JP5489061B2 - Filler powder and sealing material using the same - Google Patents

Description

The present invention relates to a full filler powder and sealing material using the same, and a suitable off filler powders and the sealing material using the same for sealing treatment by irradiating light in particular.

  Organic EL displays are attracting attention as next-generation flat display panels. Since the organic EL display can be driven by a DC voltage, the driving circuit can be simplified, and there are advantages such as a liquid crystal display that is not dependent on the viewing angle, bright due to self-emission, and has a high response speed. Currently, organic EL displays are mainly used in small portable devices such as mobile phones, but in the future, application to ultra-thin televisions is expected.

  The organic EL display is composed of two glass substrates, a negative electrode such as metal, an organic light emitting layer, a positive electrode such as ITO, and an adhesive material. The organic EL display is mainly driven by disposing an active element such as a thin film transistor (TFT) in each pixel in the same manner as a liquid crystal display. In this case, non-alkali glass is used as a glass substrate. Is done.

  Conventionally, an organic resin such as an epoxy resin having a low temperature curing property or an ultraviolet curable resin has been used as an adhesive material. However, since the organic resin cannot completely block gas intrusion, it is difficult to maintain the airtightness inside the organic EL display. As a result, the display characteristics of the organic EL display have deteriorated over time. Moreover, although organic resin has the advantage that glass substrates can be adhere | attached at low temperature, it has the fault that water resistance is low. Due to this, when the organic EL display is used for a long period of time, there is a problem that the reliability of the display is lowered. In addition, organic EL devices, such as organic EL illumination, are equipped with the same structure, and have the same technical subject.

US Pat. No. 6,416,375 JP 2006-315902 A

  On the other hand, the sealing material containing glass powder can maintain the airtightness inside the organic EL display for a long period of time, and is superior in water resistance compared to the organic resin. For this reason, when the sealing material containing glass powder is used, the said malfunction can be eliminated.

  However, since glass powder generally has a softening point of 300 ° C. or higher, it has been difficult to apply it to an organic EL display. The reason is that in order to seal the glass substrates together, it is necessary to put the entire display in an electric furnace or the like and heat-treat at a temperature equal to or higher than the softening point of the glass powder. This is because the organic light emitting layer is deteriorated.

  In view of such circumstances, a method for sealing an organic EL display by irradiating the sealing material with irradiation light such as laser light has been studied. Since laser light or the like can locally heat only a portion to be sealed, it is possible to seal glass substrates together while preventing deterioration of an active element or the like. For example, Patent Documents 1 and 2 describe that a sealing material is irradiated with laser light to seal a front glass substrate and a back glass substrate of a field emission display.

  However, Patent Documents 1 and 2 do not describe a material configuration suitable for local heating by laser light or the like, and cannot find guidelines for material development. On the other hand, in order to enhance the light absorption characteristics of the sealing material, a method of introducing an absorbing component such as a laser beam into the glass composition of the glass powder can be assumed, but depending on the glass composition system, when an absorbing component is introduced, In some cases, the thermal stability of the resin deteriorates and the sealing process cannot be performed properly.

  Therefore, the present invention improves the airtightness and reliability of organic EL displays and the like while preventing deterioration of active elements and the like by creating a sealing material that can appropriately perform local heating with a laser beam or the like. Is a technical issue.

The present inventors, as a result of extensive studies, doped with transition metal oxides in the crystal structure of full filler powder as a metal ion, if added full filler powder this the sealing material, solving the above technical problem The present invention is found and proposed as the present invention. In other words, full filler powder of the present invention, transition metal oxides in the filler powder are 20 1 to 20 wt% de-loop, and characterized in that it is produced by crystallization glass process. The transition metal oxide may be doped in a form replacing a specific element constituting the composition of the main crystal, or may be doped in a form added to a predetermined composition (theoretical composition of the main crystal). Good.

Off filler powder of the present invention comprises a transition metal oxide 20 1 to 20 wt%. When doping to full filler powder transition metal oxides, it can be off filler powder converting light energy such as laser light to efficiently heat energy. Thus, upon irradiation by thermal energy generated in the full filler powder, easily dissolved glass powder, it is possible to accurately seal the glass substrates to each other. Further, upon irradiation, since the transition metal ion in the full filler powder to some extent diffuse into the glass, it is possible to impart light absorbing properties to the glass, it is possible to further enhance the light absorption properties of the sealing material.

