electronic components can be accommodated in the internal space formed by the glass plates, and the electronic components include but are not limited to OLED semiconductors, short-wave ultraviolet rays (Ultra Violet C Radiation, UVC), light emitting diodes (Light Emitting Diode, LED), micro electromechanical systems (Micro Electro Mechanical System, MEMS), semiconductor lasers (Laser Diode, LD), semiconductor chips, photovoltaic heterojunction (Hetero Junction Technology, HJT) solar cells, perovskite solar cells, dye-sensitized solar cells, etc.

[0044] Figure 1 FIG. 1 shows a schematic diagram of a structure in which a glass cover plate and a glass substrate are sealed by a glass sealant. Figure 1As shown, first, an OLED semiconductor 2 is manufactured on a glass substrate 1, and a glass sealant 3 is coated on the periphery of a glass cover plate 4 to form a sealing pattern, which is then dried and pre-sintered to form a dense sealing pattern; then, the dense sealing pattern is directed toward the glass substrate 1 and bonded to the glass substrate 1, and then the glass cover plate 4 is irradiated with a laser to melt the glass sealant 3 from one side of the glass cover plate 4, and the molten glass sealant 3 welds and seals the glass cover plate 4 and the glass substrate 1.

[0045] Among the components of the glass sealant, the glass powder has the functions of sintering to be dense and bonding.

[0046] The modified sintering aid can help the sintering of the glass powder, making the sintered glass powder denser.

[0047] The composite ceramic powder is used to adjust the thermal expansion coefficient of the glass sealant.

[0048] The organic carrier is used to disperse glass powder, composite ceramic powder and modified sintering aid.

[0049] As an example, the first glass powder and the second glass powder in the glass sealant provided in the embodiment of the present application can be mixed and used, and good sealing performance can be obtained by adjusting the pre-sintering process and the laser welding process.

[0050] As another example, the first glass powder and the second glass powder in the glass sealant provided in the embodiment of the present application can be used separately, and good sealing performance can be obtained by adjusting the pre-sintering process and the laser welding process.

[0051] Among them, the first glass powder includes the following components according to the molar ratio of 100%: B2O3: 15.5%~30%; ZnO: 20%~40%; TeO2: 10%~40%; V2O5: 10%~30%; CuO: 4.5%~15%; Bi2O3: 0.1%~5%; SiO2: 0.1%~5%.

[0052] Exemplarily, the molar content of B2O3 can be 15.5%, 20% or 30%, etc., the molar content of ZnO can be 20%, 25%, 30%, 35% or 40%, etc., the molar content of TeO2 can be 10%, 20%, 30% or 40%, etc., the molar content of V2O5 can be 10%, 12%, 15%, 20% or 30%, etc., the molar content of CuO can be 4.5%, 8%, 13% or 15%, etc., the molar content of Bi2O3 can be 0.1%, 0.5%, 1%, 3% or 5%, etc., the molar content of SiO2 can be 0.1%, 0.5%, 1%, 3% or 5%, etc.

[0053] The softening point temperature of the first glass powder may range from 314°C to 370°C. For example, the softening point temperature of the first glass powder may be 314°C, 320°C, 330°C, 340°C, 350°C, 360°C or 370°C.

[0054] Among them, the second glass powder includes the following components according to the molar ratio of 100%: B2O3: 5%~40%; ZnO: 30%~60%; TeO2: 1%~4.9%; V2O5: 5%~30%; CuO: 5%~30%; SiO2: 1%~10%; Fe2O3: 0.1%~5%; MnO2: 0.1%~5%.

[0055] Exemplarily, the molar content of B2O3 can be 5%, 10%, 20%, 30% or 40%, etc., the molar content of ZnO can be 30%, 35%, 40%, 45%, 50%, 55% or 60%, etc., the molar content of TeO2 can be 1%, 3% or 4.9%, etc., the molar content of V2O5 can be 5%, 10%, 15%, 20% or 30%, etc., the molar content of CuO can be 5%, 10%, 20% or 30%, etc., the molar content of SiO2 can be 1%, 2%, 4%, 6%, 8% or 10%, etc., the molar content of Fe2O3 can be 0.1%, 1%, 2%, 4% or 5%, etc., the molar content of MnO2 can be 0.1%, 1%, 2%, 4% or 5%, etc.

[0056] The softening point temperature of the second glass powder may range from 376°C to 430°C. For example, the softening point temperature of the second glass powder may be 376°C, 380°C, 390°C, 400°C, 410°C or 420°C.

[0057] In applications, there is no specific limitation on the shapes of the first glass powder and the second glass powder. For example, the shapes of the first glass powder and the second glass powder can be at least one of spherical, quasi-spherical, granular, and flaky.

[0058] The properties and functions of the specific oxides in the glass powder of the present application are briefly described below.

[0059] B2O3 is a skeleton generator of the glass powder structure. The molar proportions of B2O3 in the first glass powder and the second glass powder of the present application are 15.5% to 30% and 5% to 40% respectively.

[0060] As a network intermediate, ZnO can adjust the density of the network structure of the glass powder and improve the thermal expansion coefficient of the glass powder. The molar proportions of ZnO in the first glass powder and the second glass powder of the present application are 20% to 40% and 30% to 60% respectively.

[0061] TeO2 is a glass former. The molar proportions of TeO2 in the first glass powder and the second glass powder of the present application are 10% to 40% and 1% to 4.9%, respectively.

[0062] As a glass former, V2O5 can reduce the glass transition temperature (Tg) of the glass powder and increase the light absorption capacity. The molar proportions of V2O5 in the first glass powder and the second glass powder of the present application are 10% to 30% and 5% to 30% respectively.

[0063] CuO, as a divalent network exometallic oxide, can improve the light absorption performance of the glass powder. The molar proportions of CuO in the first glass powder and the second glass powder of the present application are 4.5% to 20% and 5% to 30% respectively.

[0064] SiO2 is a glass former and has the function of adjusting Tg and reducing the thermal expansion coefficient. The molar proportions of SiO2 in the first glass powder and the second glass powder of the present application are 0.1% to 5% and 1% to 10% respectively.

[0065] Fe2O3 has the functions of absorbing light and adjusting the thermal expansion coefficient. The molar ratio of Fe2O3 in the second glass powder of the present application is 0.1% to 5%.

[0066] MnO2 has the functions of absorbing light and adjusting the thermal expansion coefficient. The molar ratio of MnO2 in the second glass powder of the present application is 0.1% to 5%.

[0067] In application, the modified sintering aid provided in the embodiment of the present application is to coat a layer of surfactant on the surface of the light absorbing material to improve the dispersion performance of the light absorbing material in the glass sealant. The light absorbing material can be one or a combination of two or more of iron manganese black, copper chrome black, iron chrome black, silicon carbide, tungsten powder, carbon powder, and graphite powder.

[0068] The surfactant may be one or a combination of two or more of polyether-modified silicone, nonionic fluorocarbon, and anionic fluorocarbon surfactants.

[0069] The modified sintering aid may be in the shape of particles, spheres, quasi-spheres, flakes, or a combination of two or more thereof.

[0070] The particle size of the modified sintering aid may range from 0.5 μm to 6 μm. For example, the particle size of the modified sintering aid may be 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm or 6 μm.

[0071] In applications, the composite ceramic powder provided in the embodiments of the present application can be one or a combination of two or more of zirconium tungstate (Zr(WO4)2), zirconium phosphotungstate (Zr2(WO4)(PO4)2), zirconium vanadate (ZrV2O7), etc. The composite ceramic powder can be purchased from a partner to obtain a coarse powder, and then crushed and ground to obtain the required composite ceramic powder. The D50 particle size of the composite ceramic powder is 0.8μm. It should be understood that D50 specifically refers to the particle size value corresponding to the cumulative distribution percentage from small to large in the particle size distribution of the composite ceramic powder reaches 50%. The composite ceramic powder can adjust the thermal expansion coefficient of the glass sealant.

[0072] In applications, the organic carrier provided in the embodiments of the present application may include an organic solvent, a polymer, a wetting and dispersing agent, a thixotropic agent, and other functional additives.

[0073] Based on 100 parts by weight of the organic carrier, the organic solvent comprises 50 to 95 parts; the polymer comprises 1 to 20 parts; the wetting and dispersing agent comprises 0.1 to 10 parts; and other functional additives comprise 0.1 to 20 parts.

[0074] Exemplarily, the organic solvent can be 50 parts, 60 parts, 70 parts, 80 parts or 95 parts, etc., the polymer can be 1 part, 5 parts, 10 parts, 15 parts or 20 parts, etc., the wetting and dispersing agent can be 0.1 part, 1 part, 5 parts, 8 parts or 10 parts, etc., and other functional additives can be 0.1 part, 1 part, 10 parts, 15 parts or 20 parts, etc.

[0075] The above-mentioned organic solvent can be at least one of pinene alcohol, tributyl citrate, butyl carbitol, butyl carbitol acetate, alcohol ester dodecaol, alcohol ester hexadecane, ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, dodecanol ester, diethylene glycol butyl ether, diethylene glycol monooctyl ether, triethylene glycol butyl ether, tripropylene glycol methyl ether, terpenes, etc.

[0076] The polymer may be selected from at least one of cellulose and its derivatives, epoxy resin, acrylic resin, alkyd resin, polyester resin and the like.

[0077] The wetting and dispersing agent can be selected from one or a mixture of two or more of fatty acids, amide derivatives of fatty acids, ester derivatives of fatty acids, polyethylene wax, and polyethylene glycol.

[0078] The above-mentioned other auxiliary agents may be anti-settling agents, surfactants, plasticizers and the like.

[0079] Second, refer to Figure 2 As shown, the embodiment of the present application provides a method for preparing a glass sealant, comprising the following steps:

[0080] S01. Processing glass raw materials to obtain glass powder.

[0081] The specific steps are as follows:

[0082] Step 1: Weigh each glass powder raw material component according to the glass powder formula provided in this application.

[0083] Step 2: Mix and melt the glass raw material components to obtain molten glass.

[0084] Step 3: quench the molten glass to obtain glass particles.

[0085] Step 4: crush and grind the glass particles to obtain glass powder.

[0086] In application, the method of grinding the glass particles is not specifically limited. For example, the glass particles can be ground by ball milling, sand milling, air flow milling, etc.

[0087] There is no specific limitation on the particle size of the glass powder. For example, the particle size of the glass powder may range from 0.1 μm to 6.0 μm. Specifically, the particle size of the glass powder may be 0.1 μm, 1.0 μm, 2.0 μm, 3.0 μm or 6.0 μm.

[0088] S02. Processing the sintering aid raw material to obtain a modified sintering aid.

[0089] The specific steps are as follows:

[0090] Step 1: Weigh each sintering aid raw material component according to the above formula provided in this application.

[0091] Step 2: Place the weighed sintering aid raw material components in an environment of 25°C to 60°C for mixing reaction.

[0092] It should be noted that in some embodiments, the mixing reaction is carried out at 25°C, in some embodiments, the mixing reaction is carried out at 45°C, and in some embodiments, the mixing reaction is carried out at 60°C.

[0093] Step 3: After the reaction is completed, filter and dry to obtain a modified sintering aid.

[0094] S03. Use Zr2(WO4)(PO4)2 as composite ceramic powder.

[0095] It should be noted that the Zr2(WO4)(PO4)2 coarse powder was purchased from a partner, and the purchased composite ceramic coarse powder was crushed and ground to obtain Zr2(WO4)(PO4)2 used as composite ceramic powder.

[0096] There is no specific limitation on the particle size of the composite ceramic powder. For example, the particle size of the composite ceramic powder may range from 0.1 μm to 6.0 μm. Specifically, the particle size of the composite ceramic powder may be 0.1 μm, 1.0 μm, 2.0 μm, 3.0 μm, 4.0 μm, 5.0 μm, or 6.0 μm.

[0097] S04. Processing the organic carrier raw material to obtain an organic carrier.

[0098] The specific steps are as follows:

[0099] Step 1: Weigh each raw material component of each organic carrier according to the above formula provided in this application.

[0100] Step 2: Mix the weighed raw material components of the organic carrier, and then react at 40° C. to 80° C. to obtain the organic carrier.

