WO2009107428A1 - Matière de scellement pour affichage el organique - Google Patents

Matière de scellement pour affichage el organique Download PDF

Info

Publication number
WO2009107428A1
WO2009107428A1 PCT/JP2009/051167 JP2009051167W WO2009107428A1 WO 2009107428 A1 WO2009107428 A1 WO 2009107428A1 JP 2009051167 W JP2009051167 W JP 2009051167W WO 2009107428 A1 WO2009107428 A1 WO 2009107428A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
organic
sealing material
bismuth
powder
Prior art date
Application number
PCT/JP2009/051167
Other languages
English (en)
Japanese (ja)
Inventor
紀彰 益田
雅章 林
Original Assignee
日本電気硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2008212424A external-priority patent/JP5440997B2/ja
Priority claimed from JP2009009410A external-priority patent/JP5458579B2/ja
Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Priority to KR1020127007801A priority Critical patent/KR101236373B1/ko
Priority to KR1020107007027A priority patent/KR101236369B1/ko
Priority to KR1020127007798A priority patent/KR101236371B1/ko
Priority to KR1020137004395A priority patent/KR101330100B1/ko
Publication of WO2009107428A1 publication Critical patent/WO2009107428A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants

Definitions

  • the present invention relates to a sealing material for an organic EL display, and specifically relates to a sealing material for an organic EL display that is subjected to a sealing process using irradiation light.
  • organic EL displays have attracted attention as 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.
  • 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.
  • an organic resin adhesive material such as an epoxy resin having a low temperature curability or an ultraviolet curable resin has been used as the adhesive material.
  • organic resin adhesive materials since it is difficult for organic resin adhesive materials to completely block gas intrusion, it is difficult to maintain the airtightness inside the organic EL display, resulting in low water resistance.
  • the organic light emitting layer is likely to be deteriorated, resulting in a problem that the display characteristics of the organic EL display deteriorate with time.
  • the organic resin adhesive material has the advantage that the glass substrates can be bonded to each other at a low temperature, but has the disadvantage that the water resistance is low, and when the organic EL display is used for a long time, the reliability of the display is lowered. It becomes easy.
  • an active element such as a thin film transistor (TFT) is disposed in each pixel and driven.
  • TFT thin film transistor
  • the sealing material using glass is superior in water resistance as compared with the organic resin adhesive material and is suitable for ensuring the airtightness inside the organic EL display.
  • the glass used for the sealing material generally has a softening point of 300 ° C. or higher, it is difficult to apply it to an organic EL display. That is, when sealing glass substrates with the above-described sealing material, it is necessary to put the entire organic EL display in an electric furnace and heat-treat at a temperature equal to or higher than the softening point of the glass.
  • the active element has only heat resistance of about 120 to 130 ° C.
  • sealing the glass substrates with this method causes the active element to be damaged by heat and deteriorate the display characteristics of the organic EL display. End up.
  • the organic light emitting material also has poor heat resistance, sealing the glass substrates by this method damages the organic light emitting material due to heat and degrades the display characteristics of the organic EL display.
  • Patent Documents 1 and 2 describe a method of sealing a front glass substrate and a rear glass substrate of a field emission display by irradiating a sealing material with laser light.
  • Patent Documents 1 and 2 do not specifically describe a glass system suitable for this method. Even if the sealing material is irradiated with laser light, the optical energy of the laser light is converted into thermal energy at the sealing site. It was difficult to efficiently convert to Therefore, in order to seal glass substrates together using these sealing materials, it is necessary to increase the output of laser light, and as a result, an unreasonable thermal history is applied to the active elements and the like, and the organic EL display There was a possibility that the display characteristics of the display deteriorated.
  • the sealing material when the sealing material is locally heated with laser light or the like, if the softening point of the glass is low, the sealing material can be sealed in a short time and the sealing strength can be increased. However, generally, when the softening point of glass is lowered, the water resistance of the glass tends to be lowered. As described above, the water resistance of the sealing material is important from the viewpoint of preventing the deterioration of the organic light emitting layer, but it should be understood that Patent Documents 1 and 2 achieve both low softening properties and high water resistance. There is no specific description of the glass system.
  • non-alkali glass for example, OA-10 manufactured by Nippon Electric Glass Co., Ltd.
  • the thermal expansion coefficient of the alkali-free glass is usually 40 ⁇ 10 ⁇ 7 / ° C. or less, and it has been difficult to match the conventional sealing material with the thermal expansion coefficient of the alkali-free glass. If the coefficients of thermal expansion of the two are inconsistent, undue stress tends to remain in the sealed part or alkali-free glass after sealing, and in some cases, cracks or the like occur in the sealed part or alkali-free glass. The airtight reliability of the EL display is impaired.
  • the present invention is suitable for local heating by irradiation light such as laser light, and by creating a sealing material for organic EL displays that has both low softening characteristics and high water resistance, a highly reliable organic Manufacturing an EL display is a technical problem.
  • the present invention is suitable for local heating by irradiation light such as laser light, and by creating a sealing material for organic EL displays having low softening characteristics, high water resistance, and low thermal expansion coefficient. Therefore, a technical problem is to produce an organic EL display with high reliability.
  • the present inventors used a sealing material containing a bismuth glass powder and a refractory filler powder as a sealing material for an organic EL display.
  • the glass composition was CuO.
  • the present inventors have found that the above technical problem can be solved by introducing a predetermined amount of either or both of Fe 2 O 3 and both, and propose as the present invention.
