JP2015137186A - Sealing material, substrate with sealing material layer and manufacturing method therefor, and sealed body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealing material preventing reduction of sealing property of a sealing layer formed by calcination and generation of air bubbles when sealing a light emitter between two substrates by the sealing material, and a sealing method of substrate by using the sealing material, and a sealed body.SOLUTION: There is provided a sealing material 3a containing a glass frit 7 and an organic binder 8 and used for forming a sealing material layer 3 bonded to a substrate 2 by calcination by irradiation of electromagnetic wave and having the remaining amount of the organic binder 8 at a grass transition temperature of the glass frit 7 of less than 50%. There is also provided a sealing material containing the glass frit 7 containing total 100 mass% or less by mixing 70 to 90 mass% of BiO, 1 to 20 mass% of ZnO and 2 to 12 mass% of BO.

Description

  Embodiments described herein relate generally to a sealing material, a substrate with a sealing material layer, a method for manufacturing the same, and a sealing body.

  In a flat panel display device (FPD) such as an organic EL display (Organic Electro-Luminescence Display: OELD), a field emission display (Field Emission Display: FED), a plasma display panel (PDP), a liquid crystal display device (LCD), etc., a light emitting element A structure in which an element substrate on which a display element is formed and a sealing substrate are opposed to each other and the display element is sealed with a package in which the two substrates are sealed is applied (see Patent Document 1). ). In solar cells such as dye-sensitized solar cells and organic thin-film solar cells, it has been studied to apply a package in which solar cell elements are sealed with two substrates (see Patent Document 2).

  As a sealing material for sealing between two substrates, for example, a sealing material using a glass frit excellent in moisture resistance or the like is known. The sealing material is produced by mixing a glass frit and a low expansion filler with an organic binder or the like. A sealing layer made of the sealing material is formed between two substrates, and the two substrates can be sealed by fixing the sealing layer to the two substrates by heat treatment.

  In the case of sealing between two substrates using the sealing material, after the sealing material is applied on one substrate, temporary baking is performed before the other substrate is bonded. Since the temporary baking temperature at this time is about 400 to 600 ° C., the characteristics of electronic element parts such as an organic EL (OEL) element and a dye-sensitized solar cell element when temporary baking is performed using a heating furnace. Will deteriorate. Further, when the substrate size is increased, a large heating furnace is required separately, and the initial cost and running cost increase. Therefore, a method has been proposed in which a laser absorbing material is contained in the sealing material, and the sealing material containing the laser absorbing material is irradiated with laser light locally to perform temporary baking (also referred to as laser temporary baking) ( (See Patent Document 3).

  However, when the conventional sealing material is used for laser temporary firing, there is a problem that the flatness of the surface of the sealing layer after laser preliminary firing is reduced, and there is a problem that bubbles are generated inside the sealing layer. . These problems lead to a decrease in sealing performance due to the sealing layer.

JP-T-2006-524419 JP 2008-115057 A JP 2011-51811 A

  The problem to be solved by the present invention is to suppress a decrease in sealing performance due to the sealing layer.

  The sealing material of the present invention includes a glass frit and an organic binder, and is a sealing material used for forming a sealing material layer that is fixed to a substrate by performing preliminary firing by irradiation with electromagnetic waves. In thermogravimetric analysis, the residual amount of organic binder when the glass transition temperature of the glass frit is reached is less than 50%.

  The substrate with the sealing material layer of the present invention is a sealing material fixed to the substrate by performing preliminary firing by irradiation of electromagnetic waves on the substrate and the coating layer of the sealing material of the present invention applied on the substrate. A layer.

  The method for producing a substrate with a sealing material layer according to the present invention includes a first step of applying the sealing material according to the present invention in a frame shape on a sealing region of the substrate, and a local process with respect to the coating layer of the sealing material. A second step of fixing the sealing material layer to the substrate by irradiating an electromagnetic wave to the substrate and pre-baking the coating layer while removing the organic binder.

  The sealing body of the present invention has a first substrate, a second substrate facing the first substrate, and an electromagnetic wave applied to the coating layer of the sealing material of the present invention coated on the first substrate. It is formed so as to be fixed to the first substrate and the second substrate by performing main firing after performing preliminary firing by irradiation, and to provide a sealing region between the first substrate and the second substrate. A sealing layer, and an electronic element portion provided in the sealing region.