[0101] S05. The glass powder obtained in step S01, the modified sintering aid obtained in step S02, the composite ceramic powder obtained in step S03, and the organic carrier obtained in step S04 are weighed according to the above proportions provided in the present application, stirred and mixed, ground with a three-roll grinder, and then filtered to obtain a laser sintering glass sealant for OLED device packaging.

[0102] The preparation method of the glass sealant provided in the embodiment of the present application is simple and easy to implement, which is conducive to industrial production.

[0103] In a third aspect, an embodiment of the present application provides an OLED device encapsulated using the above-mentioned glass sealant.

[0104] like Figure 1 As shown, the OLED device includes a glass substrate 1, a glass cover plate 4, an OLED semiconductor 2 and the above-mentioned glass sealant 3. The glass substrate 1 and the glass cover plate 4 are arranged opposite to each other. The peripheries of the glass substrate 1 and the glass cover plate 4 are welded and sealed by the glass sealant 3 to form an accommodating space. The OLED semiconductor 2 is arranged in the accommodating space.

[0105] In applications, the OLED semiconductor 2 may be an OLED semiconductor chip or the like.

[0106] The embodiment of the present application provides an OLED device encapsulated using the glass sealant of the present application. The OLED device is sealed by laser sintering glass sealant, which can effectively block water vapor and air from contacting the OLED semiconductor, thereby improving the service life and reliability of the OLED semiconductor.

[0107] Combine the following Figure 1 and Figure 3, further describing the method for using the glass sealant provided in the embodiment of the present application, and the OLED device encapsulated by the method.

[0108] like Figure 3 As shown, the specific steps are as follows:

[0109] S1. Fabrication of OLED semiconductors on glass substrates.

[0110] S2. A glass sealant is applied to the periphery of the glass cover plate to form a sealing pattern, and then dried and pre-sintered in sequence to form a dense sealing pattern attached to the periphery of the glass cover plate.

[0111] In applications, there is no specific limitation on the coating method of the glass sealant. For example, the glass sealant can be formed into a pattern of glass sealant for glass packaging by screen printing, dispensing, etc.

[0112] The above drying temperature is not specifically limited, and illustratively, the drying temperature range may be set to 120° C. to 150° C. Specifically, the drying temperature may be 120° C., 130° C., 135° C., 140° C. or 150° C., etc.

[0113] The drying time is not specifically limited, and for example, the drying time can be set in the range of 10 minutes to 30 minutes. Specifically, the drying time can be 10 minutes, 15 minutes, 20 minutes, 25 minutes or 30 minutes.

[0114] The pre-sintering temperature is not specifically limited, and for example, the pre-sintering temperature can be set in the range of 350° C. to 500° C. Specifically, the pre-sintering temperature can be 350° C., 400° C., 420° C., 480° C. or 500° C., etc.

[0115] It should be noted that, during the above-mentioned drying process at 120° C. to 150° C., part of the organic solvent volatilizes, so that the glass sealant forms a film and adheres to the glass cover plate.

[0116] During the pre-sintering process at 350° C. to 500° C., the solvent in the organic vehicle is completely volatilized, the resin is decomposed, and the glass powder is softened and partially melted to form a dense glass sealant pattern.

[0117] S3. After the side of the glass cover plate with the dense glass sealant pattern is bonded to the side of the glass substrate with the OLED semiconductor, a laser is used to irradiate the dense glass sealant pattern. The glass seal absorbs the laser energy and the temperature rises instantly, so that the glass sealant is fully melted. The molten glass sealant welds the glass cover plate and the glass substrate together to achieve a sealing effect.

[0118] It should be noted that in some usage scenarios, the above-mentioned laser welding is operated in a vacuum environment, in some usage scenarios, the above-mentioned laser welding is operated in an inert gas protection environment, and in some usage scenarios, the above-mentioned laser welding is operated in an atmospheric environment. The operating environment of laser welding is determined according to the performance requirements of the sealed electronic components.

[0119] The following uses a number of specific embodiments to illustrate the preparation method and application of the glass sealant of the present application and the glass sealant of the comparative example.

[0120] Example 1

[0121] A glass sealant for sealing an OLED device, comprising the following components in a total weight of 100 parts: glass powder: 65.0 parts, composite ceramic powder: 10.0 parts, modified sintering aid: 4.0 parts, organic carrier: 21.0 parts, wherein the weight of the first glass powder is 6 parts, the weight of the second glass powder is 59 parts, and the total weight of the first glass powder and the second glass powder is 65 parts.

[0122] The first glass powder includes the following components based on a molar ratio of 100%: B2O3: 15.5%, ZnO: 22%, TeO2: 40%, V2O5: 15%, CuO: 4.5%, Bi2O3: 2%, SiO2: 1%. The softening point temperature of the first glass powder is 314°C.

[0123] According to the above first glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the required first glass powder, whose D50 particle size is 0.8μm.

[0124] The second glass powder comprises the following components according to a molar ratio of 100%: B2O3: 5%, ZnO: 60%, TeO2: 2%, V2O5: 20%, CuO: 8%, SiO2: 2%, Fe2O3: 1.5%, and MnO2: 1.5%. The softening point temperature of the second glass powder is 430°C.

[0125] According to the above second glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the desired second glass powder, whose D50 particle size is 0.8μm.

[0126] Wherein, based on 100% by weight of the organic carrier, it includes the following components: rosin resin: 10%, acrylic resin: 10%, pine alcohol: 25%, dibutyl sebacate: 52%, fatty acid: 1%, polydimethylsiloxane: 2%.

[0127] According to the above formula, the organic carrier raw materials were weighed in sequence and mixed at 60° C. for 1 h to obtain the desired organic carrier.

[0128] The coarse composite ceramic powder Zr2(WO4)(PO4)2 was purchased from a partner. The coarse composite ceramic powder was further crushed and ground to obtain the required composite ceramic powder, whose D50 particle size was 0.8 μm.

[0129] According to the formula ratio, weigh the first glass powder: 6g, the second glass powder: 59g, the modified sintering aid: 4.0g, Zr2(WO4)(PO4)2: 10g, and the organic carrier: 21.0g, mix them, centrifuge them, and then grind them using a three-roll mill to obtain 100g of glass sealant.

[0130] Among them, the fineness of the glass sealant is less than 4μm.

[0131] Pre-sintering: screen print the prepared glass sealant onto the glass substrate to form a glass sealant ring, and pre-sinter at 420°C for 30 minutes.

[0132] The morphology of the pre-sintered glass glue sealing ring was detected under a microscope, and the width was 460μm and the height was 5μm.

[0133] Laser sintering: Place the glass cover plate on the pre-sintered glass glue sealing ring, and use a laser with a wavelength of 810nm to irradiate the glass glue sealing ring from one side of the glass cover plate. The glass glue sealing ring absorbs the laser energy and is melted and welded to the glass substrate and the glass cover plate.

[0134] Among them, the sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover.

[0135] like Figure 4 As shown, the cross-sectional morphology after pre-sintering was observed using a scanning electron microscope (SEM) and it was found that the glass sealant and the glass substrate, as well as the glass sealant and the glass cover plate were all well welded without bubbles.

[0136] Tensile test: The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover. Use double-sided tape to stick on the glass cover and glass substrate, and use a tensile machine to vertically stretch until it breaks, and the tensile force is more than 70N.

[0137] Anti-drop test: A 4.2g steel ball and a 10.0g steel ball were dropped from a height of 150cm onto the laser sintered and welded glass substrate-glass sealant-glass cover plate samples to test the anti-drop performance of the glass sealant. The steel ball was controlled to fall accurately on the position of the glass sealant sealing ring, and then a SEM microscope was used to observe the cross-section of the steel ball at the anti-drop point, as well as the bonding conditions between the glass sealant and the glass substrate, and between the glass sealant and the glass cover plate.

[0138] The results show that: under the impact of the steel ball, the glass substrate and the glass cover plate are broken, but the interface between the glass substrate and the glass cover plate and the glass sealant is well bonded, and no interface separation phenomenon is found. The microscopic morphology of the interface between the glass sealant and the glass substrate, and the glass sealant and the glass cover plate of the 4.2g steel ball and the 10.0g steel ball are analyzed by SEM, as shown in the figure. Figure 6 and Figure 8 As shown, it can be seen that the interface is well bonded without cracks or separation.

[0139] at the same time, Figure 7 and Fig. 9 The actual pictures of the glass sealant and the spliced ​​broken glass after the drop test of the 4.2g steel ball and the 10.0g steel ball are shown respectively. Figure 7 and Fig. 9 The black part is glass sealant, and the transparent part is glass, forming a sandwich structure. The steel ball falls against the black frame, and then the glass breaks. The broken glass is pieced together to form a real photo.

[0140] Water resistance test: apply glass sealant to a glass sheet, place it in a muffle furnace and bake it at 300°C for 30 minutes, then scrape off the powder and place it in a mold with a diameter of 5 mm to press it into shape, and then sinter it at 420°C to form a total of 15 cylinders. The total weight of the 15 cylinders is 4.660g. Place the 15 cylinder samples in a beaker, add deionized water, and then place the beaker in a 90°C water bath for boiling. After boiling for 24 hours, dry and weigh it, and its weight is 4.660g. No weight reduction of the glass sealant was found, indicating that the weight reduction of the glass sealant is less than the accuracy of the balance, indicating that the glass sealant is very stable in hot water.

[0141] Example 2

[0142] A glass sealant for sealing an OLED device includes the following components based on 100 parts by total weight: 65.0 parts of glass powder, 10.0 parts of composite ceramic powder, 4.0 parts of modified sintering aid, and 21.0 parts of organic carrier. Among them, the weight of the first glass powder is 59 parts, the weight of the second glass powder is 6 parts, and the total weight of the first glass powder and the second glass powder is 65 parts.

[0143] The first glass powder includes the following components based on a molar ratio of 100%: B2O3: 15.5%, ZnO: 22%, TeO2: 40%, V2O5: 15%, CuO: 4.5%, Bi2O3: 2%, SiO2: 1%. The softening point temperature of the first glass powder is 314°C.

[0144] According to the above first glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the required first glass powder, whose D50 particle size is 0.8μm.

[0145] The second glass powder comprises the following components according to a molar ratio of 100%: B2O3: 5%, ZnO: 60%, TeO2: 2%, V2O5: 20%, CuO: 8%, SiO2: 2%, Fe2O3: 1.5%, and MnO2: 1.5%. The softening point temperature of the second glass powder is 430°C.

[0146] According to the above second glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the desired second glass powder, whose D50 particle size is 0.8μm.

[0147] The organic carrier comprises the following components based on 100% by weight: rosin resin: 10%, acrylic resin: 10%, pine alcohol: 25%, dibutyl sebacate: 52%, fatty acid: 1%, and polydimethylsiloxane: 2%.

[0148] According to the above formula, the organic carrier raw materials were weighed in sequence, and mixed at 60° C. for 1 h to obtain the desired organic carrier.

[0149] The coarse composite ceramic powder Zr2(WO4)(PO4)2 was purchased from a partner. The coarse composite ceramic powder was further crushed and ground to obtain the required composite ceramic powder, whose D50 particle size was 0.8 μm.

[0150] According to the formula ratio, weigh the first glass powder: 59g, the second glass powder: 6g, the modified sintering aid: 4.0g, Zr2(WO4)(PO4)2: 10g, and the organic carrier: 21.0g, mix them, centrifuge them, and then grind them using a three-roll mill to obtain 100g of glass sealant.

[0151] Among them, the fineness of the glass sealant is less than 4μm.

[0152] Pre-sintering: screen print the prepared glass glue onto the glass substrate to form a glass glue sealing ring, and pre-sinter at 420°C for 30 minutes.

[0153] The morphology of the pre-sintered glass glue sealing ring was detected under a microscope, and the width was 460μm and the height was 5μm.

[0154] Laser sintering: Place the glass cover plate on the pre-sintered glass glue seal ring, and use a laser with a wavelength of 810nm to irradiate the glass glue seal ring from one side of the glass cover plate. The glass glue seal ring absorbs the laser energy and melts and is welded together with the glass substrate and the glass cover plate. The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover plate. The surface morphology after laser sintering is equivalent to that of Example 1 (see Example 1). Figure 4 ), microscopic observation revealed that the glass sealant and the glass substrate, as well as the glass sealant and the glass cover were well welded without bubbles.