As described above, in order to enhance the light absorption characteristics of the sealing material, a method of introducing an absorbing component such as laser light into the glass composition of the glass powder can be assumed, but depending on the glass composition system, the light absorbing component is introduced. As a result, the thermal stability of the glass decreases, and sealing may not be performed properly. However, the use of full filler powder of the present invention, even without the addition of light-absorbing component in the glass powder, it is possible to easily impart light absorbing properties to the sealing material. As a result, various glass-based glass powders can be applied to this application.

Off filler powder of the present invention, that is produced by crystallization glass process. Crystallized glass method, first melting the glass batch which is prepared to have a desired composition, shaped, after producing the glass powder was ground, firing the glass powder, and crystallized, off filler powder It is a method of producing. According to this method, by adding a material containing a predetermined transition metal element in the glass batch, it is possible to easily doped with transition metal oxides in off filler powder, and further to prepare a homogeneous off filler powder It becomes easy.

Off filler powder of the present invention, characterized by being produced by the crystallized glass method and its, not including those made by a solid phase reaction method.

Off filler powder of this invention is preferably a transition metal oxide is CuO.

Off filler powder of the present invention is preferably cordierite as a main crystal phase is precipitated.

Off filler powder of the present invention preferably has an average particle diameter _{D 50} is less than 15 [mu] m. Here, the “average particle diameter D ₅₀ ” represents a particle diameter in which the accumulated amount is 50% cumulative from the smaller particle in the volume-based cumulative particle size distribution curve measured by the laser diffraction method.

Off filler powder of the present invention preferably has a maximum particle diameter _{D max} is 30μm or less. Here, the “maximum particle diameter D _max ” represents a particle diameter in which the accumulated amount is 99% cumulative from the smaller particle in the volume-based cumulative particle size distribution curve measured by the laser diffraction method.

Sealing material of the present invention is a sealing material containing a glass powder and off filler powder is preferably off filler powder is the above described full filler powder.

Sealing material of the present invention, it is preferable that the content of off filler powder is 0.1 to 70% by volume. If it does in this way, it will become easy to match the thermal expansion coefficient of sealing material with the thermal expansion coefficient of a to-be-sealed thing.

The sealing material of the present invention is preferably subjected to a sealing treatment with irradiation light. If it does in this way, a sealing material can be heated locally and the thermal damage of an active element or an organic light emitting layer can be prevented.

It is preferable that the sealing material of this invention is used for the sealing process by a laser beam. Various lasers can be used for the sealing treatment with laser light, and semiconductor lasers, YAG lasers, CO ₂ lasers, excimer lasers, infrared lasers, and the like are particularly preferable in terms of easy handling. In order to allow the sealing material to absorb the laser beam accurately, the emission center wavelength of the laser beam is preferably 500 to 1600 nm, particularly preferably 750 to 1300 nm.

The sealing material of the present invention is preferably subjected to a sealing treatment with infrared light (such as an infrared lamp). In this way, since a wide area can be locally heated at the same time, the manufacturing efficiency of an organic EL device or the like is improved.

In the sealing material of the present invention, the glass powder preferably contains 0.1% by mass or more of a transition metal oxide as a glass composition. By doing so, since the laser beam or the like is also absorbed by the glass, the light absorption characteristics of the sealing material are improved. As the transition metal _oxide, it may be mentioned _{CuO, Fe 2 O 3, MnO} 2, NiO, and V 2 _{O 5} or the like.

It is preferable that the sealing material of the present invention does not substantially contain PbO. In this way, environmental demands in recent years can be satisfied. Here, “substantially no PbO” refers to the case where the content of PbO in the glass composition is 1000 ppm (mass) or less.

Sealing material of the present invention preferably has a thermal expansion coefficient of 55 × 10 -7 ^/ ℃ or less. If it does in this way, it will become easy to match the thermal expansion coefficient of sealing material with the thermal expansion coefficient of an alkali free glass. Here, the “thermal expansion coefficient” refers to a value measured with a push rod type thermal expansion coefficient measurement (TMA) apparatus in a measurement temperature range of 30 to 300 ° C.

The sealing material of the present invention preferably further contains 0 to 10% by volume of an oxide pigment.

The sealing material of the present invention is preferably used for sealing an organic EL device or a solar cell.