It is a figure for demonstrating the manufacturing method of a board | substrate with a sealing material layer. It is a figure which shows the structural example of the board | substrate with a sealing material layer. It is sectional drawing which shows the structural example of a light-emitting device. It is a figure which shows the TGA result of an organic binder.

(First embodiment)
In the present embodiment, a substrate with a sealing material layer using a sealing material will be described with reference to the drawings, and a sealing material used for forming the sealing material layer will also be described.

  FIG. 1 is a cross-sectional view for explaining a method for producing a substrate with a sealing material layer. First, as shown in FIG. 1A, a substrate 2 and a paste-like sealing material 3 a are prepared, and the sealing material 3 a is applied onto the substrate 2. For example, the sealing material 3a can be applied by applying a dispenser or a printing method such as screen printing or gravure printing.

  In FIG. 1A, the cross section of the sealing material 3a is rectangular for convenience. However, the shape is not limited to this, and may be, for example, tapered or semicircular. In FIG. 1, only a part of the sealing material 3 a applied on the substrate 2 is illustrated in an enlarged manner. However, the sealing material 3 a is formed on the substrate 2 in a frame shape, for example.

  It is preferable that the board | substrate 2 has a function which permeate | transmits the electromagnetic waves irradiated at the time of manufacture. As the substrate 2, for example, a glass substrate can be used. For example, alkali-free glass or soda lime glass having various known compositions can be used.

  The sealing material 3 a includes at least a glass frit 7 and an organic binder 8. For example, the pasty sealing material 3 is obtained by kneading a glass frit 7 and a vehicle in which an organic binder 8 is dissolved in a solvent by using a rotary mixer equipped with a stirring blade, a roll mill, a ball mill or the like. Can be produced.

  The viscosity of the pasty sealing material 3 may be adjusted to the viscosity corresponding to the apparatus applied to the substrate 2 and can be adjusted by, for example, the ratio of the organic binder 8 or the ratio of the components of the glass frit 7 and the vehicle. A known additive may be added to the pasty sealing material 3 as a glass paste, such as an antifoaming agent or a dispersing agent. These additives are also components that usually disappear during firing.

  After applying the sealing material 3a, for example, it is preferable to dry at a temperature of 120 ° C. or more for 10 minutes or more. The solvent in the sealing material 3a can be removed by drying. If the solvent remains in the sealing material 3a, the components to be eliminated such as the organic binder 8 may not be sufficiently removed in the subsequent firing step.

  In the applied layer of the applied sealing material 3a, organic components such as the organic binder 8 are decomposed / vaporized and removed while at least a part of the glass frit 7 is melted by temporary baking by irradiation with electromagnetic waves. At this time, when the glass frit 7 reaches a glass transition temperature (also referred to as a glass transition point), that is, when the glass frit 7 starts melting, if the organic binder 8 remains in a large amount, the glass frit 7 After melting, a large amount of organic binder 8 is decomposed. For this reason, an organic component remains in the sealing material layer, air bubbles are easily generated, and flatness of the sealing material layer is deteriorated.

  Therefore, an organic binder 8 that is mostly decomposed and vaporized before the glass frit 7 reaches the glass transition temperature is used. Thereby, when the electromagnetic wave is irradiated, the glass frit 7 can be melted while sufficiently decomposing and vaporizing the organic binder 8 before reaching the glass transition temperature. Therefore, foaming in the sealing material layer is suppressed, and the flatness of the sealing material layer can be improved. In addition, the glass transition temperature of the glass frit 7 is calculated | required by differential thermal analysis (Differential Thermal Analysis: DTA), for example. On the other hand, the decomposition temperature of the organic binder 8 is calculated | required by thermogravimetric analysis (Thermogravimetric Analysis: TGA), for example.

  For example, in TGA, it is preferable to use the glass frit 7 and the organic binder 8 in which the residual amount of the organic binder 8 at the glass transition temperature of the glass frit 7 is less than 50%. In TGA, the organic binder 8 having a residual amount at the glass transition temperature of the glass frit 7 of less than 50% and the glass frit 7 are mixed and used, so that the organic binder 8 is sufficiently decomposed and melted when the glass frit 7 is melted. Vaporization is possible, foaming is reduced in temporary baking by irradiation with electromagnetic waves, and the flatness of the sealing material layer produced by temporary baking can be improved. The residual amount of the organic binder 8 is preferably less than 30%, more preferably less than 10%, and most preferably 0%.