  • the sealing material for organic EL display of the present invention contains 25 to 100% by volume of bismuth-based glass powder and 0 to 75% by volume of refractory filler powder, and the bismuth-based glass powder has CuO + Fe 2 O as a glass composition. 3 (total amount of CuO and Fe 2 O 3 ) is contained in an amount of 0.2 to 15% by mass.
  • bismuth-based glass powder refers to a glass powder having a Bi 2 O 3 content of 50% by mass or more in the glass composition.
  • the sealing material for organic EL displays of this invention may be comprised only with the bismuth-type glass powder, without adding a refractory filler powder.
  • the sealing material for organic EL display of the present invention contains 25 to 100% by volume of bismuth glass powder and 0 to 75% by volume of refractory filler powder, it matches the thermal expansion coefficient of the sealed object such as alkali-free glass. Thus, the thermal expansion coefficient of the sealing material can be lowered.
  • the sealing material for organic EL displays of the present invention contains glass powder, H 2 O, O 2 or the like that maintains the airtightness inside the organic EL display, that is, deteriorates the organic light emitting layer, is inside the organic EL display. Can be prevented, and as a result, the long-term reliability of the organic EL display can be ensured.
  • the sealing material for organic EL displays of the present invention contains bismuth glass powder. Since bismuth-based glass is excellent in water resistance, it can prevent deterioration of the organic light emitting layer. Further, since the bismuth glass has a low softening point, it can be sealed in a short time and the sealing strength can be increased. In addition, bismuth-based glass is less likely to foam when irradiated with laser light or the like, and the mechanical strength of the sealed portion is unlikely to decrease due to foaming. Furthermore, bismuth-based glass is thermally stable, and when irradiated with laser light or the like, it is difficult for the glass to be devitrified, and a situation in which the sealing strength is reduced due to devitrification is unlikely to occur.
  • the sealing material for an organic EL display of the present invention has a bismuth glass powder as a glass composition, and a CuO + Fe 2 O 3 content of 0.2% by mass or more (preferably 0.5% by mass or more, 1% by mass or more). 1.5% by mass or more, 2% by mass or more, 3% by mass or more, particularly 3.5% by mass or more).
  • a bismuth glass powder as a glass composition
  • a CuO + Fe 2 O 3 content of 0.2% by mass or more (preferably 0.5% by mass or more, 1% by mass or more). 1.5% by mass or more, 2% by mass or more, 3% by mass or more, particularly 3.5% by mass or more).
  • the sealing material for an organic EL display of the present invention When the sealing material is locally heated with a laser beam or the like, the temperature at a part 1 mm away from the heated part is 100 ° C. or lower, and thermal damage to the active element and the organic light emitting layer can be prevented.
  • the bismuth-based glass powder regulates the content of CuO + Fe 2 O 3 to 15% by mass or less as the glass composition. If it does in this way, the situation where glass devitrifies at the time of irradiation of a laser beam etc. can be prevented.
  • the sealing material for organic EL display of the present invention preferably contains 55 to 100% by volume of bismuth-based glass powder and 0 to 45% by volume of refractory filler powder, and the bismuth-based glass powder has CuO + Fe 2 as a glass composition.
  • O 3 total amount of CuO and Fe 2 O 3 ) is contained in an amount of 0.2 to 15% by mass.
  • the sealing material for organic EL displays of the present invention preferably contains 25 to less than 60% by volume of bismuth glass powder, more than 40 to 75% by volume of refractory filler powder, and the bismuth glass powder has a glass composition. As a result, 0.5 to 15% by mass of CuO + Fe 2 O 3 is contained.
  • the bismuth-based glass powder preferably has a glass composition of Bi 2 O 3 67-90%, B 2 O 3 2- 12%, ZnO 1-20%, CuO + Fe 2 O 3 0.2-15%.
  • the bismuth-based glass powder preferably has a glass composition of Bi 2 O 3 67 to 87%, B 2 O 3 in terms of the following oxide equivalent mass%. 2 to 12%, ZnO 1 to 20%, CuO + Fe 2 O 3 0.5 to 15%.
  • the refractory filler powder is preferably cordierite, willemite, alumina, zirconium tungstate phosphate, zirconium tungstate, zirconium phosphate, zircon, zirconia, oxidation. It is 1 type, or 2 or more types chosen from tin.
  • the average particle diameter D 50 of the refractory filler powder is preferably less than 15 [mu] m, the maximum particle diameter D max of the refractory filler powder, preferably 30 ⁇ m or less.
  • the “average particle diameter D 50 ” refers to a value measured with a laser diffractometer, and in the volume-based cumulative particle size distribution curve measured by the laser diffraction method, the accumulated amount is accumulated from the smaller particle.
  • the “maximum particle size D max ” represents a particle size in which the cumulative amount is 99% cumulative from the smaller particle size.
  • the sealing material for an organic EL display of the present invention does not substantially contain PbO.
  • substantially does not contain PbO refers to a case where the content of PbO in the glass composition is 1000 ppm or less. In this way, environmental demands in recent years can be satisfied.
  • sealing material for organic EL display of the present invention may further contain 0 to 10% by volume of an oxide pigment.
  • the sealing material for organic EL displays of the present invention has a thermal expansion coefficient of 80 ⁇ 10 ⁇ 7 / ° C. or less, preferably 70 ⁇ 10 ⁇ 7 / ° C. or less, more preferably 55 ⁇ 10 ⁇ 7 / ° C. or less. More preferably, it is 50 ⁇ 10 ⁇ 7 / ° C. or less (or less) because it is easy to match the thermal expansion coefficient of the sealing object such as alkali-free glass.
  • the “thermal expansion coefficient” refers to a value measured by a push rod type thermal expansion coefficient measuring apparatus, and the measurement temperature range is 30 to 300 ° C.
  • the sealing material for organic EL display of the present invention is preferably subjected to sealing treatment with irradiation light. As described above, in this way, the sealing material can be locally heated, and thermal damage to the active element and the organic light emitting layer can be prevented.
  • the irradiation light is, for example, laser light.
  • the type of laser light source is not particularly limited.
  • a semiconductor laser, a YAG laser, a CO 2 laser, an excimer laser, an infrared laser, and the like are preferable in terms of easy handling.
