JP5458579B2 - Sealing material for organic EL display - Google Patents
Sealing material for organic EL display Download PDFInfo
- Publication number
- JP5458579B2 JP5458579B2 JP2009009410A JP2009009410A JP5458579B2 JP 5458579 B2 JP5458579 B2 JP 5458579B2 JP 2009009410 A JP2009009410 A JP 2009009410A JP 2009009410 A JP2009009410 A JP 2009009410A JP 5458579 B2 JP5458579 B2 JP 5458579B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- organic
- sealing material
- content
- display
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
- 239000003566 sealing material Substances 0.000 title claims description 67
- 239000011521 glass Substances 0.000 claims description 216
- 239000000843 powder Substances 0.000 claims description 66
- 229910052797 bismuth Inorganic materials 0.000 claims description 35
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 35
- 239000000945 filler Substances 0.000 claims description 34
- 238000007789 sealing Methods 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 25
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 10
- 239000000049 pigment Substances 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052878 cordierite Inorganic materials 0.000 claims description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052844 willemite Inorganic materials 0.000 claims description 4
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 4
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 229910052845 zircon Inorganic materials 0.000 claims description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000758 substrate Substances 0.000 description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 238000004031 devitrification Methods 0.000 description 19
- 230000001771 impaired effect Effects 0.000 description 18
- 238000002844 melting Methods 0.000 description 18
- 230000008018 melting Effects 0.000 description 18
- 230000031700 light absorption Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 3
- 229940088601 alpha-terpineol Drugs 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910000174 eucryptite Inorganic materials 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- -1 polymethylstyrene Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 230000003685 thermal hair damage Effects 0.000 description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- RPYNRYGNIGNIHL-UHFFFAOYSA-N C(COCCOCCO)O.C(CCC)OCC(C)O Chemical compound C(COCCOCCO)O.C(CCC)OCC(C)O RPYNRYGNIGNIHL-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 208000013201 Stress fracture Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012508 resin bead Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005394 sealing glass Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Glass Compositions (AREA)
Description
本発明は、有機ＥＬディスプレイ用封着材料に関し、具体的には照射光による封着処理に供される有機ＥＬディスプレイ用封着材料に関する。 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 treatment with irradiation light.
近年、フラットディスプレイパネルとして有機ＥＬディスプレイが注目されている。有機ＥＬディスプレイは、直流電圧で駆動できるため駆動回路を簡略化できるとともに、液晶ディスプレイのように視野角依存性がなく、また自己発光のため明るく、更には応答速度が速い等の利点がある。現在、有機ＥＬディスプレイは、主に携帯電話等の小型携帯機器に利用されているが、今後は超薄型テレビへの応用が期待されている。 In recent years, 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. 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.
有機ＥＬディスプレイは、２枚のガラス基板、金属等の陰電極、有機発光層、ＩＴＯ等の陽電極、接着材料等で構成される。従来、接着材料として、低温硬化性を有するエポキシ樹脂、或いは紫外線硬化樹脂等の有機樹脂系接着材料が使用されてきた。しかし、有機樹脂系接着材料は気体の侵入を完全に遮断することが困難であるため、有機ＥＬディスプレイ内部の気密性を維持することが困難であり、このことに起因して、耐水性の低い有機発光層が劣化しやすくなり、経時的に有機ＥＬディスプレイの表示特性が劣化するといった不具合が生じていた。また、有機樹脂系接着材料は、低温でガラス基板同士を接着できる利点を有するものの、耐水性が低い欠点を有し、有機ＥＬディスプレイを長期に亘って使用した場合、ディスプレイの信頼性が低下しやすくなる。 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. Conventionally, 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. However, 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. In addition, the organic resin adhesive material has the advantage that the glass substrates can be bonded to each other at a low temperature, but has a disadvantage that the water resistance is low. It becomes easy.
また、有機ＥＬディスプレイは、液晶ディスプレイと同様にして、薄膜トランジスタ（ＴＦＴ）等のアクティブ素子を各画素に配置して、駆動させる方式が主流である。 In the organic EL display, as in the liquid crystal display, an active element such as a thin film transistor (TFT) is disposed in each pixel and driven.
ガラスを用いた封着材料は、有機樹脂系接着材料に比べ、耐水性に優れるとともに、有機ＥＬディスプレイ内部の気密性を確保するのに適している。 A sealing material using glass is excellent in water resistance as compared with an organic resin adhesive material and is suitable for ensuring airtightness inside the organic EL display.
しかし、封着材料に使用されるガラスは、一般的に、軟化点が３００℃以上であるため、有機ＥＬディスプレイに適用することが困難であった。つまり、上記の封着材料でガラス基板同士を封着する場合、電気炉に有機ＥＬディスプレイ全体を投入し、ガラスの軟化点以上の温度で熱処理する必要がある。しかし、アクティブ素子は、１２０〜１３０℃程度の耐熱性しか有していないため、この方法でガラス基板同士を封着すると、アクティブ素子が熱により損傷し、有機ＥＬディスプレイの表示特性が劣化してしまう。同様にして、有機発光材料も耐熱性が乏しいため、この方法でガラス基板同士を封着すると、有機発光材料が熱により損傷し、有機ＥＬディスプレイの表示特性が劣化してしまう。 However, since the glass used for the sealing material generally has a softening point of 300 ° C. or higher, it has been difficult to apply 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. However, since the active element has only a 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. Similarly, since 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.
このような事情に鑑み、近年、封着材料にレーザー光等の照射光を照射し、有機ＥＬディスプレイを封着する方法が検討されている。レーザー光等は、封着すべき部位のみを局所加熱できることから、アクティブ素子等の劣化を防止した上で、ガラス基板同士を封着することができる。 In view of such circumstances, in recent years, methods for sealing organic EL displays by irradiating sealing materials with irradiation light such as laser light have 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 the active element or the like.
特許文献１、２には、封着材料にレーザー光を照射して、フィールドエミッションディスプレイの前面ガラス基板と背面ガラス基板を封着する方法が記載されている。しかし、特許文献１、２には、この方法に好適なガラス系について具体的な記載がなく、レーザー光を封着材料に照射しても、封着部位において、レーザー光の光エネルギーを熱エネルギーに効率良く変換させることが困難であった。それ故、これらの封着材料を用いて、ガラス基板同士を封着するためには、レーザー光の出力を上げる必要があり、その結果、アクティブ素子等に不当な熱履歴がかかり、有機ＥＬディスプレイの表示特性が劣化するおそれがあった。 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. However, 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.
また、レーザー光等で封着材料を局所加熱する場合、ガラスの軟化点が低いと、短時間で封着できるとともに、封着強度を高めることができる。しかし、一般的に、ガラスの軟化点を下げると、ガラスの耐水性が低下しやすくなる。既述の通り、封着材料の耐水性は、有機発光層の劣化を防止する観点から重要であるが、特許文献１、２には、当然のことながら、低軟化特性と高耐水性を両立させたガラス系について具体的な記載はない。 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.
そこで、本発明は、レーザー光等の照射光による局所加熱に好適であるとともに、低軟化特性と高耐水性を両立させた有機ＥＬディスプレイ用封着材料を創案することにより、信頼性の高い有機ＥＬディスプレイを作製することを技術的課題とする。 Therefore, 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.
本発明者等は、鋭意努力の結果、有機ＥＬディスプレイ用封着材料として、ビスマス系ガラス粉末と耐火性フィラー粉末を含有する封着材料を用いるとともに、ビスマス系ガラス粉末において、ガラス組成として、ＣｕＯとＦｅ２Ｏ３のいずれか、或いは双方を所定量導入することにより、上記技術的課題を解決できることを見出し、本発明として、提案するものである。すなわち、本発明の有機ＥＬディスプレイ用封着材料は、ビスマス系ガラス粉末５５〜１００体積％、耐火性フィラー粉末０〜４５体積％含有し、且つビスマス系ガラス粉末が、ガラス組成として、ＣｕＯ＋Ｆｅ２Ｏ３（ＣｕＯとＦｅ２Ｏ３の合量）を０．２〜１５質量％含有することを特徴とする。ここで、「ビスマス系ガラス粉末」とは、ガラス組成中のＢｉ２Ｏ３の含有量が５０質量％以上のガラス粉末を指す。なお、本発明の有機ＥＬディスプレイ用封着材料は、耐火性フィラー粉末を添加することなく、ビスマス系ガラス粉末のみで構成されていてもよい。 As a result of diligent efforts, 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. In the bismuth glass powder, 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. That is, the sealing material for organic EL display of the present invention contains 55 to 100% by volume of bismuth glass powder and 0 to 45% by volume of refractory filler powder, and the bismuth 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. Here, “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. In addition, 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.