  The flatness of the sealing material layer can be expressed by, for example, an average arithmetic roughness Ra (JIS B0633: '01) on the surface of the sealing material layer. For example, the average arithmetic roughness Ra on the surface of the sealing material layer can be less than 0.10 μm, and more preferably less than 0.08 μm. The average arithmetic roughness Ra can be obtained using, for example, a surface roughness profile measuring machine.

As the glass frit 7, for example, a low-melting glass can be used, and as the low-melting glass, for example, bismuth glass is preferably used. The glass frit of the bismuth-based glass is composed of 70 to 90% by mass of Bi ₂ O ₃ , 1 to 20% by mass of ZnO, and 2 to 12% by mass of B ₂ O ₃ to 100% by mass or less (basic It is preferable that the total amount is 100 mass%. Further, the glass frit of the bismuth-based glass is 100% by mass or less including 75 to 90% by mass of Bi ₂ O ₃ , 5 to 15% by mass of ZnO, and 3 to 10% by mass of B ₂ O _3. (Basically, the total amount is 100% by mass), more preferably 80 to 90% by mass of Bi ₂ O ₃ , 6 to 10% by mass of ZnO, and 4 to 8%. It is more preferable that the total amount of B ₂ O ₃ is 100% by mass or less (basically, the total amount is 100% by mass). A glass frit of bismuth glass having the above composition is suitable as a low-temperature sealing material because of its low glass transition point.

Bi ₂ O ₃ is a component that forms a glass network. When the content of Bi ₂ O ₃ is less than 70% by mass, the softening point of the low-melting glass becomes high and sealing at a low temperature becomes difficult. When the content of Bi ₂ O ₃ exceeds 90% by mass, it becomes difficult to vitrify and the thermal expansion coefficient tends to be too high.

  ZnO is a component that lowers the thermal expansion coefficient and the like. Vitrification becomes difficult when the content of ZnO is less than 1% by mass. When the content of ZnO exceeds 20% by mass, stability during low-melting glass molding is lowered, and devitrification is likely to occur.

B ₂ O ₃ is a component that forms a glass skeleton and widens the range in which vitrification is possible. When the content of B ₂ O ₃ is less than 2% by mass, vitrification becomes difficult, and when it exceeds 12% by mass, the softening point becomes too high, and even if a load is applied during sealing, sealing is performed at a low temperature. It becomes difficult.

The glass frit of the bismuth-based glass includes Al ₂ O ₃ , CeO ₂ , SiO ₂ , Ag ₂ O, MoO ₃ , Nb ₂ O ₃ , Ta ₂ O ₅ , Ga ₂ O ₃ , Sb ₂ O ₃ , Li Even if it contains an optional component such as ₂ O, Na ₂ O, K ₂ O, Cs ₂ O, CaO, SrO, BaO, WO ₃ , P ₂ O ₅ , SnO _x (x is 1 or 2). Good. However, if the content of any component is too large, the glass becomes unstable and devitrification may occur, and the glass transition point and softening point may increase. Therefore, the total content of any component is 30. It is preferable to set it as mass% or less. The glass composition in this case is adjusted so that the total amount of the basic component and the optional component is basically 100% by mass.

Examples of the low melting point glass applicable to the glass frit 7 include tin-phosphate glass. The glass frit of tin-phosphate glass is 100% by mass of 20 to 68% by mass of SnO, 0.5 to 5% by mass of SnO ₂ and 20 to 40% by mass of P ₂ O _5. It is preferable to include the following (basically, the total amount is 100% by mass). Moreover, the glass frit of tin-phosphate glass is 30 to 65% by mass of SnO, 1 to 3.5% by mass of SnO ₂ , and 25 to 40% by mass of P ₂ O _5. More preferably, it is contained so as to be less than or equal to mass% (basically, the total amount is 100 mass%). A glass frit of tin-phosphate glass having the above composition is suitable for a low-temperature sealing material because of its low glass transition point.

  SnO is a component for lowering the melting point of glass. If the SnO content is less than 20% by mass, the viscosity of the glass becomes high and the sealing temperature becomes too high, and if it exceeds 68% by mass, it will not vitrify.