[0155] Tensile test: The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover. Use double-sided tape to stick on the glass cover and glass substrate, and use a tensile machine to vertically stretch until it breaks, and the tensile force is more than 70N.

[0156] Anti-drop test: A 4.2g steel ball and a 10g steel ball were dropped from a height of 150cm onto a laser sintered and welded glass substrate-glass sealant-glass cover plate sample to test the anti-drop performance of the glass sealant. The steel ball was controlled to drop accurately on the position of the glass sealant sealing ring, and then the cross-section of the steel ball at the drop point was observed under a microscope to observe the bonding conditions between the glass sealant and the glass substrate, and between the glass sealant and the glass cover plate.

[0157] The results showed that: under the impact of the steel ball, the glass substrate and the glass cover plate were broken, but the glass substrate and the glass cover plate were well bonded to the glass sealant interface, and no interface separation was found. The microscopic morphology of the interface between the steel ball-resistant glass sealant and the glass substrate, and the glass sealant and the glass cover plate was obtained by SEM analysis, and its appearance was similar to that of Example 1 (see Example 1 Figure 6 and Figure 8 ), the interface is well bonded without cracks or separation.

[0158] Water resistance test: apply glass glue to a glass sheet, put it into a muffle furnace and bake it at 300℃ for 30 minutes, then scrape off the powder and put it into a mold with a diameter of 5mm to press it into shape, and then sinter it at 420℃. A total of 15 cylinders are pressed, and the total weight of the 15 cylinders is 4.660g. Put the 15 cylinder samples into a beaker, add deionized water, and then put the beaker into a 90℃ water bath for boiling. After boiling for 24 hours, dry and weigh it. The weight is 4.660g. No weight reduction of the glass glue was found, indicating that the weight reduction of the glass sealant is less than the accuracy of the balance, indicating that the glass sealant is very stable in hot water.

[0159] Example 3

[0160] A glass adhesive for sealing an OLED device includes the following components based on 100 parts by total weight: 65.0 parts of glass powder, 10.0 parts of composite ceramic powder, 4.0 parts of modified sintering aid, and 21.0 parts of organic carrier. Among them, the weight of the first glass powder is 4 parts, the weight of the second glass powder is 61 parts, and the total weight of the first glass powder and the second glass powder is 65 parts.

[0161] The first glass powder includes the following components based on a molar ratio of 100%: B2O3: 30.0%, ZnO: 37%, TeO2: 15.5%, V2O5: 10%, CuO: 4.5%, Bi2O3: 2%, SiO2: 1%. The softening point temperature of the first glass powder is 314°C.

[0162] According to the above first glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the required first glass powder, whose D50 particle size is 0.8μm.

[0163] The second glass powder includes the following components based on a molar ratio of 100%: B2O3: 25%, ZnO: 40%, TeO2: 3%, V2O5: 5%, CuO: 21%, SiO2: 3%, Fe2O3: 1.5%, and MnO2: 1.5%. The softening point temperature of the second glass powder is 430°C.

[0164] According to the above second glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the desired second glass powder, whose D50 particle size is 0.8μm.

[0165] The organic carrier comprises the following components based on 100% by weight: rosin resin: 10%, acrylic resin: 10%, pine alcohol: 25%, dibutyl sebacate: 52%, fatty acid: 1%, and polydimethylsiloxane: 2%.

[0166] According to the above formula, the organic carrier raw materials were weighed in sequence, and mixed at 60° C. for 1 h to obtain the desired organic carrier.

[0167] The coarse composite ceramic powder Zr2(WO4)(PO4)2 was purchased from a partner. The coarse composite ceramic powder was further crushed and ground to obtain the required composite ceramic powder, whose D50 particle size was 0.8 μm.

[0168] According to the formula ratio, weigh the first glass powder: 4g, the second glass powder: 61g, the modified sintering aid: 4.0g, Zr2(WO4)(PO4)2: 10g, and the organic carrier: 21.0g, mix them, centrifuge them, and then grind them using a three-roll mill to obtain 100g of glass sealant.

[0169] Among them, the fineness of the glass sealant is less than 4μm.

[0170] Pre-sintering: The prepared glass glue is screen-printed onto a glass substrate to form a glass glue sealing ring, which is pre-sintered at 420°C for 30 minutes. The morphology of the pre-sintered glass glue sealing ring is detected under a microscope, and the width is 460 μm and the height is 5 μm.

[0171] Laser sintering: Place the glass cover plate on the pre-sintered glass glue sealing ring, and use a laser with a wavelength of 810nm to irradiate the glass glue sealing ring from one side of the glass cover plate. The glass glue sealing ring absorbs the laser energy and is melted and welded to the glass substrate and the glass cover plate.

[0172] The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover plate. The surface morphology after laser sintering is equivalent to that of Example 1 (see Example 1). Figure 4 ), microscopic observation revealed that the glass sealant and the glass substrate, as well as the glass sealant and the glass cover were well welded without bubbles.

[0173] Tensile test: The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover. Use double-sided tape to stick on the glass cover and glass substrate, and use a tensile machine to vertically stretch until it breaks, and the tensile force is more than 70N.

[0174] Anti-drop test: A 4.2g steel ball and a 10g steel ball were dropped from a height of 150cm onto the laser sintered and welded glass substrate-glass sealant-glass cover plate samples to test the anti-drop performance of the glass sealant. The steel ball was controlled to drop accurately on the position of the glass sealant sealing ring, and then the cross-section of the steel ball at the drop point was observed under a microscope to observe the bonding conditions between the glass sealant and the glass substrate and between the glass sealant and the glass cover plate.

[0175] The results showed that: under the impact of the steel ball, the glass substrate and the glass cover plate were broken, but the glass substrate and the glass cover plate were well bonded to the glass sealant interface, and no interface separation was found. The microscopic morphology of the interface between the steel ball-resistant glass sealant and the glass substrate, and the glass sealant and the glass cover plate was obtained by SEM analysis, and its appearance was similar to that of Example 1 (see Example 1 Figure 6 and Figure 8 ), the interface is well bonded without cracks or separation.

[0176] Water resistance test: apply glass sealant to a glass sheet, place it in a muffle furnace and bake it at 300°C for 30 minutes, then scrape off the powder and place it in a mold with a diameter of 5 mm to press it into shape, and then sinter it at 420°C to form a total of 15 cylinders. The total weight of the 15 cylinders is 4.660g. Place the 15 cylinder samples in a beaker, add deionized water, and then place the beaker in a 90°C water bath for boiling. After boiling for 24 hours, dry and weigh it, and its weight is 4.660g. No weight reduction of the glass sealant was found, indicating that the weight reduction of the glass sealant is less than the accuracy of the balance, indicating that the glass sealant is very stable in hot water.

[0177] Example 4

[0178] A glass adhesive for sealing an OLED device includes the following components based on 100 parts by total weight: 65.0 parts of glass powder, 10.0 parts of composite ceramic powder, 4.0 parts of modified sintering aid, and 21.0 parts of organic carrier. The first glass powder has 61 parts by weight, the second glass powder has 4 parts by weight, and the total weight of the first glass powder and the second glass powder is 65 parts.

[0179] The first glass powder includes the following components based on a molar ratio of 100%: B2O3: 30.0%, ZnO: 37%, TeO2: 15.5%, V2O5: 10%, CuO: 4.5%, Bi2O3: 2%, SiO2: 1%. The softening point temperature of the first glass powder is 314°C.

[0180] According to the above first glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the required first glass powder, whose D50 particle size is 0.8μm.

[0181] The second glass powder includes the following components based on a molar ratio of 100%: B2O3: 25%, ZnO: 40%, TeO2: 3%, V2O5: 5%, CuO: 21%, SiO2: 3%, Fe2O3: 1.5%, and MnO2: 1.5%. The softening point temperature of the second glass powder is 430°C.

[0182] According to the above second glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the desired second glass powder, whose D50 particle size is 0.8μm.

[0183] The organic carrier comprises the following components based on 100% by weight: rosin resin: 10%, acrylic resin: 10%, pine alcohol: 25%, dibutyl sebacate: 52%, fatty acid: 1%, and polydimethylsiloxane: 2%.

[0184] According to the above formula, the organic carrier raw materials were weighed in sequence, and mixed at 60° C. for 1 h to obtain the desired organic carrier.

[0185] The coarse composite ceramic powder Zr2(WO4)(PO4)2 was purchased from a partner. The coarse composite ceramic powder was further crushed and ground to obtain the required composite ceramic powder, whose D50 particle size was 0.8 μm.

[0186] According to the formula ratio, weigh the first glass powder: 4g, the second glass powder: 61g, the modified sintering aid: 4.0g, Zr2(WO4)(PO4)2: 10g, and the organic carrier: 21.0g, mix them and stir them centrifugally, then grind them using a three-roll mill to obtain 100g of glass sealant.

[0187] Among them, the fineness of glass: glue is less than 4μm.

[0188] Pre-sintering: The prepared glass glue is screen-printed onto a glass substrate to form a glass glue sealing ring, which is pre-sintered at 420°C for 30 minutes. The morphology of the pre-sintered glass glue sealing ring is detected under a microscope, and the width is 460 μm and the height is 5 μm.

[0189] Laser sintering: Place the glass cover plate on the pre-sintered glass glue sealing ring, and use a laser with a wavelength of 810nm to irradiate the glass glue sealing ring from one side of the glass cover plate. The glass glue sealing ring absorbs the laser energy and is melted and welded to the glass substrate and the glass cover plate.

[0190] The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover plate. The surface morphology after laser sintering is equivalent to that of Example 1 (see Example 1). Figure 4 ), microscopic observation revealed that the glass sealant and the glass substrate, as well as the glass sealant and the glass cover were well welded without bubbles.

[0191] Tensile test: The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover. Use double-sided tape to stick on the glass cover and glass substrate, and use a tensile machine to vertically stretch until it breaks, and the tensile force is more than 70N.

[0192] Anti-drop test: A 4.2g steel ball and a 10g steel ball were dropped from a height of 150cm onto the laser sintered and welded glass substrate-glass sealant-glass cover plate samples to test the anti-drop performance of the glass sealant. The steel ball was controlled to drop accurately on the position of the glass sealant sealing ring, and then the cross-section of the steel ball at the drop point was observed under a microscope to observe the bonding conditions between the glass sealant and the glass substrate, and between the glass sealant and the glass cover plate.

[0193] The results showed that: under the impact of the steel ball, the glass substrate and the glass cover plate were broken, but the glass substrate and the glass cover plate were well bonded to the glass sealant interface, and no interface separation was found. The microscopic morphology of the interface between the steel ball-resistant glass sealant and the glass substrate, and the glass sealant and the glass cover plate was obtained by SEM analysis, and its appearance was similar to that of Example 1 (see Example 1 Figure 6 and Figure 8 ), the interface is well bonded without cracks or separation.

[0194] Water resistance test: apply glass sealant to a glass sheet, place it in a muffle furnace and bake it at 300°C for 30 minutes, then scrape off the powder and place it in a mold with a diameter of 5 mm to press it into shape, and then sinter it at 420°C to form a total of 15 cylinders. The total weight of the 15 cylinders is 4.660g. Place the 15 cylinder samples in a beaker, add deionized water, and then place the beaker in a 90°C water bath for boiling. After boiling for 24 hours, dry and weigh it, and its weight is 4.660g. No weight reduction of the glass sealant was found, indicating that the weight reduction of the glass sealant is less than the accuracy of the balance, indicating that the glass sealant is very stable in hot water.

[0195] Example 5

[0196] A glass adhesive for sealing an OLED device includes the following components based on 100 parts by total weight: 65.0 parts of glass powder, 10.0 parts of composite ceramic powder, 4.0 parts of modified sintering aid, and 21.0 parts of organic carrier. The first glass powder has 61 parts by weight, the second glass powder has 4 parts by weight, and the total weight of the first glass powder and the second glass powder is 65 parts.