本発明の有機ＥＬディスプレイ用封着材料は、ビスマス系ガラス粉末５５〜１００体積％、耐火性フィラー粉末０〜４５体積％含有する。このようにすれば、被封着物の熱膨張係数に整合するように、封着材料の熱膨張係数を下げることができる。 The sealing material for organic EL displays of the present invention contains 55 to 100% by volume of bismuth glass powder and 0 to 45% by volume of refractory filler powder. In this way, the thermal expansion coefficient of the sealing material can be lowered so as to match the thermal expansion coefficient of the object to be sealed.
本発明の有機ＥＬディスプレイ用封着材料は、ガラス粉末を含有する。このようにすれば、有機ＥＬディスプレイ内部の気密性を維持、つまり有機発光層を劣化させるＨ２ＯやＯ２等が有機ＥＬディスプレイ内部に侵入する事態を防止することができ、その結果、有機ＥＬディスプレイの長期信頼性を確保することができる。 The sealing material for organic EL displays of the present invention contains glass powder. In this way, it is possible to maintain the airtightness inside the organic EL display, that is, to prevent the situation where H 2 O, O 2 or the like that degrades the organic light emitting layer enters the inside of the organic EL display. Long-term reliability of the EL display can be ensured.
本発明の有機ＥＬディスプレイ用封着材料は、ビスマス系ガラス粉末を含有する。ビスマス系ガラスは、耐水性に優れているため、有機発光層の劣化を防止することができる。また、ビスマス系ガラスは、軟化点が低いため、短時間で封着できるとともに、封着強度を高めることができる。また、ビスマス系ガラスは、レーザー光等の照射の際に、ガラスに発泡が生じ難く、発泡に起因して、封着部位の機械的強度が低下する事態が生じ難い。更に、ビスマス系ガラスは、熱的に安定であり、レーザー光等の照射の際に、ガラスが失透し難く、失透に起因して、封着強度が低下する事態が生じ難い。 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.
本発明の有機ＥＬディスプレイ用封着材料は、ビスマス系ガラス粉末が、ガラス組成として、ＣｕＯ＋Ｆｅ２Ｏ３の含有量を０．２質量％以上（好ましくは０．５質量％以上、１質量％以上、１．５質量％以上、２質量％以上、特に３．５質量％以上）含有する。このようにすれば、レーザー光等の光エネルギーが効率良く熱エネルギーに変換されるため、換言すればレーザー光等が的確にガラスに吸収されるため、封着すべき部位のみを局所加熱することができる。その結果、アクティブ素子や有機発光層の熱的損傷を防止した上で、ガラス基板同士を封着することができる。なお、レーザー光等で封着材料を局所加熱する場合、加熱箇所から１ｍｍ離れた部位の温度は１００℃以下になり、アクティブ素子や有機発光層の熱的損傷を防止することができる。一方、本発明の有機ＥＬディスプレイ用封着材料は、ビスマス系ガラス粉末が、ガラス組成として、ＣｕＯ＋Ｆｅ２Ｏ３の含有量を１５質量％以下に規制している。このようにすれば、レーザー光等の照射の際に、ガラスが失透する事態を防止することができる。 In the sealing material for organic EL display of the present invention, the bismuth glass powder has a glass composition of 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, particularly 3.5% by mass or more). In this way, light energy such as laser light is efficiently converted into thermal energy. In other words, since the laser light is accurately absorbed by the glass, only the part to be sealed is locally heated. Can do. As a result, it is possible to seal the glass substrates together while preventing the active element and the organic light emitting layer from being thermally damaged. 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. On the other hand, in the sealing material for an organic EL display of the present invention, 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.
第二に、本発明の有機ＥＬディスプレイ用封着材料は、照射光による封着処理に供されることに特徴付けられる。既述の通り、このようにすれば、封着材料を局所加熱することができ、アクティブ素子や有機発光層の熱的損傷を防止することができる。 Secondly, the sealing material for organic EL displays of the present invention is characterized in that it is subjected to a 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.
第三に、本発明の有機ＥＬディスプレイ用封着材料は、上記照射光がレーザー光であることに特徴付けられる。ここで、照射光の光源として、種々のレーザー光を使用することができるが、特に、半導体レーザー、ＹＡＧレーザー、ＣＯ２レーザー、エキシマレーザー、赤外レーザー等は、取り扱いが容易な点で好適である。また、レーザー光は、ガラスに光を的確に吸収させるために、５００〜１６００ｎｍ、好ましくは７５０〜１３００ｎｍの発光中心波長を有することが好ましい。 Thirdly, the sealing material for organic EL displays of the present invention is characterized in that the irradiation light is laser light. Here, various laser beams can be used as the light source of the irradiation light. In particular, 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. is there. The laser light 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.
第四に、本発明の有機ＥＬディスプレイ用封着材料は、ビスマス系ガラス粉末が、ガラス組成として、下記酸化物換算の質量％表示で、Ｂｉ２Ｏ３ ６７〜９０％、Ｂ２Ｏ３ ２〜１２％、ＺｎＯ １〜２０％、ＣｕＯ＋Ｆｅ２Ｏ３ ０．２〜１５％含有することに特徴付けられる。 Fourth, the organic EL sealing material for a display of the present invention, the bismuth-based glass powder, as a glass composition, in mass% in terms of oxide, Bi 2 O 3 67~90%, B 2 O 3 2 ~12%, ZnO 1~20%, characterized in that it contains CuO + Fe 2 O 3 0.2~15% .
第五に、本発明の有機ＥＬディスプレイ用封着材料は、耐火性フィラー粉末が、コーディエライト、ウイレマイト、アルミナ、リン酸ジルコニウム、ジルコン、ジルコニア、酸化スズから選ばれる一種または二種以上であることに特徴付けられる。 Fifth, in the sealing material for organic EL display of the present invention, the refractory filler powder is one or more selected from cordierite, willemite, alumina, zirconium phosphate, zircon, zirconia, and tin oxide. It is characterized by that.
第六に、本発明の有機ＥＬディスプレイ用封着材料は、実質的にＰｂＯを含有しないことに特徴付けられる。ここで、「実質的にＰｂＯを含有しない」とは、ガラス組成中のＰｂＯの含有量が１０００ｐｐｍ以下の場合を指す。このようにすれば、近年の環境的要請を満たすことができる。 Sixth, the sealing material for an organic EL display of the present invention is characterized by containing substantially no PbO. Here, “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.
第七に、本発明の有機ＥＬディスプレイ用封着材料は、耐火性フィラー粉末の平均粒子径Ｄ５０が１５μｍ未満であることに特徴付けられる。ここで、「平均粒子径Ｄ５０」とは、レーザー回折装置で測定した値を指し、レーザー回折法により測定した際の体積基準の累積粒度分布曲線において、その積算量が粒子の小さい方から累積して５０％である粒子径を表す。 Seventh, organic EL sealing material for a display of the present invention has an average particle diameter D 50 of the refractory filler powder is characterized in that less than 15 [mu] m. Here, 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 particle diameter is 50%.