SnO ₂ is a component for stabilizing the glass. When the content of SnO ₂ is less than 0.5% by mass, SnO ₂ is separated and precipitated in the glass that has been softened and melted during the sealing operation, the fluidity is impaired and the sealing workability is lowered. If the content of SnO ₂ exceeds 5% by mass, SnO ₂ is likely to precipitate during melting of the low-melting glass. P ₂ O ₅ is a component for forming a glass skeleton. When the content of P ₂ O ₅ is less than 20% by mass, vitrification does not occur, and when the content exceeds 40% by mass, the weather resistance, which is a disadvantage specific to phosphate glass, may be deteriorated.

Here, the ratio (mass%) of SnO and SnO ₂ in the glass frit can be determined as follows. First, after the glass frit (low melting point glass powder) is acid-decomposed, the total amount of Sn atoms contained in the glass frit is measured by ICP emission spectroscopic analysis. Since Sn ²⁺ (SnO) can be obtained from the acid-decomposed glass frit by the iodometric titration method, Sn ⁴⁺ (SnO ₂ ) is obtained by subtracting the amount of Sn ²⁺ obtained therefrom from the total amount of Sn atoms. Can do.

The glass frit of the tin-phosphate glass is composed of a glass skeleton such as SiO ₂ , ZnO, B ₂ O ₃ , Al ₂ O ₃ , WO ₃ , MoO ₃ , Nb ₂ O ₅ , TiO ₂ , Components such as ZrO ₂ , Li ₂ O, Na ₂ O, K ₂ O, Cs ₂ O, MgO, CaO, SrO, and BaO may be optionally contained as optional components. However, if the content of any component is too large, the glass becomes unstable and devitrification may occur, and the glass transition point and softening point may increase. Therefore, the total content of any component is 30. It is preferable to set it as mass% or less. The glass composition in this case is adjusted so that the total amount of the basic component and the optional component is basically 100% by mass.

In addition to this, as the low melting point glass, for example, vanadium-tellurium glass or the like can be used. The glass frit of the vanadium-tellurium-based glass is 16 to 80% by mass of V ₂ O ₅ , 10 to 60% by mass of TeO ₂ , 7 to 40% by mass of ZnO, 4 to 50% by mass of BaO, Is preferably included so that the total amount is 100 mass% or less (basically, the total amount is 100 mass%). The glass frit of vanadium-tellurium-based glass is 30 to 60% by mass of V ₂ O ₅ , 10 to 40% by mass of TeO ₂ , 7 to 20% by mass of ZnO, and 15 to 35% by mass of BaO. And the total amount is preferably 100% by mass or less (basically, the total amount is 100% by mass). A glass frit of vanadium-tellurium glass having the above composition is suitable for a low-temperature sealing material because of its low glass transition point.

  Examples of the organic binder 8 include cellulose resins such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, propyl cellulose, nitrocellulose, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-hydroxyethyl methacrylate, butyl. Organic resins such as acrylic resins obtained by polymerizing one or more acrylic monomers such as acrylate and 2-hydroxyethyl acrylate, and aliphatic polyolefin carbonate resins such as polyethylene carbonate and polypropylene carbonate are used. Solvents such as terpineol, butyl carbitol acetate, and ethyl carbitol acetate are used in the case of cellulosic resins, and solvents such as methyl ethyl ketone, terpineol, butyl carbitol acetate, and ethyl carbitol acetate are used in the case of acrylic resins. In the case of an aliphatic polyolefin carbonate, a solvent such as propylene carbonate, triacetin, acetyltriethyl citrate is used.

  In the present embodiment, the solvent and the additive such as the organic binder 8 that disappear from the composition due to volatilization or burning during firing are excluded from the constituent components of the sealing material. The component that disappears from the composition due to volatilization or burning during firing is an essential additive in order to form a sealing material layer on the substrate surface by coating or the like. However, since this disappearing component is not a component constituting the sealing material layer, it is not a constituent component of the sealing material, and the composition excluding the component where the composition ratio of the constituent component of the sealing material is also eliminated. It is a percentage.

  Further, as shown in FIG. 1A, the sealing material 3 a preferably includes a low expansion filler 5 and an electromagnetic wave absorber 6. Note that the low expansion filler 5 and the electromagnetic wave absorbing material 6 are not necessarily included.