  • the laser beam preferably has an emission center wavelength of 500 to 1600 nm, preferably 750 to 1300 nm, in order to allow the glass to absorb light accurately.
  • infrared light such as an infrared lamp
  • the sealing material can be locally heated over a wide range, and as a result, the manufacturing efficiency of the organic EL display is improved.
  • Bi 2 O 3 is the main component for lowering the softening point, the content of 67 - 90%, preferably 67-87%, particularly 70-87%, more preferably from 70 to 85%, particularly 72 to It is 85%, more preferably 72 to 83%, particularly 75 to 83%.
  • the content of Bi 2 O 3 is less than 67%, the softening point of the glass becomes too high, and the glass is difficult to soften even when irradiated with laser light or the like.
  • the content of Bi 2 O 3 is more than 90%, the glass becomes thermally unstable, and the glass tends to devitrify during melting or irradiation.
  • B 2 O 3 is a component that forms a glass network of bismuth-based glass, and its content is 2 to 12%, preferably 3 to 10%, more preferably 4 to 10%, still more preferably 5 to 9%. It is. If the content of B 2 O 3 is less than 2%, the glass becomes thermally unstable, and the glass tends to devitrify during melting or irradiation. On the other hand, if the content of B 2 O 3 is more than 12%, the softening point of the glass becomes too high, and the glass is difficult to soften even when irradiated with laser light or the like.
  • ZnO is a component that suppresses the devitrification of the glass during melting or irradiation and lowers the thermal expansion coefficient of the glass, and its content is 1 to 20%, preferably 2 to 15%, more preferably 3 to 15 %, More preferably 3 to 12%.
  • the ZnO content is less than 1%, it is difficult to obtain an effect of suppressing devitrification of the glass at the time of melting or irradiation.
  • the content of ZnO is more than 20%, the component balance in the glass composition is impaired, and conversely, the glass is easily devitrified.
  • CuO + Fe 2 O 3 is a component having light absorption characteristics, and when irradiated with light having a predetermined emission center wavelength, CuO + Fe 2 O 3 is a component that easily absorbs light and softens the glass. CuO + Fe 2 O 3 is a component that suppresses devitrification of the glass during melting or irradiation.
  • the content of CuO + Fe 2 O 3 is 0.2 to 15%, preferably 0.5 to 15%, more preferably 0.5 to 10%, still more preferably 1 to 10%, and still more preferably 1.5 to 10%. %, In particular 2 to 10%, particularly preferably 2 to 8%, alternatively 3 to 10%, most preferably 3 to 8%, in particular 3.5 to 8%.
  • CuO is a component having a light absorption characteristic, and when irradiated with light having a predetermined emission center wavelength, it is a component that absorbs light and softens the glass, and devitrifies the glass during melting or irradiation.
  • the content is 0 to 15%, 0.2 to 15%, 0.5 to 10%, 1 to 15%, 1 to 10%, 2 to 10%, 3 to 8%, 3.5 to 7% is particularly preferable.
  • the content of CuO is more than 15%, the component balance in the glass composition is impaired, conversely, the glass is easily devitrified, and the fluidity of the glass is easily impaired.
  • a light absorption characteristic will become scarce and even if it irradiates a laser beam etc., it will become difficult to soften glass.
  • Fe 2 O 3 is a component having light absorption characteristics, and when irradiated with light having a predetermined emission center wavelength, it is a component that absorbs light and softens the glass, and is glass during melting or irradiation. Is a component that suppresses devitrification, and its content is 0 to 7%, preferably 0.05 to 7%, more preferably 0.1 to 4%, and still more preferably 0.2 to 2%. When the content of Fe 2 O 3 is more than 7%, balance of components in the glass composition is impaired, the glass is easily devitrified Conversely, the flowability of the glass is easily impaired. Incidentally, when the content of Fe 2 O 3 is small, the light absorption characteristic is poor, even when irradiated with a laser beam or the like, a glass is hardly softened.
  • Fe in the glass composition exists in the form of Fe 2+ or Fe 3+ , but in the present invention, Fe in the glass composition is limited to either Fe 2+ or Fe 3+. It doesn't matter.
  • Fe 2+ is handled after being converted to Fe 2 O 3 .
  • the ratio of Fe 2+ is 0. 0.03 or more (preferably 0.08 or more).
  • the bismuth-based glass powder in the present invention can contain, for example, up to 20% of the following components as a glass composition.
  • SiO 2 is a component that improves the water resistance of the glass. Its content is 0 to 10%, preferably 0 to 3%. If the content of SiO 2 is more than 10%, the softening point of the glass becomes too high, and the glass is difficult to soften even when irradiated with laser light or the like.
  • Al 2 O 3 is a component that improves the water resistance of the glass. Its content is 0-5%, preferably 0-2%. When the content of Al 2 O 3 is more than 5%, the softening point of the glass becomes too high, and the glass is difficult to soften even when irradiated with laser light or the like.
  • MgO + CaO + SrO + BaO (total amount of MgO, CaO, SrO and BaO) is a component that suppresses glass devitrification at the time of melting or irradiation, and the content of these components is 0 to 15% in total, preferably 0 to 10%. If the content of MgO + CaO + SrO + BaO is more than 15%, the softening point of the glass becomes too high, and the glass becomes difficult to soften even when irradiated with laser light or the like.
  • MgO is a component that suppresses devitrification of the glass during melting or irradiation, and its content is 0 to 5%, preferably 0 to 2%.
  • the content of MgO is more than 5%, the softening point of the glass becomes too high, and the glass is difficult to soften even when irradiated with laser light or the like.
  • CaO is a component that suppresses the devitrification of the glass during melting or irradiation, and its content is 0 to 5%, preferably 0 to 2%. If the content of CaO is more than 5%, the softening point of the glass becomes too high, and the glass is difficult to soften even when irradiated with laser light or the like.
  • SrO is a component that suppresses devitrification of the glass at the time of melting or irradiation, and its content is 0 to 5%, preferably 0 to 2%. If the SrO content is more than 5%, the softening point of the glass becomes too high, and the glass is difficult to soften even when irradiated with laser light or the like.
  • BaO is a component that suppresses the devitrification of the glass during melting or irradiation, and its content is 0 to 10%, preferably 0 to 8%. When the content of BaO is more than 10%, the softening point of the glass becomes too high, and the glass is difficult to soften even when irradiated with laser light or the like.
  • CeO 2 is a component that suppresses the devitrification of the glass during melting or irradiation, and its content is 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%.
  • the content of CeO 2 is more than 5%, the component balance in the glass composition is impaired, and conversely, the glass is easily devitrified.
  • it is preferable to add a small amount of CeO 2 and specifically, the content of CeO 2 is preferably 0.01% or more.
  • Sb 2 O 3 is a component for suppressing the devitrification of the glass, and its content is 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%.
  • Sb 2 O 3 has an effect of stabilizing the network structure of the bismuth-based glass. If Sb 2 O 3 is appropriately added to the bismuth-based glass, when the content of Bi 2 O 3 is large, for example, Bi 2 O 3 Even if the content of 3 is 76% or more, the thermal stability of the glass is hardly lowered. However, when the content of Sb 2 O 3 is more than 5%, balance of components in the glass composition is impaired, the glass tends to be devitrified reversed. From the viewpoint of improving the thermal stability of the glass, it is preferable to add a small amount of Sb 2 O 3. Specifically, the content of Sb 2 O 3 is preferably 0.05% or more.
  • Nd 2 O 3 is a component for suppressing the devitrification of the glass, and its content is 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%.
  • Nd 2 O 3 has an effect of stabilizing the network structure of the bismuth-based glass. If Nd 2 O 3 is appropriately added to the bismuth-based glass, the content of Bi 2 O 3 is large, for example, Bi 2 O 3 Even if the content of 3 is 76% or more, the thermal stability of the glass is hardly lowered. However, if the content of Nd 2 O 3 is more than 5%, balance of components in the glass composition is impaired, the glass tends to be devitrified reversed. Further, from the viewpoint of improving the thermal stability of the glass, dopants are preferred Nd 2 O 3, specifically, the content of Nd 2 O 3 is preferably at least 0.05%.
  • WO 3 is a component for suppressing devitrification of glass, and its content is 0 to 10%, preferably 0 to 2%. However, if the content of WO 3 is more than 10%, the component balance in the glass composition is impaired, and conversely, the glass tends to devitrify.
  • In 2 O 3 + Ga 2 O 3 (total amount of In 2 O 3 and Ga 2 O 3 ) is not an essential component, but is a component for suppressing devitrification of glass, and its content is 0 in total. -5%, preferably 0-3%. However, if the content of In 2 O 3 + Ga 2 O 3 is more than 5%, the component balance in the glass composition is impaired, and conversely, the glass is easily devitrified.
  • the In 2 O 3 content is more preferably 0 to 1%, and the Ga 2 O 3 content is more preferably 0 to 0.5%.
  • the oxides of Li, Na, K, and Cs are components that lower the softening point of the glass, but the total amount is preferably 2% or less because it has an action of promoting devitrification of the glass when melted.
  • P 2 O 5 is a component that suppresses the devitrification of the glass at the time of melting. However, if the amount of P 2 O 5 added is more than 1%, the glass is likely to phase separate at the time of melting.
  • La 2 O 3 , Y 2 O 3 and Gd 2 O 3 are components that suppress the phase separation of the glass at the time of melting, but when the total amount of these is more than 3%, the softening point of the glass becomes too high, Even when laser light or the like is irradiated, the glass becomes difficult to soften.
  • NiO is a component having light absorption characteristics, and when irradiated with light having a predetermined emission center wavelength, NiO is a component that easily absorbs light and softens the glass, and its content is 0 to 7%, preferably Is 0 to 3%. If the content of NiO is more than 7%, the glass tends to be devitrified, and the fluidity of the glass tends to be impaired.
  • V 2 O 5 is a component having light absorption characteristics, and when irradiated with light having a predetermined emission center wavelength, V 2 O 5 is a component that easily absorbs light and softens the glass, and its content is 0 to 7 %, Preferably 0 to 3%. When the content of V 2 O 5 is more than 7%, the glass tends to foam during irradiation.
  • CoO is a component having a light absorption characteristic, and is a component that absorbs light and softens the glass when irradiated with light having a predetermined emission center wavelength, and its content is preferably 0 to 7%, preferably Is 0 to 3%. When the content of CoO is more than 7%, the glass tends to devitrify, and the fluidity of the glass tends to be impaired.
  • MoO 3 is a component having light absorption characteristics, and when irradiated with light having a predetermined emission center wavelength, it is a component that absorbs light and softens the glass, and its content is 0 to 7%, Preferably, it is 0 to 3%. When the content of MoO 3 is more than 7%, the glass tends to be devitrified, the flowability of the glass is easily impaired.
  • TiO 2 is a component having a light absorption property is irradiated with light having a predetermined emission center wavelength, absorbs the light, a component which tends to soften the glass, the content thereof is from 0 to 7% Preferably, it is 0 to 3%.
  • the content of TiO 2 is more than 7%, the glass tends to be devitrified, the flowability of the glass is easily impaired.
  • the content of TiO 2 is more than 7%, the softening point of the glass becomes too high, and it becomes difficult to soften the glass even when irradiated with laser light or the like.
  • MnO 2 is a component having light absorption characteristics, and when irradiated with light having a predetermined emission center wavelength, it is a component that easily absorbs light and softens the glass, and its content is 0 to 7%, Preferably, it is 0 to 3%. When the content of MnO 2 is more than 7%, the glass is easily devitrified, and the fluidity of the glass is easily impaired.
  • PbO is not substantially contained from the environmental viewpoint.
  • the sealing material for organic EL display of the present invention preferably contains 55 to 100% by volume of bismuth glass powder and 0 to 45% by volume of refractory filler powder, and has a fire resistance of 65 to 100% by volume of bismuth glass powder. More preferably, it contains 0 to 35% by volume of filler powder, more preferably 65 to 85% by volume of bismuth glass powder and 15 to 35% by volume of refractory filler powder. Since bismuth-based glass powder has a low melting point, it flows well at low temperatures. Further, if a refractory filler powder is added to the bismuth-based glass powder, the thermal expansion coefficient of the sealing material can be adjusted, so that the thermal expansion coefficient of the sealed object can be easily matched. As a result, it is possible to prevent a situation in which undue stress remains at the sealing portion.
  • the sealing material for organic EL display of the present invention preferably contains bismuth-based glass powder 25 to less than 60% by volume, refractory filler powder 40 to 75% by volume, and bismuth-based glass powder 25 to 50% by volume. More preferably, it contains less than 50%, and more than 50 to 75% by volume of refractory filler powder, more preferably 30 to 45% by volume of bismuth glass powder and 55 to 70% by volume of refractory filler powder. Since bismuth-based glass powder has a low melting point, it flows well at low temperatures.
  • the thermal expansion coefficient of the sealing material can be easily matched with the thermal expansion coefficient of the sealed object such as non-alkali glass. As a result, it is possible to prevent a situation in which undue stress remains in the alkali-free glass or the sealing part.
  • the content of the refractory filler powder is more than 75% by volume, the content of the bismuth-based glass powder becomes relatively small, and it becomes difficult to ensure the desired fluidity.
  • the content of the refractory filler powder is more than 75 vol%, when the average particle diameter D 50 of the refractory filler powder is 10 ⁇ m or less, the refractory filler powder is easily dissolved in the glass during the irradiation, as a result , The glass tends to devitrify.
  • the above-described materials can be used as the refractory filler powder.
  • These refractory filler powders have a low mechanical expansion coefficient, a high mechanical strength, and a good compatibility with bismuth-based glass powders.
  • refractory filler powders such as quartz glass and ⁇ -eucryptite are used for adjusting the thermal expansion coefficient of the sealing material, adjusting the fluidity and improving the mechanical strength. Can be added.
  • the thermal expansion coefficient of the sealing material for organic EL displays of the present invention is desirably 80 ⁇ 10 ⁇ 7 / ° C. or less, particularly 70 ⁇ 10 ⁇ 7 / ° C. or less. If it does in this way, the stress concerning a sealing part can be made small and the stress fracture of a sealing part can be prevented.
  • the sealing material for an organic EL display of the present invention preferably further contains 0 to 10% by volume, preferably 0.1 to 5% by volume, more preferably 0.5 to 3% by volume of an oxide pigment.
  • an oxide pigment Cu-based oxides, Fe-based oxides, Cr-based oxides, Mn-based oxides and their spinel type complex oxides can be used.
  • oxide pigments Mn-based oxides can be used. (For example, 42-343B manufactured by Toago Material Co., Ltd.) is preferable. These oxide pigments can promote light absorption such as laser light, and as a result, the sealing strength of the sealing material can be increased.
  • the sealing material for organic EL displays of the present invention may further contain up to 10% by volume of glass fiber, glass beads, silica beads, resin beads, etc. as spacers in order to make the thickness of the sealing part uniform. Moreover, the sealing material for organic EL displays 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 promote light absorption.
  • the softening point is preferably 550 ° C. or less, more preferably 500 ° C. or less, and further preferably 465 ° C. or less.
  • 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 it is preferable to set the softening point to 385 ° C. or higher in consideration of the thermal stability of the glass.
  • the “softening point” refers to a value measured with a differential thermal analyzer, and the temperature rise rate is 10 ° C./min in air.
  • the average particle diameter D 50 of the refractory filler powder is preferably less than 15 [mu] m, more preferably 0.5 ⁇ 10 ⁇ m, 1 ⁇ 5 ⁇ m are more preferred.
  • the average particle diameter D 50 of the refractory filler powder is 15 ⁇ m or more, sealing portion tends to become thick, the gap increases between the glass substrates, it becomes difficult to thin the organic EL display.
  • the average particle diameter D 50 of the refractory filler powder when the average particle diameter D 50 of the refractory filler powder to less than 15 [mu] m, it is possible to reduce the gap between the glass substrates, in such a case, the difference in the thermal expansion coefficient of the glass substrate and the sealing material is larger However, cracks and the like hardly occur in the glass substrate and the sealing part.
  • the refractory filler powder effects e.g., effect of reducing the thermal expansion coefficient of the sealing material in order to accurately enjoy is to the average particle diameter D 50 of the refractory filler powder than 0.5 ⁇ m Is preferred.
  • the maximum particle diameter Dmax of the refractory filler powder is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 10 ⁇ m or less. If the maximum particle diameter Dmax of the refractory filler powder is larger than 30 ⁇ m, a portion having a thickness of 30 ⁇ m or more is generated at the sealing portion, so that the gap between the glass substrates becomes non-uniform, and the organic EL display becomes thin. It becomes difficult to convert. In addition, when the average particle diameter Dmax of the refractory filler powder is 30 ⁇ m or less, the gap between the glass substrates can be reduced. In such a case, the difference in the thermal expansion coefficient between the glass substrate and the sealing material is large. However, cracks and the like hardly occur in the glass substrate and the sealing part.
  • the average particle diameter D 50 of the bismuth glass powder is preferably less than 15 [mu] m, more preferably 0.5 ⁇ 10 ⁇ m, 1 ⁇ 5 ⁇ m are more preferred.
  • the average particle diameter D 50 of the bismuth glass powder to less than 15 [mu] m, makes it easier to reduce the gap between the glass substrates, in such a case, even if large difference in thermal expansion coefficient of the glass substrate and the sealing material, Cracks and the like are less likely to occur in the glass substrate and the sealing part, and the time required for sealing can be shortened.
  • the maximum particle diameter Dmax of the bismuth-based glass powder is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 10 ⁇ m or less.
  • the average particle diameter Dmax of the bismuth-based glass powder is 30 ⁇ m or less, it becomes easy to reduce the gap between the two glass substrates. In such a case, even if the difference in the thermal expansion coefficient between the glass substrate and the sealing material is large, Cracks and the like are less likely to occur in the glass substrate and the sealing part, and the time required for sealing can be shortened.
  • the organic EL display sealing material of the present invention may be used in powder form, but is easy to handle if it is uniformly kneaded with a vehicle and processed into a paste.
  • the vehicle mainly includes a solvent and a resin, and the resin 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 applied to a glass substrate using an applicator such as a dispenser or a screen printer, and is subjected to a binder removal process.
  • acrylic acid ester (acrylic resin), ethyl cellulose, polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, methacrylic acid ester and the like can be used.
  • acrylic acid esters and nitrocellulose are preferable because they have good thermal decomposability.
  • Solvents include N, N′-dimethylformamide (DMF), ⁇ -terpineol, higher alcohol, ⁇ -butyllactone ( ⁇ -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- Chill-2-pyrrolidone and the like can be used.
  • ⁇ -terpineol is preferable because it is highly viscous and
  • Tables 1 to 4 show examples of the present invention (sample Nos. 1 to 18) and comparative examples (sample Nos. 19 to 23).
  • Each sample described in Tables 1 to 4 was prepared as follows. First, a glass batch prepared by preparing raw materials such as various oxides and carbonates so as to have the glass composition shown in the table was prepared, and this 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 10 [mu] m.
  • each refractory filler powder has an average particle diameter D 50 of 2.5 [mu] m, maximum particle diameter D max was prepared so that the 10 [mu] m.
  • sample no. 1 to 23 were produced.
  • Sample No. 1 to 23 the glass transition point, softening point, thermal expansion coefficient, fluidity, sealing strength, foamed state and devitrified state were evaluated.
  • the glass transition point and softening point were measured with a differential thermal analyzer. 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 obtained with a push rod type thermal expansion coefficient measuring device.
  • the measurement temperature range was 30 to 300 ° C.
  • the sealing strength was evaluated as follows. First, each sample and vehicle ( ⁇ -terpineol containing acrylic resin) were uniformly kneaded with a three-roll mill and made into a paste, and then an alkali-free glass substrate (OA-10 manufactured by Nippon Electric Glass Co., Ltd., 100 mm ⁇ 100 mm ⁇ 0.5 mm thick) was applied linearly (30 ⁇ m thickness) to the outer peripheral edge, and dried in a drying oven at 150 ° C. for 10 minutes. Next, the temperature was raised from room temperature at 10 ° C./minute, baked at 450 ° C. for 20 minutes, and then lowered to room temperature at 10 ° C./minute to perform a binder removal treatment.
  • OA-10 manufactured by Nippon Electric Glass Co., Ltd., 100 mm ⁇ 100 mm ⁇ 0.5 mm thick
  • the cross section of the sealing part formed by the above-described evaluation of the sealing strength is observed with an optical microscope, and “O” indicates that there are less than 5 bubbles of ⁇ 5 ⁇ m or more in an area of 100 ⁇ m ⁇ 100 ⁇ m, and ⁇ 5 ⁇ m Those having 5 or more bubbles were evaluated as “x”.
  • the surface of the sealed portion formed by the above-described evaluation of the sealing strength is observed with an optical microscope (100 times), and “ ⁇ ” indicates that the crystal is observed on the surface, and the crystal is observed on the surface. Those not present were evaluated as “x”.
  • sample No. Nos. 1 to 18 have good evaluation of fluidity, sealing strength, foamability and devitrification state, and can be judged to be suitable for sealing materials for organic EL displays.
  • Tables 5 to 7 show examples of the present invention (Sample Nos. 2-1 to 2-12) and comparative examples (Samples Nos. 2-13 to 2-16).
  • Each sample described in Tables 5 to 7 was prepared as follows. First, a glass batch prepared by preparing raw materials such as various oxides and carbonates so as to have the glass composition shown in the table was prepared, and this 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 10 [mu] m.
  • each refractory filler powder has an average particle diameter D 50 of 2.5 [mu] m, maximum particle diameter D max was prepared so that the 10 [mu] m.
  • sample no. 2-1 to 2-16 were produced.
  • the glass transition point and softening point were measured with a differential thermal analyzer. 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 obtained with a push rod type thermal expansion coefficient measuring device.
  • the measurement temperature range was 30 to 300 ° C.
  • 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.
  • a non-alkali glass substrate obtained by processing this paste into a strip shape (OA-10, manufactured by Nippon Electric Glass Co., Ltd., 10 mm ⁇ 50 mm ⁇ 0.7 mm thickness, coefficient of thermal expansion (30 to 380 ° C.) 38 ⁇ 10 ⁇ 7 / ° C.) After printing and coating so that the line width was 0.8 mm ⁇ length 4 mm ⁇ thickness 20 ⁇ m, was dried in a drying oven at 120 ° C. for 30 minutes.
  • 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 the alkali-free glass substrate processed into a strip of the same shape on the alkali-free glass substrate on which the glaze film is formed, the glaze film from the glass substrate side on which the glaze film is not formed Were irradiated with a semiconductor laser having a wavelength of 808 nm (output 20 W, scanning speed 2 mm / s).
  • Sample No. 2-1 to 2-12 have a thermal expansion coefficient of 50 ⁇ 10 ⁇ 7 / ° C. or less and a small difference in thermal expansion coefficient from non-alkali glass, so that the amount of strain remaining on the glass substrate after bonding becomes small, No cracks were observed on the glass substrate. Therefore, sample no. It is considered that 2-1 to 2-12 can be suitably used for an organic EL display using an alkali-free glass substrate.
  • Sample No. 2-16 was an evaluation of “unbondable”. This is thought to be due to the glass being devitrified during laser irradiation and the softening deformation being inhibited because the content of the refractory filler powder is as large as 76% by volume.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention porte sur une matière de scellement pour des affichages EL organiques, qui contient de 25 à 100 % en volume d'une poudre de verre de bismuth et de 0 à 75 % en volume d'une poudre de charge résistante au feu. La poudre de verre de bismuth contient de 0,2 à 15 % en masse de CuO + Fe2O3 en tant que composition de verre.
PCT/JP2009/051167 2008-02-28 2009-01-26 Matière de scellement pour affichage el organique WO2009107428A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020127007801A KR101236373B1 (ko) 2008-02-28 2009-01-26 유기 ｅｌ 디스플레이의 제조 방법
KR1020107007027A KR101236369B1 (ko) 2008-02-28 2009-01-26 유기 el 디스플레이용 봉착 재료
KR1020127007798A KR101236371B1 (ko) 2008-02-28 2009-01-26 유기 ｅｌ 디스플레이용 글레이즈막 부착 무알칼리 유리 기판
KR1020137004395A KR101330100B1 (ko) 2008-02-28 2009-01-26 유기 ｅｌ 디스플레이용 봉착 재료

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2008047533 2008-02-28
JP2008-047533 2008-02-28
JP2008212424A JP5440997B2 (ja) 2008-08-21 2008-08-21 有機ｅｌディスプレイ用封着材料
JP2008-212424 2008-08-21
JP2009009410A JP5458579B2 (ja) 2008-02-28 2009-01-20 有機ｅｌディスプレイ用封着材料
JP2009-009410 2009-01-20

Publications (1)

Publication Number Publication Date
WO2009107428A1 true WO2009107428A1 (fr) 2009-09-03

Family

ID=41015834

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/051167 WO2009107428A1 (fr) 2008-02-28 2009-01-26 Matière de scellement pour affichage el organique

Country Status (1)

Country Link
WO (1) WO2009107428A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011036605A1 (fr) * 2009-09-22 2011-03-31 Koninklijke Philips Electronics N.V. Conditionnement en verre pour l'étanchéisation d'un dispositif, et système comportant un conditionnement en verre
CN102939270A (zh) * 2010-06-14 2013-02-20 旭硝子株式会社 密封材料糊以及使用其的电子器件的制造方法
JP2014001134A (ja) * 2008-02-28 2014-01-09 Nippon Electric Glass Co Ltd 有機ｅｌディスプレイの製造方法
US8778469B2 (en) 2010-03-19 2014-07-15 Asahi Glass Company, Limited Electronic device and method for manufacturing same
CN108883971A (zh) * 2016-04-01 2018-11-23 日本电气硝子株式会社 玻璃粉末及使用其的密封材料
US20200199005A1 (en) * 2017-09-04 2020-06-25 Nippon Electric Glass Co., Ltd. Method and device for manufacturing a glass article, and a powder for forming a bonded body