第八に、本発明の有機ＥＬディスプレイ用封着材料は、耐火性フィラー粉末の最大粒子径Ｄｍａｘが３０μｍ以下であることに特徴付けられる。ここで、「最大粒子径Ｄｍａｘ」とは、レーザー回折装置で測定した値を指し、レーザー回折法により測定した際の体積基準の累積粒度分布曲線において、その積算量が粒子の小さい方から累積して９９％である粒子径を表す。 Eighth, the sealing material for organic EL display of the present invention is characterized in that the maximum particle diameter Dmax of the refractory filler powder is 30 μm or less. Here, the “maximum particle diameter D max ” refers to a value measured by 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 particle size is 99%.
第九に、本発明の有機ＥＬディスプレイ用封着材料は、更に、酸化物顔料を０〜１０体積％含有することに特徴付けられる。 Ninthly, the sealing material for organic EL displays of the present invention is further characterized by containing 0 to 10% by volume of an oxide pigment.
本発明の封着材料において、ビスマス系ガラス粉末のガラス組成範囲を上記のように限定した理由を下記に示す。なお、以下の％表示は、特に断りがある場合を除き、質量％を指す。 The reason for limiting the glass composition range of the bismuth-based glass powder as described above in the sealing material of the present invention will be described below. In addition, the following% display points out the mass% except the case where there is particular notice.
Ｂｉ２Ｏ３は、軟化点を下げるための主要成分であり、その含有量は６７〜９０％、好ましくは７０〜８７％、より好ましくは７２〜８５％、更に好ましくは７５〜８３％である。Ｂｉ２Ｏ３の含有量が６７％より少ないと、ガラスの軟化点が高くなり過ぎ、レーザー光等を照射しても、ガラスが軟化し難くなる。一方、Ｂｉ２Ｏ３の含有量が９０％より多いと、ガラスが熱的に不安定になり、溶融時または照射時にガラスが失透しやすくなる。 Bi 2 O 3 is a main component for lowering the softening point, and its content is 67 to 90%, preferably 70 to 87%, more preferably 72 to 85%, still more preferably 75 to 83%. . When 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. On the other hand, if 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.
Ｂ２Ｏ３は、ビスマス系ガラスのガラスネットワークを形成する成分であり、その含有量は２〜１２％、好ましくは３〜１０％、より好ましくは４〜１０％、更に好ましくは５〜９％である。Ｂ２Ｏ３の含有量が２％より少ないと、ガラスが熱的に不安定になり、溶融時または照射時にガラスが失透しやすくなる。一方、Ｂ２Ｏ３の含有量が１２％より多いと、ガラスの軟化点が高くなり過ぎ、レーザー光等を照射しても、ガラスが軟化し難くなる。 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は、溶融時または照射時にガラスの失透を抑制し、ガラスの熱膨張係数を低下させる成分であり、その含有量は１〜２０％、好ましくは２〜１５％、より好ましくは３〜１５％、更に好ましくは３〜１２％である。ＺｎＯの含有量が１％より少ないと、溶融時または照射時にガラスの失透を抑制する効果が得られ難くなる。ＺｎＯの含有量が２０％より多いと、ガラス組成内の成分バランスが損なわれ、逆にガラスが失透しやすくなる。 ZnO is a component that suppresses the devitrification of the glass at the time of 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%. When 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. When 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＋Ｆｅ２Ｏ３は、光吸収特性を有する成分であり、所定の発光中心波長を有する光を照射すると、光を吸収して、ガラスを軟化させやすくする成分である。また、ＣｕＯ＋Ｆｅ２Ｏ３は、溶融時または照射時にガラスの失透を抑制する成分である。ＣｕＯ＋Ｆｅ２Ｏ３の含有量は０．２〜１５％、好ましくは０．５〜１０％、より好ましくは１〜１０％、更に好ましくは１．５〜１０％、特に好ましくは２〜８％、最も好ましくは３．５〜８％である。ＣｕＯ＋Ｆｅ２Ｏ３の含有量が０．２％より少ないと、光吸収特性が乏しくなり、レーザー光等を照射しても、ガラスが軟化し難くなる。一方、ＣｕＯ＋Ｆｅ２Ｏ３の含有量が１５％より多いと、ガラス組成内の成分バランスが損なわれ、逆にガラスが失透しやすくなり、ガラスの流動性が損なわれやすくなる。 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 10%, more preferably 1 to 10%, still more preferably 1.5 to 10%, particularly preferably 2 to 8%, Most preferably, it is 3.5 to 8%. When the content of CuO + Fe 2 O 3 is less than 0.2%, the light absorption characteristics are poor, and the glass is difficult to soften even when irradiated with laser light or the like. On the other hand, when the content of CuO + Fe 2 O 3 is more than 15%, the component balance in the glass composition is impaired, and conversely, the glass is easily devitrified, and the fluidity of the glass is easily impaired.
ガラス組成中のＦｅは、Ｆｅ２＋、或いはＦｅ３＋の形で存在することが想定されるが、本発明においては、ガラス組成中のＦｅは、Ｆｅ２＋、或いはＦｅ３＋のいずれかに限定されるものではなく、いずれであっても構わない。ここで、本発明では、Ｆｅ２＋の場合はＦｅ２Ｏ３に換算した上で取り扱う。特に、照射光として赤外レーザーを使用する場合、Ｆｅ２＋は赤外域に吸収ピークを有することから、Ｆｅ２＋の割合を高くする方が好ましく、酸化鉄中のＦｅ２＋／Ｆｅ３＋の比率を０．０３以上（望ましくは０．０８以上）にすることが好ましい。 It is assumed that 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. Here, in the present invention, the case of Fe 2+ is handled after being converted to Fe 2 O 3 . In particular, when an infrared laser is used as the irradiation light, since Fe 2+ has an absorption peak in the infrared region, it is preferable to increase the ratio of Fe 2+ , and the ratio of Fe 2+ / Fe 3+ in iron oxide is 0. 0.03 or more (preferably 0.08 or more).
ＣｕＯは、光吸収特性を有する成分であり、所定の発光中心波長を有する光を照射すると、光を吸収して、ガラスを軟化させやすくする成分であるとともに、溶融時または照射時にガラスの失透を抑制する成分であり、その含有量は０〜１５％、０．２〜１５％、０．５〜１０％、１〜１０％、特に３．５〜７％が好ましい。ＣｕＯの含有量が１５％より多いと、ガラス組成内の成分バランスが損なわれ、逆にガラスが失透しやすくなり、ガラスの流動性が損なわれやすくなる。なお、ＣｕＯの含有量が少ないと、光吸収特性が乏しくなり、レーザー光等を照射しても、ガラスが軟化し難くなる。 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 10%, particularly preferably 3.5 to 7%. When 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. In addition, when there is little content of CuO, a light absorption characteristic will become scarce and even if it irradiates a laser beam etc., it will become difficult to soften glass.
Ｆｅ２Ｏ３は、光吸収特性を有する成分であり、所定の発光中心波長を有する光を照射すると、光を吸収して、ガラスを軟化させやすくする成分であるとともに、溶融時または照射時にガラスの失透を抑制する成分であり、その含有量は０〜７％、好ましくは０．０５〜７％、より好ましくは０．１〜４％、更に好ましくは０．２〜２％である。Ｆｅ２Ｏ３の含有量が７％より多いと、ガラス組成内の成分バランスが損なわれ、逆にガラスが失透しやすくなり、ガラスの流動性が損なわれやすくなる。なお、Ｆｅ２Ｏ３の含有量が少ないと、光吸収特性が乏しくなり、レーザー光等を照射しても、ガラスが軟化し難くなる。 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. The 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.
本発明に係るビスマス系ガラス粉末は、ガラス組成として、例えば、以下の成分を２０％まで含有することができる。 The bismuth-based glass powder according to the present invention can contain, for example, the following components up to 20% as a glass composition.
ＳｉＯ２は、ガラスの耐水性を向上させる成分である。その含有量は０〜１０％、好ましくは０〜３％である。ＳｉＯ２の含有量が１０％より多いと、ガラスの軟化点が高くなり過ぎ、レーザー光等を照射しても、ガラスが軟化し難くなる。 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.