  The low expansion filler 5 has a function of reducing the linear expansion coefficient. The linear expansion coefficient of the low expansion filler 5 is smaller than that of the glass frit 7. The content of the low expansion filler 5 is preferably 5 to 40% by volume. When the proportion of the low expansion filler 5 is less than 5% by volume, the coefficient of linear expansion coefficient mismatch between the substrate 2 and the sealing material layer becomes too large, and cracks are likely to occur. There is a possibility that the amount of glass in the material layer is reduced and sufficient sealing cannot be performed.

  Here, the residual stress σ generated in the substrate is obtained from the following equation (1).

σ = E (| α ₂ −α ₃ |) ΔT / (1-ρ) (1)

In the above formula (1), E represents the Young's modulus of the sealing material layer or the substrate, ρ represents the Poisson's ratio of the sealing material layer or the substrate 2, α ₂ represents the linear expansion coefficient of the substrate, α ₃ represents the linear expansion coefficient of the sealing material layer, and ΔT is the temperature difference at the time of sealing (temperature difference from the melting temperature (processing temperature) of the sealing material layer to the normal temperature) divided by the cooling time. Value.

  As can be seen from Equation (1), the stress generated in the substrate depends on the linear expansion coefficient of the sealing material layer. Therefore, when the linear expansion coefficient of the sealing material layer increases, the stress applied to the substrate or the sealing material layer increases, and cracks or cracks of the substrate or the sealing material layer easily occur due to distortion based on the stress. . On the other hand, since the thermal expansion coefficient of the sealing material layer can be lowered by adding the low expansion filler, the stress applied to the substrate and the sealing material layer can be reduced.

As the low expansion filler 5, for example, cordierite is preferably used. In addition, for example, at least selected from the group consisting of silica, alumina, zirconia, zirconium silicate, aluminum titanate, mullite, eucryptite, spodumene, zirconium phosphate compounds, quartz solid solution, soda lime glass, and borosilicate glass One type can be used. Examples of the zirconium phosphate-based compound include (ZrO) ₂ P ₂ O ₇ , NaZr ₂ (PO ₄ ) ₃ , KZr ₂ (PO ₄ ) ₃ , Ca _0.5 Zr ₂ (PO ₄ ) ₃ , and NbZr (PO ₄ ). ₃ , Zr ₂ (WO ₃ ) (PO ₄ ) ₂ , and complex compounds thereof.

  The electromagnetic wave absorber 6 has a function of absorbing electromagnetic waves such as laser light. By using the electromagnetic wave absorber 6, the glass frit 7 can be easily melted. As the electromagnetic wave absorber 6, for example, an inorganic pigment is preferably included, and the inorganic pigment preferably includes a transition metal oxide. As the electromagnetic wave absorber 6, for example, a compound such as at least one metal selected from the group consisting of Fe, Cr, Mn, Co, Ni, and Cu, or an oxide containing the above metal can be used. Note that an inorganic filler other than the low expansion filler 5 and the electromagnetic wave absorber 6 may be included in the sealing material 3a.

  Next, as shown in FIG. 1B, the coating layer of the sealing material 3a is temporarily fired. In the pre-baking of the coating layer, by irradiating the coating layer with electromagnetic waves, at least a part of the glass frit 7 is melted while the organic binder 8 and the like are removed. As described above, the difference between the glass transition temperature of the glass frit 7 and the decomposition temperature of the organic binder 8 using the glass frit 7 and the organic binder 8 having a large difference between the glass transition temperature of the glass frit 7 and the decomposition temperature of the organic binder 8. By setting the value to a certain value or more, foaming is reduced in temporary baking by irradiation of electromagnetic waves, and the flatness of the sealing material layer produced by temporary baking can be improved. Here, as shown in FIG. 1B, the laser beam 9 is irradiated. In addition, the heating temperature at this time can be measured, for example with a radiation thermometer.

  As the laser beam 9, for example, a laser beam from a semiconductor laser, a carbon dioxide laser, an excimer laser, a YAG laser, a HeNe laser, or the like can be used.

  Through the above steps, the sealing material layer 3 fixed to the substrate 2 can be formed as shown in FIG. At this time, as shown in FIG. 1C, the glass region 4 may be formed by melting the glass frit 7 in the sealing material layer 3.

  An example of a substrate with a sealing material layer that can be produced by the above production method will be described. 2A is a perspective view illustrating a structural example of the substrate 1 with a sealing material layer of the present embodiment, and FIG. 2B is a cross-sectional view taken along line XY in FIG.

  The sealing material layer 3 corresponds to the sealing material layer 3 shown in FIG. 1C, and is provided on the substrate 2 in a frame shape as shown in FIGS. 2A and 2B. Here, the frame shape is not limited to a shape formed by only a curved line such as a circle (also referred to as a loop shape), for example, a polygonal shape including a straight line such as a quadrangular shape, a rounded square shape, or the like The shape including a straight line and a curve is also included. Further, a layer other than the sealing material layer 3 may be provided on the substrate 2. For example, another layer such as a color filter may be provided in a region surrounded by the sealing material layer 3 of the substrate 2.

  As described above, in the present embodiment, in DTA, foaming and flatness of the sealing material layer due to irradiation of electromagnetic waves by using an organic binder and glass frit whose residual amount at the glass transition temperature of the glass frit is less than a certain amount. Can be suppressed. In the sealing body produced using the board | substrate with which the said sealing material layer was formed, the sealing performance by a sealing layer is high.

(Second Embodiment)
This embodiment demonstrates an example of the sealing body manufactured using the board | substrate with the sealing material layer of 1st Embodiment.

  The sealing body in the present embodiment is formed such that a sealing region is provided between the first substrate, the second substrate facing the first substrate, and the first substrate and the second substrate. And an electronic element portion provided in the sealing region.

  Furthermore, a light emitting device will be described as an example of a sealing body in the present embodiment.

  FIG. 3 is a cross-sectional view showing an example of the structure of the light emitting device according to this embodiment. 3 includes a substrate 11, an element formation layer 12 provided on the substrate 11, a substrate 13 facing the substrate 11, a color filter layer 14 provided on the substrate 13, the substrate 11 and the substrate. And a sealing layer 15 that seals the gaps 13.

  As the substrate 11, for example, a glass substrate such as a soda lime glass substrate or a non-alkali glass substrate can be used. Note that a substrate provided with an insulating layer may be used as the substrate 11.

  The element forming layer 12 is provided in the electronic element portion, and is provided in a sealing region sealed by the substrate 11 with the sealing layer 15 and the substrate 13. In the element forming layer 12, for example, a light emitting element is provided as an electronic element. As the light emitting element, for example, an organic EL element that emits white light can be used. Note that a stack of a transistor and a light-emitting element may be provided in the element formation layer 12 with an insulating layer interposed therebetween. At this time, for example, a field effect transistor can be used as the transistor. The transistor is electrically connected to the light-emitting element through an opening provided in the insulating layer. At this time, the light emission luminance of the light emitting element can be controlled by controlling the amount of current supplied to the light emitting element by the transistor.

  As the substrate 13, for example, the substrate 2 in the first embodiment can be applied.

  The color filter layer 14 is a layer composed of a plurality of color filters including at least three primary colors. Each color filter is provided in the sealing region. The color filter layer 14 includes at least red (R), green (G), and blue (B) color filters provided on the substrate 13. The color filter of the color filter layer 14 is superimposed on the light emitting element.

  The sealing layer 15 is formed so that a sealing region is provided between the substrate 11 and the substrate 13. The sealing layer 15 is formed, for example, by subjecting the sealing material layer 3 shown in the first embodiment to main firing and melting and solidifying the sealing material layer 3. The element forming layer 12 and the color filter layer 14 can be sealed by performing the main baking of the sealing material layer 3 to form the sealing layer 15. The main baking is performed, for example, by irradiating an electromagnetic wave such as a laser beam.

  The thickness of the sealing layer 15 is preferably 6 μm or more, for example. Whereas the thickness of the sealing layer of a light emitting device having a light emitting element formed by a conventional coating method is about 4 to 5 μm, in a method combining a light emitting element and a color filter as in this embodiment, When the thickness of the sealing layer is less than 6 μm, the distance between the substrates becomes unnecessarily narrow, and for example, Newton rings are generated. Therefore, by setting the thickness of the sealing layer 15 to 6 μm or more, the distance between the substrates can be maintained at a certain level or more, so that the light emitting state can be improved.