In full filler powders of the present invention, the content of the transition metal oxide is at least 1 mass%, considering the light absorption characteristics of the sealing material 2 mass% or more, particularly 3 or more% by mass. When the content of the transition metal oxide is less than 1% by mass, the light absorption characteristics of the sealing material are likely to be lowered. On the other hand, when there is too much content of a transition metal oxide, there exists a possibility of having a bad influence on a main crystal phase or a crystal structure. Therefore, the content of the transition metal oxide is 20% by mass or less , and particularly preferably less than 12% by mass.

In full filler powder of the present invention, the transition metal oxide is Cu, Fe, V, Cr, Mn, Co, one or two or more are preferred oxides such as Ni, particularly CuO is preferred. If doping these transition metal oxides in off filler powder, light energy such as laser light can be converted into heat energy. In particular, since Cu ²⁺ has a large absorption in the infrared region, light energy such as laser light can be efficiently converted into heat energy.

As off filler powder, cordierite, willemite, zircon, zirconium phosphate, zirconium tungstate, zirconium tungstate, beta-eucryptite, beta-quartz and the like. In particular, cordierite has a low coefficient of thermal expansion, so it tends to lower the coefficient of thermal expansion of the sealing material and has good compatibility with various glass powders.

In the sealing material of the present invention, the content of the off filler powder is 0.1 to 70 vol%, 15 to 65 vol%, 20 to 60% by volume, in particular 40 super 55% by volume is preferred. When the content of the off filler powder is less than 0.1 vol%, the effect of adding full filler powder become poor, the light absorption properties of the sealing material is lowered. On the other hand, if the content of off filler powder is more than 70 vol%, it is relatively small amount of glass powder is flux, decreases the fluidity of the sealing material, the sealing strength tends to decrease . Incidentally, if the content of the off filler powder is more than 40% by volume, consisting of thermal expansion coefficient of the sealing material tends to match the thermal expansion coefficient, such as alkali-free glass.

Next, a method for manufacturing a full filler powder of the present invention.

Off filler powder of the present invention, that is produced by crystallization glass process. As described above, in the crystallized glass method, a glass batch prepared to have a desired composition is first melted, molded and pulverized to produce a glass powder, and then the glass powder is fired and crystallized. a method of making a full filler powder. By adopting this method, it is possible to easily doped with transition metal oxides in off filler powder, more easily manufactured homogeneous off filler powder. In the crystallized glass method, it is preferable to grind and mix the glass batch before melting. In this way, since the glass batch is mixed in a fine powder state under mechanical impact, the glass batch becomes homogeneous and the melting time can be shortened. Furthermore, after producing glass powder, it is preferable to add 1-5 mass% of fine powder (Al fine powder etc.) which has fire resistance, when baking this glass powder. In this way, since the fusion of the glass powder particles is suppressed, since the easily beating resulting fired body, or off filler powder is easily spheroidized by surface tension, flow of sealing material Improves.

Off filler powder of the present invention is characterized by being manufactured by the crystallized glass method, it does not include those made by a solid phase reaction method.

In full filler powder of the present invention, the average particle size _{D 50} is preferably less than 15 [mu] m, more preferably 0.5 to 10 [mu] m, more preferably 1 to 5 [mu] m. When full filler average particle diameter D ₅₀ of the powder is 15μm or more, sealing portion becomes thick, it becomes difficult to thin the organic EL display or the like. On the other hand, when the average particle diameter D ₅₀ of the full filler powder to less than 15 [mu] m, the transition metal ion of the full filler powder is easily diffused into the glass during the irradiation, as a result, improved light absorption properties of the sealing material. Further, when the average particle diameter D ₅₀ of the full filler powder to less than 15 [mu] m, it is possible to narrow the sealing thickness, in such a case, even if large difference in thermal expansion coefficient of the glass substrate and the sealing material, Cracks and the like hardly occur in the glass substrate and the sealing part. We note that full filler powder effects (e.g., effect of reducing the thermal expansion coefficient of the sealing material) in order to accurately receive the average particle diameter D ₅₀ of the full filler powder is preferably at least 0.5 [mu] m.

In full filler powder of the present invention, the maximum particle diameter _{D max} is 30μm or less, 20 [mu] m or less, particularly 10μm or less. And the maximum particle diameter D _max of the full filler powder is greater than 30 [mu] m, because the glaze surface portion of the full filler powder easily exposed, it becomes difficult to equalize the gap between the two glass substrates. On the other hand, when the maximum particle diameter D _max of the full filler powder to 30μm or less, it is possible to narrow the sealing thickness, in such a case, even if large difference in thermal expansion coefficient of the glass substrate and the sealing material, Cracks and the like hardly occur in the glass substrate and the sealing part.

Sealing material of the present invention is a composite material containing glass powder and off filler powder. Sealing material of the present invention, upon irradiation, transition metal ions in the off filler powder to some extent diffuse into the glass, can also be provided with light absorbing properties to the glass, as a result, the light energy of the laser beam or the like It can be efficiently converted into thermal energy. That is, when doped with transition metal oxides in off filler absorbs off filler powder with a laser beam or the like, can absorb glass also laser beam or the like. As a result, the light absorption characteristics of the sealing material are improved, and light energy such as laser light is efficiently converted into heat energy. Cu ²⁺ has a property of easily diffusing into glass upon irradiation.

Various glasses can be used as the glass powder. For example, Bi ₂ O ₃ —B ₂ O ₃ glass, Bi ₂ O ₃ —SiO ₂ glass, ZnO—B ₂ O ₃ —SiO ₂ glass, V ₂ O ₅ —P ₂ O ₅ glass, SnO—P ₂ O ₅ glass or the like can be used. Here, “to glass” includes an explicit component as an essential component, and the total content of the explicit component is 30 mol% or more, preferably 40 mol% or more, more preferably 50 mol% or more. Refers to the case.

Bi ₂ O ₃ -B ₂ O ₃ based glass, a glass composition, in _{mol%, Bi 2 O 3 15~50%} , B 2 O 3 15~35%, ZnO 0~45% ( preferably 1 to 40 %) Is preferable. In this way, both thermal stability and low melting point characteristics can be achieved at a high level. In addition, in order to improve thermal stability, it is preferable to add 0.1 mol% or more of BaO.

Bi ₂ O ₃ —SiO ₂ -based glass preferably contains 15% to 45% Bi ₂ O _3, 18% to 35% B ₂ O ₃ , and 0.5% to 20% SiO ₂ as a glass composition. . In this way, thermal stability, low melting point characteristics and water resistance can be achieved at a high level. In addition, in order to improve thermal stability, it is preferable to add 0.1 mol% or more of BaO.

The ZnO—B ₂ O ₃ —SiO ₂ -based glass preferably contains, as a glass composition, mol%, SiO ₂ 20 to 50%, B ₂ O ₃ 15 to 35%, and ZnO 1 to 45%. In this way, thermal stability and low expansion characteristics can be achieved at a high level. In order to lower the melting point, it is preferable to add 0.1 mol% or more of an alkali metal oxide (Li ₂ O, Na ₂ O, K ₂ O).

V ₂ O ₅ -P ₂ O ₅ based glass, a glass composition, in _{mol%, V 2 O 5 25~55%} , preferably contains _P 2 O 5 _15~45%. In this way, both thermal stability and low melting point characteristics can be achieved at a high level. _{Incidentally, V 2 O 5 -P 2 O} 5 based _glass, since V 2 _{O 5} has a light absorbing property, it is possible to increase the light absorption properties of the sealing material.

The SnO—P ₂ O ₅ -based glass preferably contains SnO 35 to 70% and P ₂ O ₅ 18 to 50% (preferably 20 to 30%) as a glass composition in mol%. In this way, both thermal stability and low melting point characteristics can be achieved at a high level. In addition, in order to improve thermal stability, it is preferable to add 1 mol% or more of ZnO.

In the glass composition system, in addition to the above components, it is preferable to add a transition metal oxide in an amount of 0.1% or more in the glass composition in order to enhance the light absorption characteristics, and in particular, CuO, Fe ₂ O ₃ , NiO, It is preferable to add 0.1% or more of V ₂ O ₅ , CoO, TiO ₂ , MoO ₃ , MnO ₂ or the like. If these components are added, the light absorption characteristics of the glass are improved, and conversion to thermal energy is facilitated during irradiation with laser light or the like. From the viewpoint of thermal stability, the total content of CuO, Fe ₂ O ₃ , NiO, V ₂ O ₅ , CoO, TiO ₂ , MoO ₃ , and MnO ₂ is preferably 10% or less.

In the sealing material of the present invention, the average particle diameter D50 of the glass powder is preferably less than 15 μm, 0.5 to 10 μm, and particularly preferably 1 to ₅ μm. When the average particle diameter D ₅₀ of the glass powder to less than 15 [mu] m, and reduced the softening point of the glass powder, together with increases flowability of the sealing material, tends to narrow the sealing thickness, in such a case, a glass substrate Even if the difference in the thermal expansion coefficient of the sealing material is large, cracks and the like hardly occur in the glass substrate and the sealing part.

In the sealing material of the present invention, the maximum particle diameter _Dmax of the glass powder is preferably 30 μm or less, 20 μm or less, and particularly preferably 10 μm or less. When the maximum particle diameter _Dmax of the glass powder is 30 μm or less, the softening point of the glass powder is lowered, the fluidity of the sealing material is increased, and the sealing thickness is easily reduced. Even if the difference in the thermal expansion coefficient of the sealing material is large, cracks and the like hardly occur in the glass substrate and the sealing part.

In the sealing material of the present invention, the thermal expansion coefficient is preferably 70 × 10 ⁻⁷ / ° C. or less, 60 × 10 ⁻⁷ / ° C. or less, 55 × 10 ⁻⁷ / ° C. or less, and particularly preferably 50 × 10 ⁻⁷ / ° C. or less. . In this way, even if it is a low-expansion sealed object, it is possible to reduce the stress remaining in the sealed object or the sealed part, and as a result, the sealed part is stress-destructed, and the organic EL display It becomes easy to prevent the situation where airtightness, such as, is impaired. In particular, when the material to be sealed is alkali-free glass (thermal expansion coefficient: about 38 × 10 ⁻⁷ / ° C.), the thermal expansion coefficient of the sealing material is preferably 10 to 55 × 10 ⁻⁷ / ° C.

  In the sealing material of the present invention, the softening point is preferably 550 ° C. or lower, 500 ° C. or lower, particularly 465 ° C. or lower. When the softening point is higher than 550 ° C., the glass tends not to soften even when irradiated with laser light or the like, and in order to increase the sealing strength between the glass substrates, it is necessary to increase the output of the laser light or the like. . The lower limit of the softening point is not particularly limited, but considering the thermal stability of the glass, the softening point is preferably 350 ° C. or higher, particularly 385 ° C. or higher. Here, the “softening point” refers to a value measured with a differential thermal analyzer (DTA), the measurement is performed in air, and the rate of temperature rise is 10 ° C.

  The sealing material of the present invention preferably further contains 0 to 10% by volume, 0.1 to 5% by volume, particularly 0.5 to 3% by volume of an oxide pigment. When the content of the oxide pigment is more than 10% by volume, the glass tends to be devitrified at the time of irradiation, and the fluidity of the sealing material tends to be lowered. As the oxide pigment, Cu-based oxides, Fe-based oxides, Cr-based oxides, and Mn-based oxides are preferable, and these spinel type complex oxides are preferable. In particular, a Mn-based oxide (for example, 42-343B manufactured by Toago Material Co., Ltd.) is preferable in terms of light absorption characteristics, environmental influences, and compatibility with glass powder. Since these oxide pigments can promote light absorption such as laser light, the sealing strength of the sealing material can be increased.

  The sealing material of the present invention may further contain glass fiber, glass beads, silica beads, resin beads and the like up to 10% by volume as a spacer in order to make the sealing thickness uniform. Further, the sealing material of the present invention may further contain up to 10% by volume of transition metal powder such as Cu, Fe, Mn and Co in order to further enhance the light absorption characteristics.

  The sealing material of the present invention may be used as it is in powder form, but it becomes easy to handle when it is kneaded uniformly with a vehicle and processed into a paste. The vehicle mainly includes a solvent and a resin binder, and the resin binder is added for the purpose of adjusting the viscosity of the paste. Moreover, surfactant, a thickener, etc. can also be added as needed. The produced paste is usually applied to a glass substrate or the like by using an applicator such as a dispenser or a screen printing machine, and then subjected to a binder removal step.

  As the resin binder, acrylic acid ester (acrylic resin), ethyl cellulose, polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, methacrylic acid ester and the like can be used.

  As the solvent, N, N′-dimethylformamide (DMF), α-terpineol, higher alcohol, γ-butyllactone (γ-BL), tetralin, butyl carbitol acetate, ethyl acetate, isoamyl acetate, diethylene glycol monoethyl ether, Diethylene glycol monoethyl ether acetate, benzyl alcohol, toluene, 3-methoxy-3-methylbutanol, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, triethylene glycol Propylene glycol monobutyl ether, propylene carbonate, dimethyl sulfoxide (DMSO), N-me -2-pyrrolidone and the like can be used. In particular, α-terpineol is preferable because it has high viscosity and good solubility in a resin binder and the like.

  The sealing material of the present invention is preferably used for sealing an organic EL device. The reason is that since the organic EL device includes a member having low heat resistance, it is highly necessary to perform a sealing process using irradiation light. In particular, there is a high need for organic EL displays and organic EL lighting.

The sealing material of the present invention is preferably used for sealing solar cells, and more preferably used for sealing dye-sensitized solar cells. Dye-sensitized solar cells developed by Gretcher et al. Are expected as next-generation solar cells. The dye-sensitized solar cell includes a transparent electrode substrate on which a transparent conductive film is formed, and a porous oxide semiconductor electrode composed of a porous oxide semiconductor layer (mainly a TiO ₂ layer) formed on the transparent electrode substrate, It comprises a dye such as Ru dye adsorbed on the porous oxide semiconductor electrode, an iodine electrolyte containing iodine, a counter electrode substrate on which a catalyst film and a transparent conductive film are formed, and the like. When the sealing material of the present invention is used for a dye-sensitized solar cell, gas entry can be completely blocked, so that a situation in which iodine electrolyte leaks from the solar cell can be prevented while preventing deterioration of battery characteristics. Can do. In addition, when the sealing material of the present invention is used for a dye-sensitized solar cell, it is possible to perform a sealing process by irradiation light. The substrate and the counter electrode substrate can be sealed.

  Hereinafter, the present invention will be described in detail based on examples.

Table 1 shows examples of the present invention (sample No. 1 , 2, 4, 6, 7) and a comparative example (sample No. 8). Sample No. Reference numerals 3 and 5 are reference examples.

  Each sample shown in Table 1 was prepared as follows.

Sample No. 1, 2, 4, and 6-8 were produced by the crystallized glass method. That is, sample no. Various oxides were prepared so that the transition metal oxides in the table were replaced (doped) with the theoretical compositions of the main crystals of 1, 2, 4, 6-8, and pulverized and mixed for 24 to 48 hours with a ball mill. Then, a glass batch was produced. Next, this glass batch was put in a platinum crucible and melted at 1500 to 1580 ° C. for 3 hours, and then the molten glass was formed into a flaky glass film with a water-cooled roller. Subsequently, the glass film was pulverized with a ball mill and processed into a glass powder having an average particle diameter D50 of ₅ to 8 μm. The glass powder was put in an alumina crucible and baked at 1250 to 1300 ° C. for 10 hours. . Finally, the resulting fired product disintegrated, and air classification, the average particle diameter _{D 50} of 2.5 [mu] m, maximum particle diameter _{D max} to obtain a full filler powder 20 [mu] m.

Sample No. 3 and 5 were prepared by a solid phase reaction method. That is, sample no. Various oxides were prepared so that the transition metal oxide in the table was replaced (doped) with the theoretical composition of 3, 5 main crystals, and pulverized and mixed in a ball mill for 24 to 72 hours. This pulverized product was put in an alumina crucible and fired at 1420 ° C. for 20 to 24 hours. Finally, the resulting fired product disintegrated, and air classification, the average particle diameter _{D 50} of 2.5 [mu] m, maximum particle diameter _{D max} to obtain a full filler powder 20 [mu] m.

  Table 2 shows a glass composition example (sample a) of the glass powder.

Samples listed in Table 2 were prepared as follows. First, a glass batch in which raw materials such as various oxides and carbonates were prepared so as to have the glass composition in the table was prepared, and the glass batch was put in a platinum crucible and melted at 1100 ° C. for 1 hour. Next, the molten glass was formed into a thin piece with a water-cooled roller. Finally, after grinding the flaky glass ball mill, and air classification, the average particle diameter _{D 50} of 2.5 [mu] m, maximum particle diameter _{D max} to obtain each glass powder of 20 [mu] m.

  The glass transition point and softening point were measured with a DTA apparatus. The measurement was performed in the atmosphere at a temperature rising rate of 10 ° C./min, and the measurement was started from room temperature.

  The thermal expansion coefficient was determined with a TMA apparatus. The measurement temperature range was 30 to 300 ° C.

Table 3 shows examples of the sealing material of the present invention (samples A to C, E, G, H ) and a comparative example (sample I). Samples D and F are reference examples. Each sample in Table 3 is the full filler powder according to Table 1, the glass powder shown in Table 2 in a mixing ratio described in Table. In addition, the oxide pigment was added as an outer cover, and a Mn-based oxide (42-343B manufactured by Toago Material Co., Ltd., average particle diameter D ₅₀ = 2 μm) was used.

  About each sample, the glass transition point, the softening point, the thermal expansion coefficient, and the possibility of joining were evaluated.

  The glass transition point and softening point were measured with a DTA apparatus. The measurement was performed in the atmosphere at a temperature rising rate of 10 ° C./min, and the measurement was started from room temperature.

  The thermal expansion coefficient was measured with a TMA apparatus. The measurement temperature range was 30 to 300 ° C. In addition, the measurement sample used what each sample sintered precisely.

  First, each sample and an ethylcellulose-based vehicle were kneaded and prepared so as to have a viscosity of about 150 Pa · s, and then kneaded uniformly with a three-roll mill to form a paste. This paste was printed and applied to the center of a glass substrate processed into a strip shape so as to have a line width of 0.8 mm × length of 4 mm × thickness of 20 μm, and then dried in a drying oven at 120 ° C. for 30 minutes. Next, the resin component contained in the vehicle was debindered by baking for 120 minutes at the softening point shown in the table. During firing, the temperature raising / lowering rate was 10 ° C./min. Subsequently, after accurately stacking a glass substrate processed into a strip of the same shape on the glass substrate on which the obtained glaze film is formed, along the glaze film from the glass substrate side on which the glaze film is not formed Then, a semiconductor laser having a wavelength of 808 nm (output 20 W, scanning speed 2 mm / s) was irradiated. The sealing material is softened and flown by laser light and both glass substrates are bonded is evaluated as “OK”, and the sealing material is not softened and flown and both glass substrates are bonded is evaluated as “Not OK”. did.

As apparent from Table 3, the sample A~H, since the transition metal oxide such as CuO having excellent light absorption characteristics in the off filler powder is doped, it is possible to bond the two glass substrates by laser beam It was. On the other hand, Sample I, since the transition metal oxide during off filler powder is not doped, it is not possible to properly absorb the laser light, it was not possible to bond the two glass substrates by laser light.

Claims (17)

Transition metal oxide filler powder are 20 1 to 20 wt% de-loop, and you characterized in that it is produced by crystallization glass process off filler powder. Off filler powder according to claim 1, the transition metal oxide is characterized by a CuO. Off filler powder according to claim 1 or 2, characterized in that it is cordierite precipitated as a main crystal phase. Off filler powder according to any one of claims 1 to 3, wherein the average particle diameter D ₅₀ is less than 15 [mu] m. Off filler powder according to any one of claims 1 to 4, the maximum particle diameter _{D max} is equal to or is 30μm or less. In sealing material containing a glass powder and off filler powder,
Sealing material, wherein the full filler powder is a full filler powder according to any one of claims 1-5. Sealing material according to claim 6 in which the content of the off filler powder is characterized in that 0.1 to 70% by volume. The sealing material according to claim 6 or 7 , wherein the sealing material is subjected to a sealing treatment with irradiation light. The sealing material according to claim 8 , wherein the irradiation light is a laser beam. The sealing material according to claim 8 , wherein the irradiation light is infrared light. The sealing material according to any one of claims 6 to 10 , wherein the glass powder contains 0.1% by mass or more of a transition metal oxide as a glass composition. The glass powder has a glass composition of mol%, Bi ₂ O ₃   15-50%, B ₂ O ₃   The sealing material according to any one of claims 6 to 11, which contains 15 to 35% and ZnO 0 to 45%. The glass powder has a glass composition of mol%, V ₂ O ₅   25-55%, P ₂ O ₅   The sealing material according to any one of claims 6 to 11, containing 15 to 45%. The sealing material according to any one of claims 6 to 13, which does not substantially contain PbO. The sealing material according to any one of claims 6 to 14, wherein the thermal expansion coefficient is 55 x ^10-7 / ° C or less. Furthermore, the sealing material according to any one of claims 6-15, characterized by containing an oxide pigments 0-10% by volume. The sealing material according to any one of claims 6 to 16, which is used for sealing an organic EL device or a solar battery.