Ａｌ２Ｏ３は、ガラスの耐水性を向上させる成分である。その含有量は０〜５％、好ましくは０〜２％である。Ａｌ２Ｏ３の含有量が５％より多いと、ガラスの軟化点が高くなり過ぎ、レーザー光等を照射しても、ガラスが軟化し難くなる。 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（ＭｇＯ、ＣａＯ、ＳｒＯおよびＢａＯの合量）は、溶融時または照射時にガラスの失透を抑制する成分であり、これらの成分の含有量は合量で０〜１５％、好ましくは０〜１０％である。ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの含有量が１５％より多いと、ガラスの軟化点が高くなり過ぎ、レーザー光等を照射しても、ガラスが軟化し難くなる。 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%, preferably 0 to 0%. 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は、溶融時または照射時にガラスの失透を抑制する成分であり、その含有量は０〜５％、好ましくは０〜２％である。ＭｇＯの含有量が５％より多いと、ガラスの軟化点が高くなり過ぎ、レーザー光等を照射しても、ガラスが軟化し難くなる。 MgO 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%. When 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は、溶融時または照射時にガラスの失透を抑制する成分であり、その含有量は０〜５％、好ましくは０〜２％である。ＣａＯの含有量が５％より多いと、ガラスの軟化点が高くなり過ぎ、レーザー光等を照射しても、ガラスが軟化し難くなる。 CaO is a component that suppresses 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は、溶融時または照射時にガラスの失透を抑制する成分であり、その含有量は０〜５％、好ましくは０〜２％である。ＳｒＯの含有量が５％より多いと、ガラスの軟化点が高くなり過ぎ、レーザー光等を照射しても、ガラスが軟化し難くなる。 SrO is a component that suppresses devitrification of the glass during 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は、溶融時または照射時にガラスの失透を抑制する成分であり、その含有量は０〜１０％、好ましくは０〜８％である。ＢａＯの含有量が１０％より多いと、ガラスの軟化点が高くなり過ぎ、レーザー光等を照射しても、ガラスが軟化し難くなる。 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.
ＣｅＯ２は、溶融時または照射時にガラスの失透を抑制する成分であり、その含有量は０〜５％、好ましくは０〜２％、より好ましくは０〜１％である。ＣｅＯ２の含有量が５％より多いと、ガラス組成内の成分バランスが損なわれ、逆にガラスが失透しやすくなる。また、ガラスの熱的安定性を向上させる観点から、ＣｅＯ２を微量添加するのが好ましく、具体的には、ＣｅＯ２の含有量を０．０１％以上とするのが好ましい。 CeO 2 is a component that suppresses devitrification of the glass during melting or irradiation, and its content is 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%. When 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. Further, from the viewpoint of improving the thermal stability of the glass, it is preferable to add a small amount of CeO 2 , and specifically, the content of CeO 2 is preferably 0.01% or more.
Ｓｂ２Ｏ３は、ガラスの失透を抑制するための成分であり、その含有量は０〜５％、好ましくは０〜２％、より好ましくは０〜１％である。Ｓｂ２Ｏ３は、ビスマス系ガラスのネットワーク構造を安定化させる効果があり、ビスマス系ガラスにおいて、Ｓｂ２Ｏ３を適宜添加すれば、Ｂｉ２Ｏ３の含有量が多い場合、例えばＢｉ２Ｏ３の含有量が７６％以上であっても、ガラスの熱的安定性が低下し難くなる。ただし、Ｓｂ２Ｏ３の含有量が５％より多いと、ガラス組成内の成分バランスが損なわれ、逆にガラスが失透しやすくなる。また、ガラスの熱的安定性を向上させる観点から、Ｓｂ２Ｏ３を微量添加するのが好ましく、具体的には、Ｓｂ２Ｏ３の含有量は０．０５％以上が好ましい。 Sb 2 O 3 is a component for suppressing 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.
Ｎｄ２Ｏ３は、ガラスの失透を抑制するための成分であり、その含有量は０〜５％、好ましくは０〜２％、より好ましくは０〜１％である。Ｎｄ２Ｏ３は、ビスマス系ガラスのネットワーク構造を安定化させる効果があり、ビスマス系ガラスにおいて、Ｎｄ２Ｏ３を適宜添加すれば、Ｂｉ２Ｏ３の含有量が多い場合、例えばＢｉ２Ｏ３の含有量が７６％以上であっても、ガラスの熱的安定性が低下し難くなる。ただし、Ｎｄ２Ｏ３の含有量が５％より多いと、ガラス組成内の成分バランスが損なわれ、逆にガラスが失透しやすくなる。また、ガラスの熱的安定性を向上させる観点から、Ｎｄ２Ｏ３の微量添加が好ましく、具体的には、Ｎｄ２Ｏ３の含有量は０．０５％以上が好ましい。 Nd 2 O 3 is a component for suppressing devitrification of the glass, and its content is 0 to 5%, preferably 0 to 2%, and 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, addition of a small amount of Nd 2 O 3 is preferable, and specifically, the content of Nd 2 O 3 is preferably 0.05% or more.
ＷＯ３は、ガラスの失透を抑制するための成分であり、その含有量は０〜１０％、好ましくは０〜２％である。ただし、ＷＯ３の含有量が１０％より多いと、ガラス組成内の成分バランスが損なわれ、逆にガラスが失透しやすくなる。 WO 3 is a component for suppressing devitrification of the 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.
Ｉｎ２Ｏ３＋Ｇａ２Ｏ３（Ｉｎ２Ｏ３とＧａ２Ｏ３の合量）は必須成分ではないが、ガラスの失透を抑制するための成分であり、その含有量は合量で０〜５％、好ましくは０〜３％である。ただし、Ｉｎ２Ｏ３＋Ｇａ２Ｏ３の含有量が５％より多いと、ガラス組成内の成分バランスが損なわれ、逆にガラスが失透しやすくなる。なお、Ｉｎ２Ｏ３の含有量は０〜１％がより好ましく、Ｇａ２Ｏ３の含有量は０〜０．５％がより好ましい。 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. In addition, the content of In 2 O 3 is more preferably 0 to 1%, and the content of Ga 2 O 3 is more preferably 0 to 0.5%.
Ｌｉ、Ｎａ、ＫおよびＣｓの酸化物は、ガラスの軟化点を低くする成分であるが、溶融時にガラスの失透を促進する作用を有するため合量で２％以下とするのが好ましい。 The Li, Na, K, and Cs oxides are components that lower the softening point of the glass. However, since they have an action of promoting devitrification of the glass during melting, the total amount is preferably 2% or less.
Ｐ２Ｏ５は、溶融時にガラスの失透を抑制する成分であるが、その添加量が１％より多いと、溶融時にガラスが分相しやすくなる。 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 undergo phase separation at the time of melting.
Ｌａ２Ｏ３、Ｙ２Ｏ３およびＧｄ２Ｏ３は、溶融時にガラスの分相を抑制する成分であるが、これらの合量が３％より多いと、ガラスの軟化点が高くなり過ぎ、レーザー光等を照射しても、ガラスが軟化し難くなる。 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は、光吸収特性を有する成分であり、所定の発光中心波長を有する光を照射すると、光を吸収して、ガラスを軟化させやすくする成分であり、その含有量は０〜７％、好ましくは０〜３％である。ＮｉＯの含有量が７％より多いと、ガラスが失透しやすくなり、ガラスの流動性が損なわれやすくなる。 NiO is a component having light absorption characteristics, and when irradiated with light having a predetermined emission center wavelength, NiO is a component that absorbs light and softens the glass, and its content is preferably 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.
Ｖ２Ｏ５は、光吸収特性を有する成分であり、所定の発光中心波長を有する光を照射すると、光を吸収して、ガラスを軟化させやすくする成分であり、その含有量は０〜７％、好ましくは０〜３％である。Ｖ２Ｏ５の含有量が７％より多いと、照射時にガラスに発泡が生じやすくなる。 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は、光吸収特性を有する成分であり、所定の発光中心波長を有する光を照射すると、光を吸収して、ガラスを軟化させやすくする成分であり、その含有量は０〜７％、好ましくは０〜３％である。ＣｏＯの含有量が７％より多いと、ガラスが失透しやすくなり、ガラスの流動性が損なわれやすくなる。 CoO 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 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.