[0197] The first glass powder includes the following components based on a molar ratio of 100%: B2O3: 21.0%, ZnO: 30%, TeO2: 20%, V2O5: 20%, CuO: 6.0%, Bi2O3: 2%, SiO2: 1%. The softening point temperature of the first glass powder is 314°C.

[0198] According to the above first glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the required first glass powder, whose D50 particle size is 0.8μm.

[0199] The second glass powder includes the following components according to a molar ratio of 100%: B2O3: 23%, ZnO: 40%, TeO2: 4%, V2O5: 20%, CuO: 6%, SiO2: 4%, Fe2O3: 1.5%, and MnO2: 1.5%. The softening point temperature of the second glass powder is 430°C.

[0200] According to the above second glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the desired second glass powder, whose D50 particle size is 0.8μm.

[0201] The organic carrier comprises the following components based on 100% by weight: rosin resin: 10%, acrylic resin: 10%, pine alcohol: 25%, dibutyl sebacate: 52%, fatty acid: 1%, and polydimethylsiloxane: 2%.

[0202] According to the above formula, the organic carrier raw materials were weighed in sequence, and mixed at 60° C. for 1 h to obtain the desired organic carrier.

[0203] Among them, the Zr2(WO4)(PO4)2 coarse powder was purchased from a partner, and the purchased composite ceramic coarse powder was further crushed and ground to obtain the required composite ceramic powder, and the D50 particle size of the composite ceramic powder was 0.8μm.

[0204] According to the formula ratio, weigh the first glass powder: 61g, the second glass powder: 4g, the modified sintering aid: 4.0g, Zr2(WO4)(PO4)2: 10g, and the organic carrier: 21.0g, mix them, centrifuge them, and then grind them using a three-roll mill to obtain 100g of glass sealant.

[0205] Among them, the fineness of the glass sealant is less than 4μm.

[0206] Pre-sintering: The prepared glass glue is screen-printed onto a glass substrate to form a glass glue sealing ring, which is pre-sintered at 420°C for 30 minutes. The morphology of the pre-sintered glass glue sealing ring is detected under a microscope, and the width is 460 μm and the height is 5 μm.

[0207] Laser sintering: Place the glass cover plate on the pre-sintered glass glue sealing ring, and use a laser with a wavelength of 810nm to irradiate the glass glue sealing ring from one side of the glass cover plate. The glass glue sealing ring absorbs the laser energy and is melted and welded to the glass substrate and the glass cover plate.

[0208] The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover plate. The surface morphology after laser sintering is equivalent to that of Example 1 (see Example 1). Figure 4 ), microscopic observation revealed that the glass sealant and the glass substrate, as well as the glass sealant and the glass cover were well welded without bubbles.

[0209] Tensile test: The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover. Use double-sided tape to stick on the glass cover and glass substrate, and use a tensile machine to vertically stretch until it breaks, and the tensile force is more than 70N.

[0210] Anti-drop test: A 4.2g steel ball and a 10g steel ball were dropped from a height of 150cm onto the laser sintered and welded glass substrate-glass sealant-glass cover plate samples to test the anti-drop performance of the glass sealant. The steel ball was controlled to drop accurately on the position of the glass sealant sealing ring, and then the cross-section of the steel ball at the drop point was observed under a microscope to observe the bonding conditions between the glass sealant and the glass substrate and between the glass sealant and the glass cover plate.

[0211] The results show that: under the impact of the steel ball, the glass substrate and the glass cover plate are broken, but the glass substrate and the glass cover plate are well bonded to the glass sealant interface, and no interface separation phenomenon is found. The microscopic morphology of the interface between the steel ball-resistant glass sealant and the glass substrate, and the glass sealant and the glass cover plate is obtained by SEM analysis, and its morphology is equivalent to that of Example 1 (see Example 1 Figure 6 and Figure 8 ), the interface is well bonded without cracks or separation.

[0212] Water resistance test: apply glass sealant to a glass sheet, place it in a muffle furnace and bake it at 300℃ for 30 minutes, then scrape off the powder and place it in a mold with a diameter of 5mm to press it into shape, and then sinter it at 420℃. A total of 15 cylinders are pressed, and the total weight of the 15 cylinders is 4.660g. Put the 15 cylinder samples into a beaker, add deionized water, and then put the beaker into a 90℃ water bath for boiling. After boiling for 24 hours, dry and weigh it, and its weight is 4.660g. No weight reduction of the glass sealant was found, indicating that the weight reduction of the glass sealant is less than the accuracy of the balance, indicating that the glass sealant is very stable in hot water.

[0213] Example 6

[0214] A glass adhesive for sealing an OLED device includes the following components based on 100 parts by total weight: 65.0 parts of glass powder, 10.0 parts of composite ceramic powder, 4.0 parts of modified sintering aid, and 21.0 parts of organic carrier. Among them, the weight of the first glass powder is 4 parts, the weight of the second glass powder is 61 parts, and the total weight of the first glass powder and the second glass powder is 65 parts.

[0215] The first glass powder includes the following components based on a molar ratio of 100%: B2O3: 21.0%, ZnO: 30%, TeO2: 20%, V2O5: 20%, CuO: 6.0%, Bi2O3: 2%, SiO2: 1%. The softening point temperature of the first glass powder is 314°C.

[0216] According to the above first glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the required first glass powder, whose D50 particle size is 0.8μm.

[0217] The second glass powder includes the following components according to a molar ratio of 100%: B2O3: 23%, ZnO: 40%, TeO2: 4%, V2O5: 20%, CuO: 6%, SiO2: 4%, Fe2O3: 1.5%, and MnO2: 1.5%. The softening point temperature of the second glass powder is 430°C.

[0218] According to the above second glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the desired second glass powder, whose D50 particle size is 0.8μm.

[0219] The organic carrier comprises the following components based on 100% by weight: rosin resin: 10%, acrylic resin: 10%, pine alcohol: 25%, dibutyl sebacate: 52%, fatty acid: 1%, and polydimethylsiloxane: 2%.

[0220] According to the above formula, the organic carrier raw materials were weighed in sequence, and mixed at 60° C. for 1 h to obtain the desired organic carrier.

[0221] Among them, the Zr2(WO4)(PO4)2 coarse powder was purchased from a partner, and the purchased composite ceramic coarse powder was further crushed and ground to obtain the required composite ceramic powder, and the D50 particle size of the composite ceramic powder was 0.8μm.

[0222] According to the formula ratio, weigh the first glass powder: 4g, the second glass powder: 61g, the modified sintering aid: 4.0g, Zr2(WO4)(PO4)2: 10g, and the organic carrier: 21.0g, mix them, centrifuge them, and then grind them using a three-roll mill to obtain 100g of glass sealant.

[0223] Among them, the fineness of the glass sealant is less than 4μm.

[0224] Pre-sintering test: The prepared glass glue is screen-printed onto a glass substrate to form a glass glue sealing ring, which is pre-sintered at 420°C for 30 minutes. The morphology of the pre-sintered glass glue sealing ring is detected under a microscope, and the width is 460μm and the height is 5μm.

[0225] Laser sintering: Place the glass cover plate on the pre-sintered glass glue sealing ring, and use a laser with a wavelength of 810nm to irradiate the glass glue sealing ring from one side of the glass cover plate. The glass glue sealing ring absorbs the laser energy and is melted and welded to the glass substrate and the glass cover plate.

[0226] The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover plate. The surface morphology after laser sintering is equivalent to that of Example 1 (see Example 1). Figure 4 ), microscopic observation revealed that the glass sealant and the glass substrate, as well as the glass sealant and the glass cover were well welded without bubbles.

[0227] Tensile test: The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover. Use double-sided tape to stick on the glass cover and glass substrate, and use a tensile machine to vertically stretch until it breaks, and the tensile force is more than 70N.

[0228] Anti-drop test: A 4.2g steel ball and a 10g steel ball were dropped from a height of 150cm onto a laser sintered and welded glass substrate-glass sealant-glass cover plate sample to test the anti-drop performance of the glass sealant. The steel ball was controlled to drop accurately on the position of the glass sealant sealing ring, and then the cross-section of the steel ball at the drop point was observed under a microscope to observe the bonding conditions between the glass sealant and the glass substrate, and between the glass sealant and the glass cover plate.

[0229] The results showed that: under the impact of the steel ball, the glass substrate and the glass cover plate were broken, but the glass substrate and the glass cover plate were well bonded to the glass sealant interface, and no interface separation was found. The microscopic morphology of the interface between the steel ball-resistant glass sealant and the glass substrate, and the glass sealant and the glass cover plate was obtained by SEM analysis, and its appearance was similar to that of Example 1 (see Example 1 Figure 6 and Figure 8 ), the interface is well bonded without cracks or separation.

[0230] Water resistance test: apply glass sealant to a glass sheet, place it in a muffle furnace and bake it at 300℃ for 30 minutes, then scrape off the powder and place it in a mold with a diameter of 5mm to press it into shape, and then sinter it at 420℃. A total of 15 cylinders are pressed, and the total weight of the 15 cylinders is 4.660g. Put the 15 cylinder samples into a beaker, add deionized water, and then put the beaker into a 90℃ water bath for boiling. After boiling for 24 hours, dry and weigh it, and its weight is 4.660g. No weight reduction of the glass sealant was found, indicating that the weight reduction of the glass sealant is less than the accuracy of the balance, indicating that the glass sealant is very stable in hot water.

[0231] Example 7

[0232] A glass glue for sealing an OLED device comprises the following components in proportions based on 100 parts of total weight: 65.0 parts of glass powder, 10.0 parts of composite ceramic powder, 4.0 parts of modified sintering aid, and 21.0 parts of organic carrier.

[0233] Among them, the weight of the first glass powder is 61 parts, the weight of the second glass powder is 4 parts, and the total weight of the first glass powder and the second glass powder is 65 parts.

[0234] The first glass powder includes the following components based on a molar ratio of 100%: B2O3: 20.0%, ZnO: 20%, TeO2: 10%, V2O5: 30%, CuO: 17.0%, Bi2O3: 2%, SiO2: 1%. The softening point temperature of the first glass powder is 314°C.

[0235] According to the above first glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the required first glass powder, whose D50 particle size is 0.8μm.

[0236] The second glass powder comprises the following components based on a molar ratio of 100%: B2O3: 30%, ZnO: 30%, TeO2: 4.9%, V2O5: 22.5%, CuO: 5%, SiO2: 4.6%, Fe2O3: 1.5%, and MnO2: 1.5%. The softening point temperature of the second glass powder is 430°C.

[0237] According to the above second glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the desired second glass powder, whose D50 particle size is 0.8μm.

[0238] The organic carrier comprises the following components based on 100% by weight: rosin resin: 10%, acrylic resin: 10%, pine alcohol: 25%, dibutyl sebacate: 52%, fatty acid: 1%, and polydimethylsiloxane: 2%.

[0239] According to the above formula, the organic carrier raw materials were weighed in sequence, and mixed at 60° C. for 1 h to obtain the desired organic carrier.

[0240] The coarse composite ceramic powder Zr2(WO4)(PO4)2 was purchased from a partner. The coarse composite ceramic powder was further crushed and ground to obtain the required composite ceramic powder, whose D50 particle size was 0.8 μm.

[0241] According to the formula ratio, weigh the first glass powder: 61g, the second glass powder: 4g, the modified sintering aid: 4.0g, Zr2(WO4)(PO4)2: 10g, and the organic carrier: 21.0g, mix them, stir them centrifugally, and then grind them using a three-roll mill to obtain 100g of glass sealant.

[0242] Among them, the fineness of the glass sealant is less than 4μm.

[0243] Pre-sintering test: The prepared glass glue is screen-printed onto a glass substrate to form a glass glue sealing ring, which is pre-sintered at 420°C for 30 minutes. The morphology of the pre-sintered glass glue sealing ring is detected under a microscope, and the width is 460μm and the height is 5μm.

[0244] Laser sintering: Place the glass cover plate on the pre-sintered glass glue sealing ring, and use a laser with a wavelength of 810nm to irradiate the glass glue sealing ring from one side of the glass cover plate. The glass glue sealing ring absorbs the laser energy and is melted and welded to the glass substrate and the glass cover plate.

[0245] The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover plate. The surface morphology after laser sintering is equivalent to that of Example 1 (see Example 1). Figure 4 ), microscopic observation revealed that the glass sealant and the glass substrate, as well as the glass sealant and the glass cover were well welded without bubbles.

[0246] Tensile test: The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover. Use double-sided tape to stick on the glass cover and glass substrate, and use a tensile machine to vertically stretch until it breaks, and the tensile force is more than 70N.

[0247] Anti-drop test: A 4.2g steel ball and a 10g steel ball were dropped from a height of 150cm onto the laser sintered and welded glass substrate-glass sealant-glass cover plate samples to test the anti-drop performance of the glass sealant. The steel ball was controlled to drop accurately on the position of the glass sealant sealing ring, and then the cross-section of the steel ball at the drop point was observed under a microscope to observe the bonding conditions between the glass sealant and the glass substrate, and between the glass sealant and the glass cover plate.

[0248] The results showed that: under the impact of the steel ball, the glass substrate and the glass cover plate were broken, but the glass substrate and the glass cover plate were well bonded to the glass sealant interface, and no interface separation was found. The microscopic morphology of the interface between the steel ball-resistant glass sealant and the glass substrate, and the glass sealant and the glass cover plate was obtained by SEM analysis, and its appearance was similar to that of Example 1 (see Example 1 Figure 6 and Figure 8 ), the interface is well bonded without cracks or separation.

[0249] Water resistance test: apply glass sealant to a glass sheet, place it in a muffle furnace and bake it at 300℃ for 30 minutes, then scrape off the powder and place it in a mold with a diameter of 5mm to press it into shape, and then sinter it at 420℃. A total of 15 cylinders are pressed, and the total weight of the 15 cylinders is 4.660g. Put the 15 cylinder samples into a beaker, add deionized water, and then put the beaker into a 90℃ water bath for boiling. After boiling for 24 hours, dry and weigh it, and its weight is 4.660g. No weight reduction of the glass sealant was found, indicating that the weight reduction of the glass sealant is less than the accuracy of the balance, indicating that the glass sealant is very stable in hot water.

[0250] Example 8

[0251] A glass adhesive for sealing an OLED device includes the following components based on 100 parts by total weight: 65.0 parts of glass powder, 10.0 parts of composite ceramic powder, 4.0 parts of modified sintering aid, and 21.0 parts of organic carrier. Among them, the weight of the first glass powder is 4 parts, the weight of the second glass powder is 61 parts, and the total weight of the first glass powder and the second glass powder is 65 parts.

[0252] The first glass powder includes the following components based on a molar ratio of 100%: B2O3: 20.0%, ZnO: 20%, TeO2: 10%, V2O5: 30%, CuO: 17.0%, Bi2O3: 2%, SiO2: 1%. The softening point temperature of the first glass powder is 314°C.

[0253] According to the above first glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the required first glass powder, whose D50 particle size is 0.8μm.

[0254] The second glass powder includes the following components according to a molar ratio of 100%: B2O3: 30%, ZnO: 30%, TeO2:

[0255] 4.9%, V2O5: 22.5%, CuO: 5%, SiO2: 4.6%, Fe2O3: 1.5%, MnO2: 1.5%. The softening point temperature of the second glass powder is 430°C.

[0256] According to the above second glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the desired second glass powder, whose D50 particle size is 0.8μm.

[0257] The organic carrier comprises the following components based on 100% by weight: rosin resin: 10%, acrylic resin: 10%, pine alcohol: 25%, dibutyl sebacate: 52%, fatty acid: 1%, and polydimethylsiloxane: 2%.

[0258] According to the above formula, the organic carrier raw materials were weighed in sequence, and mixed at 60° C. for 1 h to obtain the desired organic carrier.

[0259] The coarse composite ceramic powder Zr2(WO4)(PO4)2 was purchased from a partner. The coarse composite ceramic powder was further crushed and ground to obtain the required composite ceramic powder, whose D50 particle size was 0.8 μm.

[0260] According to the formula ratio, weigh the first glass powder: 4g, the second glass powder: 61g, the modified sintering aid: 4.0g, Zr2(WO4)(PO4)2: 10g, and the organic carrier: 21.0g, mix them, stir them centrifugally, and then grind them using a three-roll mill to obtain 100g of glass sealant.

[0261] Among them, the fineness of the glass sealant is less than 4μm.

[0262] Pre-sintering test: The prepared glass glue is screen-printed onto a glass substrate to form a glass glue sealing ring, which is pre-sintered at 420°C for 30 minutes. The morphology of the pre-sintered glass glue sealing ring is detected under a microscope, and the width is 460μm and the height is 5μm.

[0263] Laser sintering: Place the glass cover plate on the pre-sintered glass glue sealing ring, and use a laser with a wavelength of 810nm to irradiate the glass glue sealing ring from one side of the glass cover plate. The glass glue sealing ring absorbs the laser energy and is melted and welded to the glass substrate and the glass cover plate.

[0264] The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover plate. The surface morphology after laser sintering is equivalent to that of Example 1 (see Example 1). Figure 4 ), microscopic observation revealed that the glass sealant and the glass substrate, as well as the glass sealant and the glass cover were well welded without bubbles.

[0265] Tensile test: The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover. Use double-sided tape to stick on the glass cover and glass substrate, and use a tensile machine to vertically stretch until it breaks, and the tensile force is more than 70N.

[0266] Anti-drop test: A 4.2g steel ball and a 10g steel ball were dropped from a height of 150cm onto a laser sintered and welded glass substrate-glass sealant-glass cover plate sample to test the anti-drop performance of the glass sealant. The steel ball was controlled to drop accurately on the position of the glass sealant sealing ring, and then the cross-section of the steel ball at the drop point was observed under a microscope to observe the bonding conditions between the glass sealant and the glass substrate, and between the glass sealant and the glass cover plate.

[0267] The results showed that: under the impact of the steel ball, the glass substrate and the glass cover plate were broken, but the glass substrate and the glass cover plate were well bonded to the glass sealant interface, and no interface separation was found. The microscopic morphology of the interface between the steel ball-resistant glass sealant and the glass substrate, and the glass sealant and the glass cover plate was obtained by SEM analysis, and its appearance was similar to that of Example 1 (see Example 1 Figure 6 and Figure 8 ), the interface is well bonded without cracks or separation.

[0268] Water resistance test: apply glass glue to a glass sheet, put it into a muffle furnace and bake it at 300℃ for 30 minutes, then scrape off the powder and put it into a mold with a diameter of 5mm to press it into shape, and then sinter it at 420℃. A total of 15 cylinders are pressed, and the total weight of the 15 cylinders is 4.660g. Put the 15 cylinder samples into a beaker, add deionized water, and then put the beaker into a 90℃ water bath for boiling. After boiling for 24 hours, dry and weigh it, and its weight is 4.660g. No weight reduction of the glass sealant was found, indicating that the weight reduction of the glass sealant is less than the accuracy of the balance, indicating that the glass sealant is very stable in hot water.

[0269] Example 9

[0270] A glass adhesive for sealing an OLED device includes the following components based on 100 parts by total weight: 60.0 parts of glass powder, 10.0 parts of composite ceramic powder, 4.0 parts of modified sintering aid, and 26.0 parts of organic carrier, wherein the weight of the first glass powder is 46 parts, the weight of the second glass powder is 14 parts, and the total weight of the first glass powder and the second glass powder is 60 parts.

[0271] The first glass powder includes the following components based on a molar ratio of 100%: B2O3: 15.5%, ZnO: 22%, TeO2: 40%, V2O5: 15%, CuO: 4.5%, Bi2O3: 2%, SiO2: 1%. The softening point temperature of the first glass powder is 314°C.

[0272] According to the above first glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the required first glass powder, whose D50 particle size is 0.8μm.

[0273] The second glass powder comprises the following components according to a molar ratio of 100%: B2O3: 5%, ZnO: 60%, TeO2: 2%, V2O5: 20%, CuO: 8%, SiO2: 2%, Fe2O3: 1.5%, and MnO2: 1.5%. The softening point temperature of the second glass powder is 430°C.

[0274] According to the above second glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the desired second glass powder, whose D50 particle size is 0.8μm.

[0275] The organic carrier comprises the following components based on 100% by weight: rosin resin: 10%, acrylic resin: 10%, pine alcohol: 25%, dibutyl sebacate: 52%, fatty acid: 1%, and polydimethylsiloxane: 2%.

[0276] According to the above formula, the organic carrier raw materials were weighed in sequence, and mixed at 60° C. for 1 h to obtain the desired organic carrier.

[0277] The coarse composite ceramic powder Zr2(WO4)(PO4)2 was purchased from a partner. The coarse composite ceramic powder was further crushed and ground to obtain the required composite ceramic powder, whose D50 particle size was 0.8 μm.

[0278] According to the formula ratio, weigh the first glass powder: 46g, the second glass powder: 14g, the modified sintering aid: 4.0g, Zr2(WO4)(PO4)2: 10g, and the organic carrier: 26.0g in sequence, mix them, centrifuge them, and then grind them using a three-roll mill to obtain 100g of glass sealant.

[0279] Among them, the fineness of the glass sealant is less than 4μm.

[0280] Pre-sintering: The prepared glass glue is screen-printed onto a glass substrate to form a glass glue sealing ring, which is pre-sintered at 420°C for 30 minutes. The morphology of the pre-sintered glass glue sealing ring is detected under a microscope, and the width is 460 μm and the height is 5 μm.

[0281] Laser sintering: Place the glass cover plate on the pre-sintered glass glue sealing ring, and use a laser with a wavelength of 810nm to irradiate the glass glue sealing ring from one side of the glass cover plate. The glass glue sealing ring absorbs the laser energy and is melted and welded to the glass substrate and the glass cover plate.

[0282] The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover plate. The surface morphology after laser sintering is equivalent to that of Example 1 (see Example 1). Figure 4 ), microscopic observation revealed that the glass sealant and the glass substrate, as well as the glass sealant and the glass cover were well welded without bubbles.

[0283] Tensile test: The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover. Use double-sided tape to stick on the glass cover and glass substrate, and use a tensile machine to vertically stretch until it breaks, and the tensile force is more than 70N.

[0284] Anti-drop test: A 4.2g steel ball and a 10g steel ball were dropped from a height of 150cm onto the laser sintered and welded glass substrate-glass sealant-glass cover plate samples to test the anti-drop performance of the glass sealant. The steel ball was controlled to drop accurately on the position of the glass sealant sealing ring, and then the cross-section of the steel ball at the drop point was observed under a microscope to observe the bonding conditions between the glass sealant and the glass substrate and between the glass sealant and the glass cover plate.

[0285] The results show that: under the impact of the steel ball, the glass substrate and the glass cover plate are broken, but the glass substrate and the glass cover plate are well bonded to the glass sealant interface, and no interface separation phenomenon is found. The microscopic morphology of the interface between the steel ball-resistant glass sealant and the glass substrate, and the glass sealant and the glass cover plate is as shown in Example 1. Figure 6 and Figure 8 As shown, it can be seen that the interface is well bonded without cracks or separation.

[0286] Water resistance test: apply glass sealant to a glass sheet, place it in a muffle furnace and bake it at 300℃ for 30 minutes, then scrape off the powder and place it in a mold with a diameter of 5mm to press it into shape, and then sinter it at 420℃. A total of 15 cylinders are pressed, and the total weight of the 15 cylinders is 4.660g. Put the 15 cylinder samples into a beaker, add deionized water, and then put the beaker into a 90℃ water bath for boiling. After boiling for 24 hours, dry and weigh it, and its weight is 4.660g. No weight reduction of the glass sealant was found, indicating that the weight reduction of the glass sealant is less than the accuracy of the balance, indicating that the glass sealant is very stable in hot water.

[0287] Example 10

[0288] A glass adhesive for sealing an OLED device includes the following components based on 100 parts by total weight: 70.0 parts of glass powder, 10.0 parts of composite ceramic powder, 4.0 parts of modified sintering aid, and 16.0 parts of organic carrier, wherein the weight of the first glass powder is 9 parts, the weight of the second glass powder is 61 parts, and the total weight of the first glass powder and the second glass powder is 70 parts.