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0859294A (ja) * 1994-08-17 1996-03-05 Nippon Electric Glass Co Ltd 低融点封着用組成物
JP2000128574A (ja) * 1998-10-21 2000-05-09 Nippon Electric Glass Co Ltd ビスマス系ガラス組成物
JP2006143480A (ja) * 2004-11-16 2006-06-08 Nippon Electric Glass Co Ltd Ｂｉ２Ｏ３−Ｂ２Ｏ３系ガラス組成物およびＢｉ２Ｏ３−Ｂ２Ｏ３系封着材料
JP2007031258A (ja) * 2005-06-23 2007-02-08 Asahi Techno Glass Corp 低融点ガラスおよび封着用組成物ならびに封着用ペースト
JP2007210870A (ja) * 2005-03-09 2007-08-23 Nippon Electric Glass Co Ltd ビスマス系ガラス組成物およびビスマス系封着材料
JP2008037740A (ja) * 2006-07-11 2008-02-21 Nippon Electric Glass Co Ltd 封着用ガラス組成物および封着材料

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0859294A (ja) * 1994-08-17 1996-03-05 Nippon Electric Glass Co Ltd 低融点封着用組成物
JP2000128574A (ja) * 1998-10-21 2000-05-09 Nippon Electric Glass Co Ltd ビスマス系ガラス組成物
JP2006143480A (ja) * 2004-11-16 2006-06-08 Nippon Electric Glass Co Ltd Ｂｉ２Ｏ３−Ｂ２Ｏ３系ガラス組成物およびＢｉ２Ｏ３−Ｂ２Ｏ３系封着材料
JP2007210870A (ja) * 2005-03-09 2007-08-23 Nippon Electric Glass Co Ltd ビスマス系ガラス組成物およびビスマス系封着材料
JP2007031258A (ja) * 2005-06-23 2007-02-08 Asahi Techno Glass Corp 低融点ガラスおよび封着用組成物ならびに封着用ペースト
JP2008037740A (ja) * 2006-07-11 2008-02-21 Nippon Electric Glass Co Ltd 封着用ガラス組成物および封着材料

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014001134A (ja) * 2008-02-28 2014-01-09 Nippon Electric Glass Co Ltd 有機ｅｌディスプレイの製造方法
JP2014012634A (ja) * 2008-02-28 2014-01-23 Nippon Electric Glass Co Ltd 有機ｅｌディスプレイ用乾燥膜付きガラス基板
WO2011036605A1 (fr) * 2009-09-22 2011-03-31 Koninklijke Philips Electronics N.V. Conditionnement en verre pour l'étanchéisation d'un dispositif, et système comportant un conditionnement en verre
US9028932B2 (en) 2009-09-22 2015-05-12 Koninklijkle Philips N.V. Glass package for sealing a device, and system comprising glass package
US8778469B2 (en) 2010-03-19 2014-07-15 Asahi Glass Company, Limited Electronic device and method for manufacturing same
CN102939270A (zh) * 2010-06-14 2013-02-20 旭硝子株式会社 密封材料糊以及使用其的电子器件的制造方法
CN102939270B (zh) * 2010-06-14 2015-11-25 旭硝子株式会社 密封材料糊以及使用其的电子器件的制造方法
CN108883971A (zh) * 2016-04-01 2018-11-23 日本电气硝子株式会社 玻璃粉末及使用其的密封材料
US20200199005A1 (en) * 2017-09-04 2020-06-25 Nippon Electric Glass Co., Ltd. Method and device for manufacturing a glass article, and a powder for forming a bonded body

Similar Documents

Publication Publication Date Title
JP5862972B2 (ja) 有機ｅｌディスプレイ用乾燥膜付きガラス基板
JP6455801B2 (ja) 封着材料
JP5224102B2 (ja) 有機ｅｌディスプレイ用封着材料
WO2011122218A1 (fr) Matériau d'étanchéité et pâte utilisant ce matériau
JP6075715B2 (ja) ビスマス系ガラス及びこれを用いた封着材料
JP5440997B2 (ja) 有機ｅｌディスプレイ用封着材料
JP5190671B2 (ja) バナジウム系ガラス組成物およびバナジウム系材料
JP2011057477A (ja) 封着材料
JP6269991B2 (ja) 封着材料層付きガラス基板
WO2009107428A1 (fr) Matière de scellement pour affichage el organique
JP5458648B2 (ja) 有機ｅｌ照明用封着材料
JP2010111520A (ja) ビスマス系ガラス粉末の製造方法
JP5994438B2 (ja) 封着材料層付きガラス基板の製造方法
JP5224103B2 (ja) 封着用ガラス組成物および封着材料
JP2011225426A (ja) 封着材料及びこれを用いたペースト材料
JP2013049614A (ja) 封着材料層付きガラス基板の製造方法
KR101236373B1 (ko) 유기 ｅｌ 디스플레이의 제조 방법
JP5489061B2 (ja) フィラー粉末およびこれを用いた封着材料
JP2012106900A (ja) 封着材料及びこれを用いたペースト材料
JP2013049613A (ja) 封着材料層付きガラス基板の製造方法
JP2012162441A (ja) 封着材料及びこれを用いたペースト材料

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09714771

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20107007027

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09714771

Country of ref document: EP

Kind code of ref document: A1