ＭｏＯ３は、光吸収特性を有する成分であり、所定の発光中心波長を有する光を照射すると、光を吸収して、ガラスを軟化させやすくする成分であり、その含有量は０〜７％、好ましくは０〜３％である。ＭｏＯ３の含有量が７％より多いと、ガラスが失透しやすくなり、ガラスの流動性が損なわれやすくなる。 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.
ＴｉＯ２は、光吸収特性を有する成分であり、所定の発光中心波長を有する光を照射すると、光を吸収して、ガラスを軟化させやすくする成分であり、その含有量は０〜７％、好ましくは０〜３％である。ＴｉＯ２の含有量が７％より多いと、ガラスが失透しやすくなり、ガラスの流動性が損なわれやすくなる。また、ＴｉＯ２の含有量が７％より多いと、ガラスの軟化点が高くなり過ぎ、レーザー光等を照射しても、ガラスが軟化し難くなる。 TiO 2 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 TiO 2 is more than 7%, the glass tends to be devitrified, the flowability of the glass is easily impaired. On the other hand, if 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.
ＭｎＯ２は、光吸収特性を有する成分であり、所定の発光中心波長を有する光を照射すると、光を吸収して、ガラスを軟化させやすくする成分であり、その含有量は０〜７％、好ましくは０〜３％である。ＭｎＯ２の含有量が７％より多いと、ガラスが失透しやすくなり、ガラスの流動性が損なわれやすくなる。 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 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.
また、その他の成分であっても、ガラスの特性を損なわない範囲で１５％（好ましくは５％）までガラス組成中に添加することができる。ただし、ＰｂＯは、既述の通り、環境的観点から、実質的に含有しないことが好ましい。 Moreover, even if it is another component, it can add to a glass composition to 15% (preferably 5%) in the range which does not impair the characteristic of glass. However, as described above, it is preferable that PbO is not substantially contained from the environmental viewpoint.
本発明の有機ＥＬディスプレイ用封着材料は、ビスマス系ガラス粉末５５〜１００体積％、耐火性フィラー粉末０〜４５体積％を含有し、ビスマス系ガラス粉末６５〜１００体積％と耐火性フィラー粉末０〜３５体積％を含有することが好ましく、ビスマス系ガラス粉末６５〜８５体積％と耐火性フィラー粉末１５〜３５体積％を含有することがより好ましい。ビスマス系ガラス粉末は、低融点であることから、低温で良好に流動する。また、ビスマス系ガラス粉末に耐火性フィラー粉末を添加すれば、封着材料の熱膨張係数を調整できるため、被封着物の熱膨張係数に容易に整合させることができる。その結果、封着部位に不当な応力が残留する事態を防止することができる。ただし、耐火性フィラーの含有量が４５体積％より多いと、ビスマス系ガラス粉末の含有量が相対的に少なくなって、所望の流動性を確保することが困難になる。また、耐火性フィラーの含有量が４５体積％より多いと、耐火性フィラー粉末の平均粒子径Ｄ５０が１０μｍ以下の場合、照射時にガラス中に耐火性フィラー粉末が溶解しやすくなり、その結果、ガラスが失透しやすくなる。 The sealing material for organic EL displays of the present invention contains 55 to 100% by volume of bismuth-based glass powder and 0 to 45% by volume of refractory filler powder, and 65 to 100% by volume of bismuth-based glass powder and refractory filler powder 0. It is preferable to contain -35 volume%, and it is more preferable to contain 65-85 volume% of bismuth-type glass powder and 15-35 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. However, if the content of the refractory filler is more than 45% by volume, the content of the bismuth-based glass powder becomes relatively small, and it becomes difficult to ensure the desired fluidity. If the content of the refractory filler is more than 45 vol%, when the average particle diameter D 50 of the refractory filler powder is 10μm or less, refractory filler powder in the glass it becomes more soluble upon irradiation, as a result, Glass tends to devitrify.
本発明の有機ＥＬディスプレイ用封着材料は、耐火性フィラー粉末として、コーディエライト、ウイレマイト、アルミナ、リン酸ジルコニウム、ジルコン、ジルコニア、酸化スズから選ばれる一種または二種以上を組み合わせて使用することができる。これらの耐火性フィラー粉末は、熱膨張係数が低いことに加えて、機械的強度高く、しかもビスマス系ガラス粉末との適合性が良好である。更に、上記の耐火性フィラー粉末以外にも、封着材料の熱膨張係数の調整、流動性の調整および機械的強度の改善のために、石英ガラス、β−ユークリプタイト等の耐火性フィラー粉末を添加することができる。 The sealing material for organic EL display of the present invention is used as a refractory filler powder by using one or a combination of two or more selected from cordierite, willemite, alumina, zirconium phosphate, zircon, zirconia and tin oxide. Can do. These refractory filler powders have a low mechanical expansion coefficient, a high mechanical strength, and a good compatibility with bismuth-based glass powders. Furthermore, in addition to the above-mentioned refractory filler powder, refractory filler powders such as quartz glass and β-eucryptite are used for adjusting the thermal expansion coefficient of the sealing material, adjusting the fluidity and improving the mechanical strength. Can be added.
現在、有機ＥＬディスプレイは、駆動方式として、ＴＦＴ等のアクティブ素子を各画素に配置して駆動するアクティブマトリクス駆動が採用されており、そのため、有機ＥＬディスプレイ用ガラス基板には、無アルカリガラス（例えば、日本電気硝子株式会社製ＯＡ−１０）が使用される。無アルカリガラスの熱膨張係数は、通常、４０×１０−７／℃以下であるため、有機ＥＬディスプレイ用封着材料の熱膨張係数を無アルカリガラスの熱膨張係数に厳密に適合させることは困難である。しかし、有機ＥＬディスプレイ用封着材料の熱膨張係数をできるだけ低くすることは重要であり、具体的には、有機ＥＬディスプレイ用封着材料の熱膨張係数は８０×１０−７／℃以下、特に７０×１０−７／℃以下が望ましい。このようにすれば、封着部位にかかる応力を小さくすることができ、封着部位の応力破壊を防ぐことができる。ここで、「熱膨張係数」は、押棒式熱膨張係数測定装置で測定した値を指し、測定温度範囲は３０〜３００℃とする。 Currently, an active matrix driving in which an active element such as a TFT is arranged and driven in each pixel is employed as an organic EL display as a driving method. Therefore, a non-alkali glass (for example, an organic EL display glass substrate) OA-10) manufactured by Nippon Electric Glass Co., Ltd. is used. Since the thermal expansion coefficient of the alkali-free glass is usually 40 × 10 −7 / ° C. or less, it is difficult to strictly match the thermal expansion coefficient of the sealing material for organic EL displays with the thermal expansion coefficient of the alkali-free glass. It is. However, it is important to make the coefficient of thermal expansion of the sealing material for organic EL display as low as possible. Specifically, the coefficient of thermal expansion of the sealing material for organic EL display is 80 × 10 −7 / ° C. or less. 70 * 10 < -7 > / degrees C or less is desirable. 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. Here, 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.
本発明の有機ＥＬディスプレイ用封着材料は、更に、酸化物顔料を０〜１０体積％、好ましくは０．１〜５体積％、より好ましくは０．５〜３体積％含有することが好ましい。酸化物顔料の含有量が１０体積％より多いと、ガラスが失透しやすくなり、ガラスの流動性が損なわれやすくなる。酸化物顔料として、Ｃｕ系酸化物、Ｆｅ系酸化物、Ｃｒ系酸化物、Ｍｎ系酸化物およびこれらのスピネル型複合酸化物等が使用可能であり、特に、酸化物顔料として、Ｍｎ系酸化物（例えば、東罐マテリアル株式会社製４２−３４３Ｂ）が好ましい。これらの酸化物顔料は、レーザー光等の光吸収を促進させることが可能であり、その結果、封着材料の封着強度を高めることができる。 The sealing material for organic EL display of the present invention further preferably 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. When there is more content of an oxide pigment than 10 volume%, it will become easy to devitrify glass and the fluidity | liquidity of glass will be impaired easily. As oxide pigments, Cu-based oxides, Fe-based oxides, Cr-based oxides, Mn-based oxides and their spinel type complex oxides can be used. In particular, as oxide pigments, Mn-based oxides can be used. (For example, 42-343B made 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.