[0289] The first glass powder includes the following components based on a molar ratio of 100%: B2O3: 15.5%, ZnO: 22%, TeO2: 40%, V2O5: 15%, CuO: 4.5%, Bi2O3: 2%, SiO2: 1%. The softening point temperature of the first glass powder is 314°C.

[0290] According to the above first glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the required first glass powder, whose D50 particle size is 0.8μm.

[0291] The second glass powder comprises the following components according to a molar ratio of 100%: B2O3: 5%, ZnO: 60%, TeO2: 2%, V2O5: 20%, CuO: 8%, SiO2: 2%, Fe2O3: 1.5%, and MnO2: 1.5%. The softening point temperature of the second glass powder is 430°C.

[0292] According to the above second glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the desired second glass powder, whose D50 particle size is 0.8μm.

[0293] The organic carrier comprises the following components based on 100% by weight: rosin resin: 10%, acrylic resin: 10%, pine alcohol: 25%, dibutyl sebacate: 52%, fatty acid: 1%, and polydimethylsiloxane: 2%.

[0294] According to the above formula, the organic carrier raw materials were weighed in sequence, and mixed at 60° C. for 1 h to obtain the desired organic carrier.

[0295] The coarse composite ceramic powder Zr2(WO4)(PO4)2 was purchased from a partner. The coarse composite ceramic powder was further crushed and ground to obtain the required composite ceramic powder, whose D50 particle size was 0.8 μm.

[0296] According to the formula ratio, weigh the first glass powder: 9g, the second glass powder: 61g, the modified sintering aid: 4.0g, Zr2(WO4)(PO4)2: 10g, and the organic carrier: 16.0g, mix them, stir them centrifugally, and then grind them using a three-roll mill to obtain 100g of glass sealant.

[0297] Among them, the fineness of the glass sealant is less than 4μm.

[0298] Pre-sintering: The prepared glass glue is screen-printed onto a glass substrate to form a glass glue sealing ring, which is pre-sintered at 420°C for 30 minutes. The morphology of the pre-sintered glass glue sealing ring is detected under a microscope, and the width is 460 μm and the height is 5 μm.

[0299] Laser sintering: Place the glass cover plate on the pre-sintered glass glue seal ring, and use a laser with a wavelength of 810nm to irradiate the glass glue seal ring from one side of the glass cover plate. The glass glue seal ring absorbs the laser energy and melts and is welded together with the glass substrate and the glass cover plate. The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover plate. The surface morphology after laser sintering is equivalent to that of Example 1 (see Example 1). Figure 4 ), microscopic observation revealed that the glass sealant and the glass substrate, as well as the glass sealant and the glass cover were well welded without bubbles.

[0300] Tensile test: The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover. Use double-sided tape to stick on the glass cover and glass substrate, and use a tensile machine to vertically stretch until it breaks, and the tensile force is more than 70N.

[0301] Anti-drop test: A 4.2g steel ball and a 10g steel ball were dropped from a height of 150cm onto a laser sintered and welded glass substrate-glass sealant-glass cover plate sample to test the anti-drop performance of the glass sealant. The steel ball was controlled to drop accurately on the position of the glass sealant sealing ring, and then the cross-section of the steel ball at the drop point was observed under a microscope to observe the bonding conditions between the glass sealant and the glass substrate, and between the glass sealant and the glass cover plate.

[0302] The results showed that: under the impact of the steel ball, the glass substrate and the glass cover plate were broken, but the glass substrate and the glass cover plate were well bonded to the glass sealant interface, and no interface separation was found. The microscopic morphology of the interface between the steel ball-resistant glass sealant and the glass substrate, and the glass sealant and the glass cover plate was obtained by SEM analysis, and its appearance was similar to that of Example 1 (see Example 1 Figure 6 and Figure 8 ), the interface is well bonded without cracks or separation.

[0303] Water resistance test: apply glass sealant to a glass sheet, place it in a muffle furnace and bake it at 300℃ for 30 minutes, then scrape off the powder and place it in a mold with a diameter of 5mm to press it into shape, and then sinter it at 420℃. A total of 15 cylinders are pressed, and the total weight of the 15 cylinders is 4.660g. Put the 15 cylinder samples into a beaker, add deionized water, and then put the beaker into a 90℃ water bath for boiling. After boiling for 24 hours, dry and weigh it, and its weight is 4.660g. No weight reduction of the glass sealant was found, indicating that the weight reduction of the glass sealant is less than the accuracy of the balance, indicating that the glass sealant is very stable in hot water.

[0304] Embodiment 11

[0305] A glass glue for sealing an OLED device comprises the following components in proportions based on 100 parts of total weight: 65.0 parts of glass powder, 10.0 parts of composite ceramic powder, 4.0 parts of modified sintering aid, and 21.0 parts of organic carrier.

[0306] Among them, the weight of the first glass powder is 65 parts, the weight of the second glass powder is 0 parts, and the total weight of the first glass powder and the second glass powder is 65 parts.

[0307] The first glass powder includes the following components based on a molar ratio of 100%: B2O3: 15.5%, ZnO: 22%, TeO2: 40%, V2O5: 15%, CuO: 4.5%, Bi2O3: 2%, SiO2: 1%. The softening point temperature of the first glass powder is 314°C.

[0308] According to the above first glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the required first glass powder, whose D50 particle size is 0.8μm.

[0309] The organic carrier comprises the following components based on 100% by weight: rosin resin: 10%, acrylic resin: 10%, pine alcohol: 25%, dibutyl sebacate: 52%, fatty acid: 1%, and polydimethylsiloxane: 2%.

[0310] According to the above formula, the organic carrier raw materials were weighed in sequence, and mixed at 60° C. for 1 h to obtain the desired organic carrier.

[0311] The coarse composite ceramic powder Zr2(WO4)(PO4)2 was purchased from a partner. The coarse composite ceramic powder was further crushed and ground to obtain the required composite ceramic powder, whose D50 particle size was 0.8 μm.

[0312] According to the formula ratio, the first glass powder: 65g, the modified sintering aid: 4.0g, Zr2(WO4)(PO4)2: 10g, and the organic carrier: 21.0g were weighed in sequence, mixed and centrifuged, and then ground using a three-roll mill to obtain 100g of glass sealant.

[0313] Among them, the fineness of the glass sealant is less than 4μm.

[0314] Pre-sintering: The prepared glass glue is screen-printed onto a glass substrate to form a glass glue sealing ring, which is pre-sintered at 410°C for 30 minutes. The morphology of the pre-sintered glass glue sealing ring is detected under a microscope, and the width is 460 μm and the height is 5 μm.

[0315] Laser sintering: Place the glass cover plate on the pre-sintered glass glue seal ring, and use a laser with a wavelength of 810nm to irradiate the glass glue seal ring from one side of the glass cover plate. The glass glue seal ring absorbs the laser energy and melts and is welded together with the glass substrate and the glass cover plate. The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover plate. The surface morphology after laser sintering is equivalent to that of Example 1 (see Example 1). Figure 4 ), microscopic observation revealed that the glass glue and the glass substrate, the glass sealant and the glass cover were well welded without bubbles.

[0316] Tensile test: The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover. Use double-sided tape to stick on the glass cover and glass substrate, and use a tensile machine to stretch vertically until it breaks, and the tensile force is more than 50N.

[0317] It should be noted that the tensile force is not as high as that of Examples 1-10 but still meets the requirements for OLED packaging.

[0318] Anti-drop test: A 4.2g steel ball and a 10g steel ball were dropped from a height of 150cm onto the laser sintered and welded glass substrate-glass sealant-glass cover plate sample to test the anti-drop performance of the glass sealant. The steel ball was controlled to drop accurately on the position of the glass sealant sealing ring, and then the cross-section of the steel ball at the drop point was observed under a microscope to observe the bonding conditions between the glass sealant and the glass substrate and between the glass sealant and the glass cover plate.

[0319] The results showed that: under the impact of the steel ball, the glass substrate and the glass cover plate were broken, but the glass substrate and the glass cover plate were well bonded to the glass sealant interface, and no interface separation was found. The microscopic morphology of the interface between the steel ball-resistant glass sealant and the glass substrate, and the glass sealant and the glass cover plate was obtained by SEM analysis, and its appearance was similar to that of Example 1 (see Example 1 Figure 6 and Figure 8), the interface is well bonded without cracks or separation.

[0320] Water resistance test: apply glass sealant to a glass sheet, place it in a muffle furnace and bake it at 300℃ for 30 minutes, then scrape off the powder and place it in a mold with a diameter of 5mm to press it into shape, and then sinter it at 420℃. A total of 15 cylinders are pressed, and the total weight of the 15 cylinders is 4.660g. Put the 15 cylinder samples into a beaker, add deionized water, and then put the beaker into a 90℃ water bath for boiling. After boiling for 24 hours, dry and weigh it, and its weight is 4.660g. No weight reduction of the glass sealant was found, indicating that the weight reduction of the glass sealant is less than the accuracy of the balance, indicating that the glass sealant is very stable in hot water.

[0321] Example 12

[0322] A glass sealant for sealing an OLED device comprises the following components in proportions based on 100 parts by total weight: 65.0 parts of glass powder, 10.0 parts of composite ceramic powder, 4.0 parts of modified sintering aid, and 21.0 parts of organic carrier.

[0323] Among them, the weight of the first glass powder is 0 parts, the weight of the second glass powder is 65 parts, and the total weight of the first glass powder and the second glass powder is 65 parts.

[0324] The second glass powder comprises the following components according to a molar ratio of 100%: B2O3: 5%, ZnO: 60%, TeO2: 2%, V2O5: 20%, CuO: 8%, SiO2: 2%, Fe2O3: 1.5%, and MnO2: 1.5%. The softening point temperature of the second glass powder is 430°C.

[0325] According to the above second glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the desired second glass powder, whose D50 particle size is 0.8μm.

[0326] The organic carrier comprises the following components based on 100% by weight: rosin resin: 10%, acrylic resin: 10%, pine alcohol: 25%, dibutyl sebacate: 52%, fatty acid: 1%, and polydimethylsiloxane: 2%.

[0327] According to the above formula, the organic carrier raw materials were weighed in sequence, and mixed at 60° C. for 1 h to obtain the desired organic carrier.

[0328] The coarse composite ceramic powder Zr2(WO4)(PO4)2 was purchased from a partner. The coarse composite ceramic powder was further crushed and ground to obtain the required composite ceramic powder, whose D50 particle size was 0.8 μm.

[0329] According to the formula ratio, weigh the first glass powder: 0g, the second glass powder: 65g, the modified sintering aid: 4.0g, Zr2(WO4)(PO4)2: 10g, and the organic carrier: 21.0g, mix them, stir them centrifugally, and then grind them using a three-roll mill to obtain 100g of glass sealant.

[0330] Among them, the fineness of the glass sealant is less than 4μm.

[0331] Pre-sintering: The prepared glass glue is screen-printed onto a glass substrate to form a glass glue sealing ring, which is pre-sintered at 430°C for 30 minutes. The morphology of the pre-sintered glass glue sealing ring is detected under a microscope, and the width is 460 μm and the height is 5 μm.

[0332] Laser sintering: Place the glass cover plate on the pre-sintered glass glue seal ring, and use a laser with a wavelength of 810nm to irradiate the glass glue seal ring from one side of the glass cover plate. The glass glue seal ring absorbs the laser energy and melts and is welded together with the glass substrate and the glass cover plate. The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover plate. The surface morphology after laser sintering is equivalent to that of Example 1 (see Example 1). Figure 4 ), microscopic observation revealed that the glass sealant and the glass substrate, the glass sealant and the glass cover were well welded, with a small amount of bubbles on the interface, which still met the requirements for OLED packaging.

[0333] Tensile test: The sample structure of laser sintering welding is: glass substrate-glass sealant-glass cover. Use double-sided tape to stick on the glass cover and glass substrate, and use a tensile machine to stretch vertically until it breaks, and the tensile force is more than 50N.

[0334] Anti-drop test: A 4.2g steel ball and a 10g steel ball were dropped from a height of 150cm onto the laser sintered and welded glass substrate-glass sealant-glass cover plate samples to test the anti-drop performance of the glass sealant. The steel ball was controlled to drop accurately on the position of the glass sealant sealing ring, and then the cross-section of the steel ball at the drop point was observed under a microscope to observe the bonding conditions between the glass sealant and the glass substrate, and between the glass sealant and the glass cover plate.

[0335] The results showed that: under the impact of the steel ball, the glass substrate and the glass cover plate were broken, but the glass substrate and the glass cover plate were well bonded to the glass sealant interface, and no interface separation was found. The microscopic morphology of the interface between the steel ball-resistant glass sealant and the glass substrate and the glass sealant and the glass cover plate was obtained by SEM analysis, and its appearance was similar to that of Example 1 (see Example 1). Figure 6 and Figure 8 ), the interface is well bonded without cracks or separation.

[0336] Water resistance test: apply glass sealant to a glass sheet, place it in a muffle furnace and bake it at 300℃ for 30 minutes, then scrape off the powder and place it in a mold with a diameter of 5mm to press it into shape, and then sinter it at 420℃. A total of 15 cylinders are pressed, and the total weight of the 15 cylinders is 4.660g. Put the 15 cylinder samples into a beaker, add deionized water, and then put the beaker into a 90℃ water bath for boiling. After boiling for 24 hours, dry and weigh it, and its weight is 4.660g. No weight reduction of the glass sealant was found, indicating that the weight reduction of the glass sealant is less than the accuracy of the balance, indicating that the glass sealant is very stable in hot water.

[0337] Comparative Example 1

[0338] A glass adhesive for sealing an OLED device includes the following components based on 100 parts by total weight: 65.0 parts of glass powder, 10.0 parts of composite ceramic powder, 4.0 parts of modified sintering aid, and 21.0 parts of organic carrier. The first glass powder has 60 parts by weight, the second glass powder has 5 parts by weight, and the total weight of the first glass powder and the second glass powder is 65 parts.

[0339] Among them, the first glass powder includes the following components according to the molar ratio of 100%: B2O3: 14.5%, ZnO: 30%, TeO2: 20%, V2O5: 22.5%, CuO: 10.0%, Bi2O3: 2%, SiO2: 1%.

[0340] According to the above first glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the required first glass powder, whose D50 particle size is 0.8μm.

[0341] Among them, the second glass powder includes the following components according to the molar ratio of 100%: B2O3: 30%, ZnO: 30%, TeO2: 5.5%, V2O5: 21.5%, CuO: 5%, SiO2: 5%, Fe2O3: 1.5%, and MnO2: 1.5%.

[0342] According to the above second glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the desired second glass powder, whose D50 particle size is 0.8μm.

[0343] The organic carrier comprises the following components based on 100% by weight: rosin resin: 10%, acrylic resin: 10%, pine alcohol: 25%, dibutyl sebacate: 52%, fatty acid: 1%, and polydimethylsiloxane: 2%.

[0344] According to the above formula, the organic carrier raw materials were weighed in sequence, and mixed at 60° C. for 1 h to obtain the desired organic carrier.

[0345] Among them, the composite ceramic powder Zr2(WO4)(PO4)2 coarse powder is purchased from a partner. The purchased composite ceramic coarse powder is further crushed and ground to obtain the required composite ceramic powder, and the D50 particle size of the composite ceramic powder is 0.8μm.

[0346] According to the formula ratio, weigh the first glass powder: 60g, the second glass powder: 5g, the modified sintering aid: 4.0g, Zr2(WO4)(PO4)2: 10g, and the organic carrier: 21.0g, mix them, centrifuge them, and then grind them using a three-roll mill to obtain 100g of glass glue.

[0347] Among them, the fineness of the glass glue is less than 4μm.

[0348] Pre-sintering: The prepared glass glue is screen-printed onto a glass substrate to form a glass glue sealing ring, which is pre-sintered at 420°C for 30 minutes. The morphology of the pre-sintered glass glue sealing ring is detected under a microscope, and the width is 460 μm and the height is 5 μm.

[0349] Laser sintering: Place the glass cover plate on the pre-sintered glass glue sealing ring, and use a laser with a wavelength of 810nm to irradiate the glass glue sealing ring from one side of the glass cover plate. The glass glue sealing ring absorbs the laser energy and is melted and welded to the glass substrate and the glass cover plate.

[0350] The sample structure of laser sintering welding is: glass substrate-glass adhesive-glass cover. The cross-sectional morphology after laser sintering is as follows: Figure 5 As shown, microscopic observation revealed that the glass glue and the glass substrate, as well as the glass glue and the glass cover were not well welded and there were bubbles.

[0351] Tensile test: The sample structure of laser sintering welding is: glass substrate-glass adhesive-glass cover. Use double-sided tape to stick on the glass cover and glass substrate, and use a tensile machine to vertically stretch until it breaks. The tensile force is less than 30N.

[0352] Drop test: A 4.2g steel ball and a 10g steel ball were dropped from a height of 150cm on a laser sintered glass substrate-glass glue-glass cover plate sample to test the drop resistance of the glass glue. The steel ball was controlled to drop accurately on the position of the glass glue sealing ring, and then the cross section of the steel ball where it fell was observed under a microscope to observe the bonding between the glass glue and the glass substrate and the glass glue and the glass cover plate. The results showed that under the impact of the steel ball, the glass substrate and the glass cover plate were broken, and separation was found at the bonding interface between the glass substrate and the glass cover plate and the glass glue interface.

[0353] Water resistance test: apply glass glue on a glass sheet, put it into a muffle furnace and bake it at 300℃ for 30 minutes, then scrape off the powder and put it into a mold with a diameter of 5mm to press it into shape, and then sinter it at 420℃. A total of 15 cylinders are pressed, and the total weight of the 15 cylinders is 4.660g. Put the 15 cylinder samples into a beaker, add deionized water, and then put the beaker into a 90℃ water bath for boiling. After boiling for 24 hours, dry and weigh it. The weight is 4.660g. No weight reduction of the glass glue is found, indicating that the weight reduction of the glass glue is less than the accuracy of the balance, which means that the glass glue is very stable in hot water.

[0354] Comparative Example 2

[0355] A glass adhesive for sealing an OLED device includes the following components based on 100 parts by total weight: 65.0 parts of glass powder, 10.0 parts of composite ceramic powder, 4.0 parts of modified sintering aid, and 21.0 parts of organic carrier, wherein the weight of the first glass powder is 5 parts, the weight of the second glass powder is 60 parts, and the total weight of the first glass powder and the second glass powder is 65 parts.

[0356] Among them, the first glass powder includes the following components according to the molar ratio of 100%: B2O3: 14.5%, ZnO: 30%, TeO2: 20%, V2O5: 22.5%, CuO: 10.0%, Bi2O3: 2%, SiO2: 1%.

[0357] According to the above first glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the required first glass powder, whose D50 particle size is 0.8μm.

[0358] Among them, the second glass powder includes the following components according to the molar ratio of 100%: B2O3: 30%, ZnO: 30%, TeO2: 5.5%, V2O5: 21.5%, CuO: 5%, SiO2: 5%, Fe2O3: 1.5%, and MnO2: 1.5%.

[0359] According to the above second glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the desired second glass powder, whose D50 particle size is 0.8μm.

[0360] The organic carrier comprises the following components based on 100% by weight: rosin resin: 10%, acrylic resin: 10%, pine alcohol: 25%, dibutyl sebacate: 52%, fatty acid: 1%, and polydimethylsiloxane: 2%.

[0361] According to the above formula, the organic carrier raw materials were weighed in sequence, and mixed at 60° C. for 1 h to obtain the desired organic carrier.

[0362] Among them, the composite ceramic powder Zr2(WO4)(PO4)2 coarse powder is purchased from a partner. The purchased composite ceramic coarse powder is further crushed and ground to obtain the required composite ceramic powder, and the D50 particle size of the composite ceramic powder is 0.8μm.

[0363] According to the formula ratio, weigh the first glass powder: 5g, the second glass powder: 60g, the modified sintering aid: 4.0g, Zr2(WO4)(PO4)2: 10g, and the organic carrier: 21.0g, mix them, centrifuge them, and then grind them using a three-roll mill to obtain 100g of glass glue with a fineness of less than 4μm.

[0364] Pre-sintering: The prepared glass glue is screen-printed onto a glass substrate to form a glass glue sealing ring, which is pre-sintered at 420°C for 30 minutes. The morphology of the pre-sintered glass glue sealing ring is detected under a microscope, and the width is 460 μm and the height is 5 μm.

[0365] Laser sintering: Place the glass cover plate on the pre-sintered glass glue sealing ring, and use a laser with a wavelength of 810nm to irradiate the glass glue sealing ring from one side of the glass cover plate. The glass glue sealing ring absorbs the laser energy and melts and is welded together with the glass substrate and the glass cover plate. The sample structure of laser sintering welding is: glass substrate-glass glue-glass cover plate. The surface morphology after laser sintering is similar to that of comparative example 1 (refer to comparative example 1). Figure 5 ), microscopic observation revealed that the glass glue and the glass substrate, as well as the glass glue and the glass cover were not well welded and there were bubbles.

[0366] Tensile test: The sample structure of laser sintering welding is: glass substrate-glass adhesive-glass cover. Use double-sided tape to stick on the glass cover and glass substrate, and use a tensile machine to vertically stretch until it breaks. The tensile force is less than 30N.

[0367] Drop test: A 4.2g steel ball and a 10g steel ball were dropped from a height of 150cm on the laser sintered glass substrate-glass glue-glass cover plate sample to test the drop resistance of the glass glue. The steel ball was controlled to drop accurately on the position of the glass glue sealing ring, and then the cross section of the steel ball where it fell was observed under a microscope to observe the bonding between the glass glue and the glass substrate and the glass glue and the glass cover plate. The results showed that under the impact of the steel ball, the glass substrate and the glass cover plate were broken, and separation was found at the bonding interface between the glass substrate and the glass cover plate and the glass glue interface.

[0368] Water resistance test: apply glass glue on a glass sheet, put it into a muffle furnace and bake it at 300℃ for 30 minutes, then scrape off the powder and put it into a mold with a diameter of 5mm to press it into shape, and then sinter it at 420℃. A total of 15 cylinders are pressed, and the total weight of the 15 cylinders is 4.660g. Put the 15 cylinder samples into a beaker, add deionized water, and then put the beaker into a 90℃ water bath for boiling. After boiling for 24 hours, dry and weigh it. The weight is 4.660g. No weight reduction of the glass glue is found, indicating that the weight reduction of the glass glue is less than the accuracy of the balance, which means that the glass glue is very stable in hot water.

[0369] Comparative Example 3

[0370] A glass adhesive for sealing an OLED device includes the following components based on 100 parts by total weight: 65.0 parts of glass powder, 10.0 parts of composite ceramic powder, 4.0 parts of modified sintering aid, and 21.0 parts of organic carrier. The first glass powder has 65 parts by weight, the second glass powder has 0 parts by weight, and the total of the first glass powder and the second glass powder is 65 parts by weight.

[0371] Among them, the first glass powder includes the following components according to the molar ratio of 100%: B2O3: 10.0%, ZnO: 30%, TeO2: 20%, V2O5: 22.5%, CuO: 14.5%, Bi2O3: 2%, SiO2: 1%.

[0372] According to the above first glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the required first glass powder, whose D50 particle size is 0.8μm.

[0373] The organic carrier comprises the following components based on 100% by weight: rosin resin: 10%, acrylic resin: 10%, pine alcohol: 25%, dibutyl sebacate: 52%, fatty acid: 1%, and polydimethylsiloxane: 2%.

[0374] According to the above formula, the organic carrier raw materials were weighed in sequence, and mixed at 60° C. for 1 h to obtain the desired organic carrier.

[0375] Among them, the composite ceramic powder Zr2(WO4)(PO4)2 coarse powder is purchased from a partner. The purchased composite ceramic coarse powder is further crushed and ground to obtain the required composite ceramic powder, and the D50 particle size of the composite ceramic powder is 0.8μm.