  The light emitting element provided in the element forming layer 12 is easily deteriorated by impurities such as water, and the light emission characteristics are remarkably deteriorated by the deterioration. Therefore, by sealing the region between the substrate 11 and the substrate 13 with the sealing layer 15, it is possible to prevent intrusion of impurities and suppress deterioration of the light emitting element.

  In the light emitting device shown in FIG. 3, white light emitted from the light emitting element is irradiated to the color filters of the three primary colors, and light of various colors composed of combinations of the three primary colors is realized by the mixed light obtained through the color filters. can do. The light emitting device of this embodiment can also be applied to a lighting device, a display device, and the like.

  In this embodiment, the case of the light emitting device as the sealing body has been described. However, the present invention is not limited to this. It can form using the board | substrate with the sealing material layer of 1 embodiment.

  As described above, in the present embodiment, since the sealing body such as a light emitting device is configured using the substrate with the sealing material layer of the first embodiment, the sealing performance by the sealing layer can be improved. The reliability of the sealing body can be improved.

  In this example, an actually manufactured substrate with a sealing material layer will be described.

<Material preparation>
Two types of glass frit, bismuth glass frit and different glass transition temperatures, Bi ₂ O ₃ -A and Bi ₂ O ₃ -B, are prepared, and ethyl cellulose (EC) showing different decomposition behavior as an organic binder Two types of binders, a polypropylene binder (PPC) binder, were prepared. When the glass transition temperatures of the above Bi ₂ O ₃ -A and Bi ₂ O ₃ -B were determined by DTA, Bi ₂ O ₃ -A was 355 ° C, and Bi ₂ O ₃ -B was 345 ° C.

  In addition, TGA of EC binder and PPC binder was performed, and the decomposition behavior of each binder was examined. TGA was performed using Q600 manufactured by TA Instruments. At this time, an aluminum cell was used as the measurement cell, and the mass of the measurement sample was 5.0 mg. The measurement temperature range was 50 ° C. to 600 ° C., and the temperature increase rate was 10 ° C./min. Further, nitrogen was supplied into the measuring apparatus at a flow rate of 100 ml / min, and the inside of the measuring apparatus was made a nitrogen atmosphere. The results of DTA are shown in FIG.

  FIG. 4A is a diagram showing the binder decomposition behavior by DTA, in which the horizontal axis represents temperature and the vertical axis represents the residual amount of resin. As shown in FIG. 4A, the PPC binder was significantly decomposed in the range of 250 ° C. to 300 ° C., and the EC binder was significantly decomposed in the range of 300 ° C. to 400 ° C.

Further, FIG. 4B is an enlarged view of the range of 300 ° C. to 400 ° C. in FIG. Figure 4 (B) a chain line shown in Tg _{(Bi 2} O 3 -B) _is Bi _{2 O} 3 -B glass transition temperature (345 ° C.) indicates, the dashed line Tg _{(Bi 2} O 3 -A) is It shows a Bi ₂ O ₃ -A glass transition temperature (355 ° C.).

As shown in FIG. 4B, at 355 ° C., which is the glass transition temperature of Bi ₂ O ₃ -A, the binder is decomposed until the residual amount of EC binder becomes less than 50% of the charged amount (initial amount). ing. On the other hand, at 345 ° C., which is the glass transition temperature of Bi ₂ O ₃ —B, the EC binder remains at 50% or more of the charged amount. This suggests that more than half of the binder component remains when the glass frit is melted by temporary firing. On the other hand, in the PPC binder, it can be seen that the binder is sufficiently removed at both 345 ° C. and 355 ° C.

<Sample preparation>
Using the glass frit and the organic binder, the substrates with the sealing material layers of Sample 1, Sample 2, Sample 3, and Sample 4 were prepared by the following procedure.

A glass frit, a low expansion filler made of cordierite powder, and an electromagnetic wave absorber made of a transition metal oxide were prepared. The above materials and the organic binder were roughly kneaded with a raikai machine, and then precision kneaded with a three-roll mill. Then, a pasty sealing material was prepared by diluting the viscosity so as to be in a certain range. Table 1 shows the constituent materials of each sample and the residual amount of the organic binder at the glass frit transition temperature in TGA. As can be seen from Table 1, Bi ₂ O ₃ -A or Bi ₂ O ₃ -B was used as the glass frit, and an EC binder or PPC binder was used as the organic binder. Further, in Samples 1 to 4, the combination of glass frit and organic binder used was varied. In Table 1, CS-12 is 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.

  Next, the produced sealing material was apply | coated on a glass substrate, the sealing material layer was formed, and it was made to dry for 10 minutes at 120 degreeC after that.

  Next, the sealing material layer formed on the glass substrate was temporarily fired. Here, laser light (semiconductor laser) having a wavelength of 808 nm, an output of 6.9 W, and a spot diameter of 1.5 mm was irradiated at a scanning speed of 5 mm / s, and the sealing material layer was melted and rapidly solidified. At this time, the temperature of the sealing material layer measured with the radiation thermometer was 650 degreeC.

<Sample observation>
The cross section of the substrate with the sealing material layer was observed with a scanning electron microscope (SEM) to confirm the presence or absence of foaming. Moreover, arithmetic mean roughness Ra of the sealing material layer was calculated | required using Tokyo Seimitsu Co., Ltd. SURFCOM1400D. The observation results are shown in Table 2. As shown in Table 2, foaming was not confirmed in samples 1 to 3, whereas foaming was confirmed in sample 4. Samples 1 to 3 had an average arithmetic roughness Ra higher than that of sample 4. From this, by making the residual amount of the organic binder less than 50% at the glass transition temperature of the glass frit by TGA, foaming can be suppressed and the flatness of the surface of the sealing material layer can be improved. It turns out that the sealing performance by a sealing layer can be improved using a sealing material layer.

  In addition, although several embodiment of this invention was described, these embodiment is shown as an example and is not intending limiting the range of invention. These novel embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.

  DESCRIPTION OF SYMBOLS 1 ... Substrate with sealing material layer, 2 ... Substrate, 3 ... Sealing material layer, 3a ... Sealing material, 4 ... Glass region, 5 ... Low expansion filler, 6 ... Electromagnetic wave absorber, 7 ... Glass frit, 8 DESCRIPTION OF SYMBOLS ... Organic binder, 9 ... Laser beam, 10 ... Light-emitting device, 11 ... Substrate, 12 ... Element formation layer, 13 ... Substrate, 14 ... Color filter layer, 15 ... Sealing layer.

Claims (8)

A sealing material that includes a glass frit and an organic binder, and is used for forming a sealing material layer that is fixed to the substrate by pre-baking by irradiation with electromagnetic waves,
A sealing material in which the residual amount of the organic binder is less than 50% when the glass transition temperature of the glass frit is reached in thermogravimetric analysis. In the glass frit, 70 to 90% by mass of Bi ₂ O ₃ , 1 to 20% by mass of ZnO, and 2 to 12% by mass of B ₂ O ₃ are combined to be 100% by mass or less. The sealing material according to claim 1. The sealing material includes a low expansion filler;
The sealing material according to claim 1 or 2, wherein the content of the low expansion filler is 5 to 40% by volume.   2. The low-expansion filler is at least one selected from the group consisting of cordierite, silica, alumina, zirconia, zirconium silicate, aluminum titanate, mullite, eucryptite, spodumene, and a zirconium phosphate compound. The sealing material according to any one of claims 3 to 4.   The sealing material according to claim 4, wherein the sealing material includes an electromagnetic wave absorber having an inorganic pigment. A sealing member fixed to the substrate by subjecting the substrate and a coating layer of the sealing material according to any one of claims 1 to 5 applied on the substrate to provisional firing by irradiation of electromagnetic waves. A substrate with a sealing material layer comprising: a bonding material layer. A first step of applying the sealing material according to any one of claims 1 to 5 in a frame shape on a sealing region of a substrate;
A second step of fixing the sealing material layer to the substrate by locally irradiating the coating layer of the sealing material with electromagnetic waves and pre-baking the coating layer while removing the organic binder; The manufacturing method of the board | substrate with the sealing material layer which comprises these. A first substrate;
A second substrate facing the first substrate;
By carrying out main baking after performing preliminary baking by irradiation of electromagnetic waves on the coating layer of the sealing material according to any one of claims 1 to 5 applied on the first substrate. A sealing layer that is fixed to the first substrate and the second substrate, and is formed so that a sealing region is provided between the first substrate and the second substrate;
And an electronic element portion provided in the sealing region.

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