本発明の有機ＥＬディスプレイ用封着材料は、更に、封着部位の厚みを均一化するために、ガラスファイバー、ガラスビーズ、シリカビーズ、樹脂ビーズ等をスペーサーとして１０体積％まで含有してもよい。また、本発明の有機ＥＬディスプレイ用封着材料は、更に、光吸収を促進させるために、Ｃｕ、Ｆｅ、Ｍｎ、Ｃｏ等の遷移金属粉末等を１０体積％まで含有してもよい。 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.
本発明の有機ＥＬディスプレイ用封着材料において、軟化点は５５０℃以下が好ましく、５００℃以下がより好ましく、４６５℃以下が更に好ましい。軟化点が５５０℃より高いと、レーザー光等を照射しても、ガラスが軟化し難い傾向があり、ガラス基板同士の封着強度を高めるためには、レーザー光等の出力を上げる必要がある。軟化点の下限は特に限定されないが、ガラスの熱的安定性を考慮すれば、軟化点を３８５℃以上に設定することが好ましい。ここで、「軟化点」とは、示差熱分析装置で測定した値を指し、空気中で昇温速度は１０℃とする。 In the sealing material for organic EL displays of the present invention, the softening point is preferably 550 ° C. or lower, more preferably 500 ° C. or lower, and further preferably 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 it is preferable to set the softening point to 385 ° C. or higher in consideration of the thermal stability of the glass. Here, the “softening point” refers to a value measured with a differential thermal analyzer, and the heating rate is 10 ° C. in air.
本発明の有機ＥＬディスプレイ用封着材料において、耐火性フィラー粉末の平均粒子径Ｄ５０は１５μｍ未満が好ましく、０．５〜１０μｍがより好ましく、１〜５μｍが更に好ましい。耐火性フィラー粉末の平均粒子径Ｄ５０が１５μｍ以上であると、封着部位が厚くなりやすく、両ガラス基板間のギャップが大きくなり、有機ＥＬディスプレイを薄型化し難くなる。また、耐火性フィラー粉末の平均粒子径Ｄ５０を１５μｍ未満にすると、両ガラス基板間のギャップを小さくすることができ、このような場合、ガラス基板と封着材料の熱膨張係数の差が大きくても、ガラス基板および封着部位にクラック等が発生し難くなる。なお、耐火性フィラー粉末の効果（例えば、封着材料の熱膨張係数を低下させる効果）を的確に享受するためには、耐火性フィラー粉末の平均粒子径Ｄ５０を０．５μｍ以上にするのが好ましい。 In the sealing material for organic EL displays of the present invention, the average particle diameter D50 of the refractory filler powder is preferably less than 15 μm, more preferably 0.5 to 10 μm, and even more preferably 1 to 5 μm. When the average particle diameter D 50 of the refractory filler powder is 15μm or more, sealing portion tends to become thick, the gap increases between the glass substrates, it becomes difficult to thin the organic EL display. Further, 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. Incidentally, 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 0.5μm Is preferred.
本発明の有機ＥＬディスプレイ用封着材料において、耐火性フィラー粉末の最大粒子径Ｄｍａｘは３０μｍ以下が好ましく、２０μｍ以下がより好ましく、１０μｍ以下が更に好ましい。耐火性フィラー粉末の最大粒子径Ｄｍａｘが３０μｍより大きいと、封着部位において、３０μｍ以上の厚みを有する箇所が発生するため、両ガラス基板間のギャップが不均一になり、有機ＥＬディスプレイを薄型化し難くなる。また、耐火性フィラー粉末の平均粒子径Ｄｍａｘを３０μｍ以下にすると、両ガラス基板間のギャップを小さくすることができ、このような場合、ガラス基板と封着材料の熱膨張係数の差が大きくても、ガラス基板および封着部位にクラック等が発生し難くなる。 In the sealing material for organic EL displays of the present invention, the maximum particle diameter Dmax of the refractory filler powder is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less. If the maximum particle diameter Dmax of the refractory filler powder is larger than 30 μm, a portion having a thickness of 30 μm 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 μm 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.
本発明の有機ＥＬディスプレイ用封着材料において、ビスマス系ガラス粉末の平均粒子径Ｄ５０は１５μｍ未満が好ましく、０．５〜１０μｍがより好ましく、１〜５μｍが更に好ましい。ビスマス系ガラス粉末の平均粒子径Ｄ５０を１５μｍ未満にすると、両ガラス基板間のギャップを小さくしやすくなり、このような場合、ガラス基板と封着材料の熱膨張係数の差が大きくても、ガラス基板および封着部位にクラック等が発生し難くなるとともに、封着に要する時間を短縮することができる。 In the sealing material for organic EL displays of the present invention, the average particle diameter D50 of the bismuth-based glass powder is preferably less than 15 μm, more preferably 0.5 to 10 μm, and even more preferably 1 to 5 μm. When 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.
本発明の有機ＥＬディスプレイ用封着材料において、ビスマス系ガラス粉末の最大粒子径Ｄｍａｘは３０μｍ以下が好ましく、２０μｍ以下がより好ましく、１０μｍ以下が更に好ましい。ビスマス系ガラス粉末の平均粒子径Ｄｍａｘを３０μｍ以下にすると、両ガラス基板間のギャップを小さくしやすくなり、このような場合、ガラス基板と封着材料の熱膨張係数の差が大きくても、ガラス基板および封着部位にクラック等が発生し難くなるとともに、封着に要する時間を短縮することができる。 In the sealing material for organic EL displays of the present invention, the maximum particle diameter Dmax of the bismuth-based glass powder is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less. When the average particle diameter Dmax of the bismuth-based glass powder is 30 μm 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.
本発明の有機ＥＬディスプレイ用封着材料は、粉末のまま使用に供してもよいが、ビークルと均一に混練し、ペーストに加工すると取り扱いやすい。ビークルは、主に溶媒と樹脂とからなり、樹脂はペーストの粘性を調整する目的で添加される。また、必要に応じて、界面活性剤、増粘剤等を添加することもできる。作製されたペーストは、ディスペンサーやスクリーン印刷機等の塗布機を用いてガラス基板に塗布され、脱バインダー工程に供される。 The sealing material for organic EL displays of the present invention may be used as it is in powder form, but it is easy to handle if it is kneaded uniformly 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.
樹脂としては、アクリル酸エステル（アクリル樹脂）、エチルセルロース、ポリエチレングリコール誘導体、ニトロセルロース、ポリメチルスチレン、ポリエチレンカーボネート、メタクリル酸エステル等が使用可能である。特に、アクリル酸エステル、ニトロセルロースは、熱分解性が良好であるため、好ましい。 As the resin, acrylic acid ester (acrylic resin), ethyl cellulose, polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, methacrylic acid ester and the like can be used. In particular, acrylic acid esters and nitrocellulose are preferable because they have good thermal decomposability.
溶媒としては、Ｎ、Ｎ’−ジメチルホルムアミド（ＤＭＦ）、α−ターピネオール、高級アルコール、γ−ブチルラクトン（γ−ＢＬ）、テトラリン、ブチルカルビトールアセテート、酢酸エチル、酢酸イソアミル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ベンジルアルコール、トルエン、３−メトキシ−３−メチルブタノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールジメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノブチルエーテル、プロピレンカーボネート、ジメチルスルホキシド（ＤＭＳＯ）、Ｎ−メチル−２−ピロリドン等が使用可能である。特に、α−ターピネオールは、高粘性であり、樹脂等の溶解性も良好であるため、好ましい。 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 is highly viscous and has good solubility in resins and the like.