[0376] According to the formula ratio, weigh the first glass powder: 65g, the second glass powder: 0g, the modified sintering aid: 4.0g, Zr2(WO4)(PO4)2: 10g, and the organic carrier: 21.0g, mix them and stir them centrifugally, then grind them using a three-roll mill to obtain 100g of glass glue with a fineness of <4μm.

[0377] Pre-sintering: The prepared glass glue is screen-printed onto a glass substrate to form a glass glue sealing ring, which is pre-sintered at 420°C for 30 minutes. The morphology of the pre-sintered glass glue sealing ring is detected under a microscope, and the width is 460 μm and the height is 5 μm.

[0378] Laser sintering: Place the glass cover plate on the pre-sintered glass glue sealing ring, and use a laser with a wavelength of 810nm to irradiate the glass glue sealing ring from one side of the glass cover plate. The glass glue sealing ring absorbs the laser energy and melts and is welded together with the glass substrate and the glass cover plate. The sample structure of laser sintering welding is: glass substrate-glass glue-glass cover plate. The surface morphology after laser sintering is similar to that of comparative example 1 (refer to Figure 5 ), microscopic observation revealed that the glass glue and the glass substrate, as well as the glass glue and the glass cover were not well welded and there were bubbles.

[0379] Tensile test: The sample structure of laser sintering welding is: glass substrate-glass adhesive-glass cover. Use double-sided tape to stick on the glass cover and glass substrate, and use a tensile machine to stretch vertically until it breaks. The tensile force is less than 20N.

[0380] Drop test: A 4.2g steel ball and a 10g steel ball were dropped from a height of 150cm on a laser sintered glass substrate-glass glue-glass cover plate sample to test the drop resistance of the glass glue. The steel ball was controlled to drop accurately on the position of the glass glue sealing ring, and then the cross section of the steel ball where it fell was observed under a microscope to observe the bonding between the glass glue and the glass substrate and the glass glue and the glass cover plate. The results showed that under the impact of the steel ball, the glass substrate and the glass cover plate were broken, and separation was found at the bonding interface between the glass substrate and the glass cover plate and the glass glue interface.

[0381] Water resistance test: apply glass glue on a glass sheet, put it into a muffle furnace and bake it at 300℃ for 30 minutes, then scrape off the powder and put it into a mold with a diameter of 5mm to press it into shape, and then sinter it at 420℃. A total of 15 cylinders are pressed, and the total weight of the 15 cylinders is 4.660g. Put the 15 cylinder samples into a beaker, add deionized water, and then put the beaker into a 90℃ water bath for boiling. After boiling for 24 hours, dry and weigh it. The weight is 4.660g. No weight reduction of the glass glue is found, indicating that the weight reduction of the glass glue is less than the accuracy of the balance, which means that the glass glue is very stable in hot water.

[0382] Comparative Example 4

[0383] A glass adhesive for sealing an OLED device includes the following components based on a total weight of 100 parts: 65.0 parts of glass powder, 10.0 parts of composite ceramic powder, 4.0 parts of modified sintering aid, and 21.0 parts of organic carrier, wherein the weight of the first glass powder is 0 parts, the weight of the second glass powder is 65 parts, and the total weight of the first glass powder and the second glass powder is 70 parts.

[0384] Wherein, the second glass powder includes the following components according to a molar ratio of 100%: B2O3: 30%, ZnO: 24.5%, TeO2: 10.0%, V2O5: 22.5%, CuO: 8%, SiO2: 5%.

[0385] According to the above second glass powder formula, the oxide raw materials are weighed in sequence, mixed evenly, poured into a platinum crucible, placed in a muffle furnace and heated to 1200°C for melting, kept warm for 60 minutes, and then the molten glass material is poured into deionized water for quenching to obtain glass particles. The obtained glass particles are ground to obtain the desired second glass powder, whose D50 particle size is 0.8μm.

[0386] The organic carrier comprises the following components based on 100% by weight: rosin resin: 10%, acrylic resin: 10%, pine alcohol: 25%, dibutyl sebacate: 52%, fatty acid: 1%, and polydimethylsiloxane: 2%.

[0387] According to the above formula, the organic carrier raw materials were weighed in sequence, and mixed at 60° C. for 1 h to obtain the desired organic carrier.

[0388] Among them, the composite ceramic powder Zr2(WO4)(PO4)2 coarse powder is purchased from a partner. The purchased composite ceramic coarse powder is further crushed and ground to obtain the required composite ceramic powder, and the D50 particle size of the composite ceramic powder is 0.8μm.

[0389] According to the formula ratio, weigh the first glass powder: 0g, the second glass powder: 65g, the modified sintering aid: 4.0g, Zr2(WO4)(PO4)2: 10g, and the organic carrier: 21.0g, mix them and stir them centrifugally, then grind them with a three-roll mill to obtain 100g of glass glue with a fineness of <4μm.

[0390] Pre-sintering: The prepared glass glue is screen-printed onto a glass substrate to form a glass glue sealing ring, which is pre-sintered at 420°C for 30 minutes. The morphology of the pre-sintered glass glue sealing ring is detected under a microscope, and the width is 460 μm and the height is 5 μm.

[0391] Laser sintering: Place the glass cover plate on the pre-sintered glass glue sealing ring, and use a laser with a wavelength of 810nm to irradiate the glass glue sealing ring from one side of the glass cover plate. The glass glue sealing ring absorbs the laser energy and melts and is welded together with the glass substrate and the glass cover plate. The sample structure of laser sintering welding is: glass substrate-glass glue-glass cover plate. The surface morphology after laser sintering is similar to that of comparative example 1 (refer to Figure 5 ), microscopic observation revealed that the glass glue and the glass substrate, as well as the glass glue and the glass cover were not well welded and there were bubbles.

[0392] Tensile test: The sample structure of laser sintering welding is: glass substrate-glass adhesive-glass cover. Use double-sided tape to stick on the glass cover and glass substrate, and use a tensile machine to stretch vertically until it breaks. The tensile force is less than 20N.

[0393] Drop test: A 4.2g steel ball and a 10g steel ball were dropped from a height of 150cm on a laser sintered glass substrate-glass glue-glass cover plate sample to test the drop resistance of the glass glue. The steel ball was controlled to drop accurately on the position of the glass glue sealing ring, and then the cross section of the steel ball where it fell was observed under a microscope to observe the bonding between the glass glue and the glass substrate and the glass glue and the glass cover plate. The results showed that under the impact of the steel ball, the glass substrate and the glass cover plate were broken, and separation was found at the bonding interface between the glass substrate and the glass cover plate and the glass glue interface.

[0394] Water resistance test: apply glass glue on a glass sheet, put it into a muffle furnace and bake it at 300℃ for 30 minutes, then scrape off the powder and put it into a mold with a diameter of 5mm to press it into shape, and then sinter it at 420℃. A total of 15 cylinders are pressed, and the total weight of the 15 cylinders is 4.660g. Put the 15 cylinder samples into a beaker, add deionized water, and then put the beaker into a 90℃ water bath for boiling. After boiling for 24 hours, dry and weigh it. The weight is 4.660g. No weight reduction of the glass glue is found, indicating that the weight reduction of the glass glue is less than the accuracy of the balance, which means that the glass glue is very stable in hot water.

[0395] discuss

[0396] The glass sealant in Examples 1-10 of the present application uses a mixed powder formed by a first glass powder and a second glass powder. The glass sealant has excellent pre-sintering performance. After pre-sintering, the glass sealant is dense and bright. After laser welding, there are few or no bubbles. The tensile force is above 70N, and it has excellent anti-drop performance and good water resistance.

[0397] Embodiments 11 and 12 of the present application respectively use the first glass powder and the second glass powder as glass powders. The tensile force of the glass sealant is slightly lower than that of Embodiments 1-10 of the present application, but meets the packaging requirements. Other properties are equivalent to those of Embodiments 1-10 of the present application, and have excellent pre-sintering performance, drop resistance and water resistance.

[0398] The glass powder component used in the glass glue in Comparative Examples 1-4 is different from the glass powder component of the present application. The surface of the glass glue after pre-sintering is dark, indicating that its pre-sintering performance is poor.

[0399] Depend on Figure 5 It can be clearly seen that there are a large number of bubbles on the surface of the glass glue in Comparative Examples 1-4 after laser welding, indicating that the laser sintering performance of the glass glue is poor.

[0400] The glass glue in Comparative Examples 1-4 has low tensile force, indicating that the glass glue is not well integrated with the glass cover plate and the glass substrate.

[0401] The glass glue in Comparative Examples 1-4 has poor drop resistance, and the steel ball drop resistance test results show that the glass glue is separated from the glass cover plate and the glass substrate.

[0402] Comparative Examples 1-2 used two kinds of glass powder mixtures, and Comparative Examples 3-4 used single glass powders, but their glass powder components were completely different from the first glass powder and the second glass powder of the present application, and the difference in composition resulted in relatively poor performance.

[0403] Table 1 shows the performance test results of the glass sealants of Examples 1-12 of the present application and the glass sealants of Comparative Examples 1-4.

[0404] Table 1

[0405]

[0406] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them; although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application, and they should all be included in the scope of the claims and specification of the present application. In particular, as long as there is no structural conflict, the various technical features mentioned in the various embodiments can be combined in any way. The present application is not limited to the specific embodiments disclosed herein, but includes all technical solutions that fall within the scope of the claims.

Claims

1. A glass sealant, characterized in that: Taking the total weight of the glass sealant as 100%, the glass sealant includes the following components: Glass powder: 45%~85%; Composite ceramic powder: 2% to 15%; Organic carrier: 12% to 40%; Modified sintering aid: 1%~5%; The glass powder includes at least one of a first glass powder and a second glass powder, and the softening point temperature of the first glass powder is lower than the softening point temperature of the second glass powder.

2. The glass sealant according to claim 1, characterized in that: The difference between the softening point temperature of the second glass powder and the softening point temperature of the first glass powder is in the range of 20°C to 100°C.

3. The glass sealant according to claim 1 or 2, characterized in that: The first glass powder comprises the following components according to a molar ratio of 100%: B2O3: 15.5%~30%; ZnO: 20%~40%; TeO2: 10%~40%; V2O5: 10%~30%; CuO: 4.5%~15%; Bi2O3: 0.1%~5%; SiO2: 0.1%~5%.

4. The glass sealant according to claim 1 or 2, characterized in that: The second glass powder comprises the following components according to a molar ratio of 100%: B2O3: 5%~40%; ZnO: 30%~60%; TeO2: 1%~4.9%; V2O5: 5%~30%; CuO: 5%~30%; SiO2: 1%~10%; Fe2O3: 0.1%~5%; MnO2: 0.1%~5%.

5. The glass sealant according to claim 1 or 2, characterized in that: The composite ceramic powder is at least one of zirconium tungstate, zirconium phosphotungstate and zirconium vanadate.

6. The glass sealant according to claim 1 or 2, characterized in that: The modified sintering aid is at least one of iron manganese black, copper chrome black and iron chrome black coated with polyether modified silicone.

7. A method for preparing a glass sealant as claimed in any one of claims 1 to 6, characterized in that: The steps include: The glass powder, the composite ceramic powder, the organic carrier and the modified sintering aid are uniformly mixed, ground and filtered to obtain the glass sealant.

8. A packaging structure, characterized in that: The invention comprises a glass substrate, a glass cover plate and the glass sealant according to any one of claims 1 to 6, wherein the glass substrate and the glass cover plate are arranged opposite to each other, the glass substrate and the glass cover plate are sealed by the glass sealant and form an accommodating space.

9. The packaging structure according to claim 8, characterized in that: The packaging structure further includes an electronic component, which is located on the glass substrate. The electronic component is also arranged in the accommodating space formed by sealing the glass substrate, the glass cover plate and the glass sealant.

10. A packaging method for the packaging structure according to claim 8 or 9, characterized in that: The steps include: The glass sealant is applied on the glass cover plate to form a sealing pattern, and then dried and pre-sintered in sequence to form a dense sealing pattern attached to the glass cover plate; After the side of the glass cover plate having the dense sealing pattern is bonded to the side of the glass substrate, the glass sealant is irradiated with laser until it melts, thereby obtaining the packaging structure.

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