以下、実施例に基づいて本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail based on examples.
表１〜４は本発明の実施例（試料Ｎｏ．１〜１８）および比較例（試料Ｎｏ．１９〜２３）を示している。 Tables 1 to 4 show examples (samples Nos. 1 to 18) and comparative examples (samples Nos. 19 to 23) of the present invention.
次のようにして表１〜４に記載の各試料を調製した。まず、表に示したガラス組成となるように各種酸化物、炭酸塩等の原料を調合したガラスバッチを準備し、これを白金坩堝に入れて１１００℃で１時間溶融した。次に、水冷ローラーにより、溶融ガラスを薄片状に成形した。最後に、薄片状のガラスをボールミルにて粉砕後、空気分級し、平均粒子径Ｄ５０が２．５μｍ、最大粒子径Ｄｍａｘが１０μｍの各ガラス粉末を得た。 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.
耐火物フィラー粉末は、コーディエライト、ウイレマイト、β−ユークリプタイト、リン酸ジルコニウムを用いた。各耐火性フィラー粉末は、平均粒子径Ｄ５０が２．５μｍ、最大粒子径Ｄｍａｘが１０μｍになるように調製した。 Cordierite, willemite, β-eucryptite and zirconium phosphate were used as the refractory filler powder. 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.
表中に示す通り、ビスマス系ガラス粉末と耐火性フィラー粉末を混合し、試料Ｎｏ．１〜２３を作製した。試料Ｎｏ．１〜２３につき、ガラス転移点、軟化点、熱膨張係数、流動性、封着強度、発泡状態および失透状態を評価した。 As shown in the table, bismuth-based glass powder and refractory filler powder were mixed, and sample No. 1-23 were produced. Sample No. About 1-23, the glass transition point, the softening point, the thermal expansion coefficient, the fluidity, the sealing strength, the foaming state, and the devitrification state were evaluated.
ガラス転移点、軟化点は、示差熱分析装置で測定した。測定は、大気中において、昇温速度１０℃／分で行い、室温から測定を開始した。 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.
熱膨張係数は、押棒式熱膨張係数測定装置で求めた。測定温度範囲は３０〜３００℃とした。 The thermal expansion coefficient was determined by a push rod type thermal expansion coefficient measuring device. The measurement temperature range was 30 to 300 ° C.
流動性は、各試料を厚さ２ｍｍに加圧成形した後、各加圧体に波長１０６０ｎｍのＹＡＧレーザー（出力６００ｍＷ、パワー密度５ｋＷ／ｃｍ２）を照射することで評価した。ＹＡＧレーザーを照射した後、ガラスが溶解する状態を顕微鏡でその場観察し、ガラスが軟化変形しているものを「○」、ガラスが軟化変形していないものを「×」として評価した。 The fluidity was evaluated by pressing each sample to a thickness of 2 mm and irradiating each pressed body with a YAG laser having a wavelength of 1060 nm (output 600 mW, power density 5 kW / cm 2 ). After irradiation with the YAG laser, the state in which the glass was melted was observed in-situ with a microscope, and the case where the glass was softened and deformed was evaluated as “◯”, and the case where the glass was not softened and deformed was evaluated as “x”.
次のようにして封着強度を評価した。まず、各試料とビークル（アクリル樹脂含有のα−ターピネオール）を三本ロールミルで均一に混錬し、ペースト化した後、無アルカリガラス基板（日本電気硝子株式会社製ＯＡ−１０、□１００ｍｍ×０．５ｍｍ厚）の外周端に線状（３０μｍ厚）に塗布し、乾燥オーブンで１５０℃１０分間乾燥した。次に、室温から１０℃／分で昇温し、４５０℃で２０分間焼成した後、室温まで１０℃／分で降温し、脱バインダー処理を行なった。次に、乾燥膜が形成された無アルカリガラス基板の上に、別の無アルカリガラス基板（日本電気硝子株式会社製ＯＡ−１０、□１００ｍｍ×０．５ｍｍ厚）を正確に重ねた後、乾燥膜に沿って、波長１０６０ｎｍのＹＡＧレーザー（出力６００ｍＷ、パワー密度５ｋＷ／ｃｍ２）を照射し、両ガラス基板を封着した。封着後の両ガラス基板を上方１ｍからコンクリート上に落下させ、両ガラス基板が剥離しなかったものを「○」、両ガラス基板が剥離したものを「×」として評価した。 The sealing strength was evaluated as follows. First, after each sample and vehicle (acrylic resin-containing α-terpineol) were uniformly kneaded with a three-roll mill and formed into a paste, an alkali-free glass substrate (OA-10, Nippon Electric Glass Co., Ltd., □ 100 mm × 0) 0.5 mm thickness) was applied in a linear shape (30 μm thickness) 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. Next, another alkali-free glass substrate (OA-10 manufactured by Nippon Electric Glass Co., Ltd., □ 100 mm × 0.5 mm thickness) is accurately stacked on the alkali-free glass substrate on which the dry film is formed, and then dried. Along the film, YAG laser (output 600 mW, power density 5 kW / cm 2 ) with a wavelength of 1060 nm was irradiated to seal both glass substrates. Both glass substrates after sealing were dropped onto concrete from 1 m above, and “○” was evaluated when both glass substrates were not peeled off, and “X” was evaluated when both glass substrates were peeled off.
発泡状態は、上記封着強度の評価で形成された封着部位の断面を光学顕微鏡で観察し、１００μｍ×１００μｍの面積中にφ５μｍ以上の泡が５個未満のものを「○」、φ５μｍ以上の泡が５個以上のものを「×」として評価した。 For the foamed state, 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 φ5 μm or more in an area of 100 μm × 100 μm, and φ5 μm or more. Those having 5 or more bubbles were evaluated as “x”.
失透状態は、上記封着強度の評価で形成された封着部位の表面を光学顕微鏡（１００倍）で観察し、表面に結晶が観察されたものを「○」、表面に結晶が観察されなかったものを「×」として評価した。 In the devitrification state, 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”.
表１〜３から明らかなように、試料Ｎｏ．１〜１８は、流動性、封着強度、発泡性および失透状態の評価が良好であり、有機ＥＬディスプレイ用封着材料に好適であると判断できる。 As is apparent from Tables 1 to 3, 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.
表４から明らかなように、試料Ｎｏ．１９〜２２は、ガラス組成中にＣｕＯおよびＦｅ２Ｏ３を含有していないため、流動性および封着強度の評価が不良であった。試料Ｎｏ．２３は、バナジウム系ガラス粉末を使用したため、発泡性の評価が不良であった。 As is apparent from Table 4, sample No. 19-22, since in the glass composition does not contain CuO and Fe 2 O 3, evaluation of flowability and sealing strength was poor. Sample No. Since No. 23 used vanadium-based glass powder, the evaluation of foamability was poor.
Claims (9)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009009410A JP5458579B2 (en) | 2008-02-28 | 2009-01-20 | Sealing material for organic EL display |
| KR1020127007795A KR20120046321A (en) | 2008-02-28 | 2009-01-26 | Sealing material for organic el display |
| KR1020127007801A KR101236373B1 (en) | 2008-02-28 | 2009-01-26 | Manufacturing method for organic el display |
| KR1020107007027A KR101236369B1 (en) | 2008-02-28 | 2009-01-26 | Sealing material for organic el display |
| KR1020127007798A KR101236371B1 (en) | 2008-02-28 | 2009-01-26 | Alkali-free glass substrate having glaze layer for organic el display |
| PCT/JP2009/051167 WO2009107428A1 (en) | 2008-02-28 | 2009-01-26 | Sealing material for organic el display |
| KR1020137004395A KR101330100B1 (en) | 2008-02-28 | 2009-01-26 | Sealing material for organic el display |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008047533 | 2008-02-28 | ||
| JP2008047533 | 2008-02-28 | ||
| JP2009009410A JP5458579B2 (en) | 2008-02-28 | 2009-01-20 | Sealing material for organic EL display |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013167962A Division JP5862973B2 (en) | 2008-02-28 | 2013-08-13 | Manufacturing method of organic EL display |
| JP2013167961A Division JP5862972B2 (en) | 2008-02-28 | 2013-08-13 | Glass substrate with dry film for organic EL display |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009227566A JP2009227566A (en) | 2009-10-08 |
| JP5458579B2 true JP5458579B2 (en) | 2014-04-02 |
Family
ID=41243394
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009009410A Active JP5458579B2 (en) | 2008-02-28 | 2009-01-20 | Sealing material for organic EL display |
| JP2013167962A Active JP5862973B2 (en) | 2008-02-28 | 2013-08-13 | Manufacturing method of organic EL display |
| JP2013167961A Active JP5862972B2 (en) | 2008-02-28 | 2013-08-13 | Glass substrate with dry film for organic EL display |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013167962A Active JP5862973B2 (en) | 2008-02-28 | 2013-08-13 | Manufacturing method of organic EL display |
| JP2013167961A Active JP5862972B2 (en) | 2008-02-28 | 2013-08-13 | Glass substrate with dry film for organic EL display |
Country Status (1)
| Country | Link |
|---|---|
| JP (3) | JP5458579B2 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5440997B2 (en) * | 2008-08-21 | 2014-03-12 | 日本電気硝子株式会社 | Sealing material for organic EL display |
| JP5458579B2 (en) * | 2008-02-28 | 2014-04-02 | 日本電気硝子株式会社 | Sealing material for organic EL display |
| US20100330309A1 (en) * | 2009-06-30 | 2010-12-30 | Guardian Industries Corp. | Frit or solder glass compound including beads, and assemblies incorporating the same |
| WO2011036605A1 (en) * | 2009-09-22 | 2011-03-31 | Koninklijke Philips Electronics N.V. | Glass package for sealing a device, and system comprising glass package |
| WO2011115266A1 (en) | 2010-03-19 | 2011-09-22 | 旭硝子株式会社 | Electronic device and method for manufacturing same |
| JP5664894B2 (en) * | 2010-05-10 | 2015-02-04 | 日本電気硝子株式会社 | Crystalline sealing material |
| CN102939270B (en) | 2010-06-14 | 2015-11-25 | 旭硝子株式会社 | Sealing material is stuck with paste and is used its manufacture method of electron device |
| JP6031846B2 (en) * | 2011-07-27 | 2016-11-24 | 日本電気硝子株式会社 | Glass substrate with sealing material layer and organic EL device using the same |
| JP5957847B2 (en) * | 2011-10-13 | 2016-07-27 | セントラル硝子株式会社 | Bismuth glass composition |
| CN105358498A (en) * | 2013-10-21 | 2016-02-24 | 日本电气硝子株式会社 | Sealing material |
| JP2015137186A (en) * | 2014-01-20 | 2015-07-30 | 旭硝子株式会社 | Sealing material, substrate with sealing material layer and manufacturing method therefor, and sealed body |
| JP6963214B2 (en) * | 2016-04-01 | 2021-11-05 | 日本電気硝子株式会社 | Glass powder and sealing material using it |
| JP6840982B2 (en) * | 2016-10-13 | 2021-03-10 | 日本電気硝子株式会社 | Bismuth glass and sealing materials using it |
| JP2018177600A (en) | 2017-04-17 | 2018-11-15 | 日本電気硝子株式会社 | Cover glass and hermetic package therewith |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3424219B2 (en) * | 1994-08-17 | 2003-07-07 | 日本電気硝子株式会社 | Low melting point sealing composition |
| JP3814810B2 (en) * | 1996-04-05 | 2006-08-30 | 日本電気硝子株式会社 | Bismuth glass composition |
| JP4016507B2 (en) * | 1998-10-21 | 2007-12-05 | 日本電気硝子株式会社 | Bismuth glass composition |
| JP2001319775A (en) * | 2000-05-10 | 2001-11-16 | Auto Network Gijutsu Kenkyusho:Kk | Sealing method of organic el display device and sealing structure |
| JP2004296572A (en) * | 2003-03-26 | 2004-10-21 | Kyocera Corp | Container for housing electronic component |
| US6998776B2 (en) * | 2003-04-16 | 2006-02-14 | Corning Incorporated | Glass package that is hermetically sealed with a frit and method of fabrication |
| JP4774721B2 (en) * | 2004-11-12 | 2011-09-14 | 旭硝子株式会社 | Low melting glass, sealing composition and sealing paste |
| JP4815975B2 (en) * | 2005-06-23 | 2011-11-16 | 旭硝子株式会社 | Low melting glass, sealing composition and sealing paste |
| JP2006143480A (en) * | 2004-11-16 | 2006-06-08 | Nippon Electric Glass Co Ltd | Bi2O3-B2O3-BASED GLASS COMPOSITION AND Bi2O3-B2O3-BASED SEALING MATERIAL |
| JP4972954B2 (en) * | 2005-03-09 | 2012-07-11 | 日本電気硝子株式会社 | Bismuth-based glass composition and bismuth-based sealing material |
| JP2008037740A (en) * | 2006-07-11 | 2008-02-21 | Nippon Electric Glass Co Ltd | Glass composition for sealing and sealing material |
| JP2008115057A (en) * | 2006-11-07 | 2008-05-22 | Electric Power Dev Co Ltd | Sealant, manufacturing process of glass panel and dye-sensitized solar cell |
| JP5413562B2 (en) * | 2007-12-06 | 2014-02-12 | 日本電気硝子株式会社 | Sealing material |
| JP5458579B2 (en) * | 2008-02-28 | 2014-04-02 | 日本電気硝子株式会社 | Sealing material for organic EL display |
| WO2009107428A1 (en) * | 2008-02-28 | 2009-09-03 | 日本電気硝子株式会社 | Sealing material for organic el display |
-
2009
- 2009-01-20 JP JP2009009410A patent/JP5458579B2/en active Active
-
2013
- 2013-08-13 JP JP2013167962A patent/JP5862973B2/en active Active
- 2013-08-13 JP JP2013167961A patent/JP5862972B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP5862973B2 (en) | 2016-02-16 |
| JP2014001134A (en) | 2014-01-09 |
| JP2014012634A (en) | 2014-01-23 |
| JP2009227566A (en) | 2009-10-08 |
| JP5862972B2 (en) | 2016-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5458579B2 (en) | Sealing material for organic EL display | |
| JP6455801B2 (en) | Sealing material | |
| JP5224102B2 (en) | Sealing material for organic EL display | |
| WO2011122218A1 (en) | Sealing material and paste material using same | |
| JP6075715B2 (en) | Bismuth glass and sealing material using the same | |
| JP5500079B2 (en) | Glass member with sealing material layer and manufacturing method thereof, and electronic device and manufacturing method thereof | |
| JP5440997B2 (en) | Sealing material for organic EL display | |
| JP2011057477A (en) | Sealing material | |
| JP6269991B2 (en) | Glass substrate with sealing material layer | |
| JP5458648B2 (en) | Sealing material for organic EL lighting | |
| WO2009107428A1 (en) | Sealing material for organic el display | |
| JP5994438B2 (en) | Method for producing glass substrate with sealing material layer | |
| JP5224103B2 (en) | Sealing glass composition and sealing material | |
| JP2011225426A (en) | Sealing material and paste material using the same | |
| JP5489061B2 (en) | Filler powder and sealing material using the same | |
| KR101330100B1 (en) | Sealing material for organic el display | |
| JP6840982B2 (en) | Bismuth glass and sealing materials using it | |
| JP2012106900A (en) | Sealing material, and paste material using the same | |
| JP2013049613A (en) | Method for producing glass substrate with sealing material layer | |
| JP2012162441A (en) | Sealing material and paste material using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20111202 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A132 Effective date: 20130729 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20131217 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20131230 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5458579 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |