JP2009256116A - Glass composition for sealing and sealing material - Google Patents
Glass composition for sealing and sealing material Download PDFInfo
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- JP2009256116A JP2009256116A JP2008104269A JP2008104269A JP2009256116A JP 2009256116 A JP2009256116 A JP 2009256116A JP 2008104269 A JP2008104269 A JP 2008104269A JP 2008104269 A JP2008104269 A JP 2008104269A JP 2009256116 A JP2009256116 A JP 2009256116A
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- 239000011521 glass Substances 0.000 title claims abstract description 192
- 238000007789 sealing Methods 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 239000003566 sealing material Substances 0.000 title claims description 45
- 239000000843 powder Substances 0.000 claims description 32
- 239000000945 filler Substances 0.000 claims description 19
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 12
- 239000005394 sealing glass Substances 0.000 claims description 9
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract description 5
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- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical class [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 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
- 229910000505 Al2TiO5 Inorganic materials 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
- 229910019142 PO4 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
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
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- 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
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
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- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 238000005187 foaming Methods 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
- 150000002500 ions Chemical class 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
- 229910052749 magnesium Inorganic materials 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
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 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
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance 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
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052844 willemite Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- 229910000500 β-quartz Inorganic materials 0.000 description 1
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Abstract
Description
本発明は、封着用ガラス組成物および封着材料に関し、特にレーザー光による封着処理に供される封着用ガラス組成物および封着材料に関する。 The present invention relates to a sealing glass composition and a sealing material, and particularly relates to a sealing glass composition and a sealing material that are subjected to a sealing treatment with a laser beam.
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保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, organic resin adhesives have the advantage that glass substrates can be bonded together at low temperatures, but they have the disadvantage of low water resistance. When organic EL displays are used over a long period of time, the reliability of the display decreases. 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。
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 laser light irradiation light have been studied. Since the laser beam can locally heat only the site to be sealed, it is possible to seal the 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、短時間で封着することができるとともに、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。 Further, when locally heating the sealing material with laser light, 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封着用ガラス組成物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 of laser light, and by creating a glass composition for sealing that has both low softening characteristics and high water resistance, a highly reliable organic EL display can be obtained. Making it a technical issue.
本発明者等は、鋭意努力の結果、封着用ガラス組成物として、ＳｉＯ2、Ｂ2Ｏ3およびＺｎＯを主成分とするガラス組成を採用するとともに、ガラス組成中にＣｕＯ、Ｆｅ2Ｏ3、Ｖ2Ｏ5、ＴｉＯ2およびＭｎＯ2の一種または二種以上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、本発明の封着用ガラス組成物は、ガラス組成として、下記酸化物換算のモル％で、ＳｉＯ2 ５〜３０％、Ｂ2Ｏ3 ３１〜５５％、ＺｎＯ １５〜５５％、ＣｕＯ＋Ｆｅ2Ｏ3＋Ｖ2Ｏ5＋ＴｉＯ2＋ＭｎＯ2（ＣｕＯ、Ｆｅ2Ｏ3、Ｖ2Ｏ5、ＴｉＯ2およびＭｎＯ2の合量） ０．１〜２５％含有することを特徴とする。 As a result of diligent efforts, the present inventors adopted a glass composition mainly composed of SiO 2 , B 2 O 3 and ZnO as a sealing glass composition, and CuO, Fe 2 O 3 , The present inventors have found that the above technical problem can be solved by introducing a predetermined amount of one or more of V 2 O 5 , TiO 2 and MnO 2 , and propose the present invention. In other words, the sealing glass composition of the present invention has a glass composition, in mol% terms of oxide, SiO 2 5~30%, B 2 O 3 31~55%, ZnO 15~55%, CuO + Fe 2 O 3 + V 2 O 5 + TiO 2 + MnO 2 (CuO, Fe 2 O 3 , V 2 O 5 , TiO 2 and MnO 2 ) 0.1 to 25%
本発明の封着用ガラス組成物は、ＳｉＯ2、Ｂ2Ｏ3およびＺｎＯを所定範囲に規制している。このように成分範囲を規制すれば、ガラスの耐水性を向上させることができ、有機発光層の劣化を防止することができる。また、このように成分範囲を規制すれば、熱膨張係数を不当に上昇させることなく、ガラスの軟化点を低下させることができる。その結果、被封着物に不当な応力を残留させることなく、封着を短時間で完了できることに加えて、ガラス基板同士の封着強度を高めることができる。さらに、このように成分範囲を規制すれば、ガラスの熱的安定性を向上させることができるため、レーザー光の照射の際に、ガラスが失透し難くなり、失透に起因して、封着強度が低下する事態を防止することができる。 The glass composition for sealing of the present invention regulates SiO 2 , B 2 O 3 and ZnO within a predetermined range. By regulating the component range in this way, the water resistance of the glass can be improved, and the deterioration of the organic light emitting layer can be prevented. Moreover, if the component range is regulated in this way, the softening point of the glass can be lowered without unduly increasing the thermal expansion coefficient. As a result, it is possible to increase the sealing strength between the glass substrates in addition to completing the sealing in a short time without leaving an undue stress on the object to be sealed. Furthermore, if the component range is regulated in this way, the thermal stability of the glass can be improved, so that it becomes difficult for the glass to be devitrified when irradiated with laser light. A situation in which the wearing strength is reduced can be prevented.
本発明の封着用ガラス組成物は、ＣｕＯ＋Ｆｅ2Ｏ3＋Ｖ2Ｏ5＋ＴｉＯ2＋ＭｎＯ2の含有量を０．１モル％以上に規制している。このようにすれば、レーザー光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。一方、本発明の封着用ガラス組成物は、ＣｕＯ＋Ｆｅ2Ｏ3＋Ｖ2Ｏ5＋ＴｉＯ2＋ＭｎＯ2の含有量を２５モル％以下に規制している。このようにすれば、レーザー光の照射の際に、ガラスが失透する事態を防止することができる。 The glass composition for sealing of the present invention regulates the content of CuO + Fe 2 O 3 + V 2 O 5 + TiO 2 + MnO 2 to 0.1 mol% or more. In this way, since the light energy of the laser light is efficiently converted into thermal energy, in other words, since the laser light is accurately absorbed by the glass, only the portion to be sealed can be locally heated. . 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. On the other hand, the glass composition for sealing of the present invention regulates the content of CuO + Fe 2 O 3 + V 2 O 5 + TiO 2 + MnO 2 to 25 mol% or less. If it does in this way, the situation where glass devitrifies at the time of irradiation of a laser beam can be prevented.
本発明の封着用ガラス組成物は、モル比ＺｎＯ／Ｂ2Ｏ3の値が１．５未満であることを特徴とする。このようにすれば、ガラスの熱的安定性を低下させずに、ガラスの軟化点を低下させることができる。 The glass composition for sealing of the present invention is characterized in that the molar ratio ZnO / B 2 O 3 is less than 1.5. If it does in this way, the softening point of glass can be reduced, without reducing the thermal stability of glass.
本発明の封着用ガラス組成物は、Ｂ2Ｏ3の含有量が４０〜５５モル％（但し、４０モル％は含まない）であることを特徴とする。 The glass composition for sealing of the present invention is characterized in that the content of B 2 O 3 is 40 to 55 mol% (however, 40 mol% is not included).
本発明の封着用ガラス組成物は、更に、ガラス組成として、Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏ（Ｌｉ2Ｏ、Ｎａ2ＯおよびＫ2Ｏの合量）を２〜２０モル％含有することを特徴とする。 The glass composition for sealing of the present invention further contains 2 to 20 mol% of Li 2 O + Na 2 O + K 2 O (total amount of Li 2 O, Na 2 O and K 2 O) as a glass composition. And
本発明の封着用ガラス組成物は、レーザー光による封着処理に供されることを特徴とする。このようにすれば、封着すべき部位のみ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。なお、レーザー光で局所加熱する場合、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。 The glass composition for sealing of the present invention is characterized by being subjected to a sealing treatment with a laser beam. In this way, only the part to be sealed can be locally heated, and thermal damage to the active element and the organic light emitting layer can be prevented. In addition, when carrying out local heating with a laser beam, the temperature of the site | part 1 mm away from the heating location will be 100 degrees C or less, and the thermal damage of an active element or an organic light emitting layer can be prevented.
本発明の封着材料において、レーザー光として、種々のレーザーを使用することができる。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、取扱いが容易な点で好ましい。 In the sealing material of the present invention, various lasers can be used as the laser 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.
本発明の封着用ガラス組成物は、有機ＥＬディスプレイの封着に用いることを特徴とする。 The glass composition for sealing of the present invention is used for sealing organic EL displays.
本発明の封着材料は、上記の封着用ガラス組成物からなるガラス粉末を６５〜１００体積％含有することを特徴とする。なお、本発明の封着材料は、上記の封着用ガラス組成物からなるガラス粉末のみで構成される態様を含むものである。 The sealing material of the present invention is characterized by containing 65 to 100% by volume of a glass powder made of the above-described sealing glass composition. In addition, the sealing material of this invention contains the aspect comprised only with the glass powder which consists of said glass composition for sealing.
本発明の封着材料は、実質的に耐火性フィラー粉末を含有しないことを特徴とする。ここで、「実質的に耐火性フィラー粉末を含有しない」とは、封着材料中の耐火性フィラー粉末の含有量が０．２質量％以下の場合を指す。このようにすれば、封着部位の厚みを均一化しやすくなり、特に封着部位に表面突起が発生する事態を防止しやすくなり、製品歩留まりを向上させることができる。 The sealing material of the present invention is characterized by containing substantially no refractory filler powder. Here, “substantially no refractory filler powder” refers to the case where the content of the refractory filler powder in the sealing material is 0.2% by mass or less. In this way, it becomes easy to make the thickness of the sealing part uniform, and in particular, it becomes easy to prevent the occurrence of surface protrusions at the sealing part, and the product yield can be improved.
本発明の封着材料は、熱膨張係数が８５×１０-7／℃以下であることを特徴とする。ここで、「熱膨張係数」とは、押棒式熱膨張係数測定（ＴＭＡ）装置により、３０〜３８０℃の温度範囲で測定した値を指す。 The sealing material of the present invention has a thermal expansion coefficient of 85 × 10 −7 / ° C. or less. Here, the “thermal expansion coefficient” refers to a value measured in a temperature range of 30 to 380 ° C. by a push rod type thermal expansion coefficient measurement (TMA) apparatus.
本発明の封着材料は、軟化点が６００℃以下であることを特徴とする。ここで、「軟化点」とは、マクロ型示差熱分析（ＤＴＡ）装置で測定した値を指し、ＤＴＡは室温から測定を開始し、昇温速度は１０℃／分とする。なお、マクロ型ＤＴＡ装置で測定した軟化点は、図１に示す第四屈曲点の温度（Ｔｓ）を指す。 The sealing material of the present invention has a softening point of 600 ° C. or lower. Here, the “softening point” refers to a value measured with a macro-type differential thermal analysis (DTA) apparatus, DTA starts measurement from room temperature, and the rate of temperature rise is 10 ° C./min. In addition, the softening point measured with the macro type | mold DTA apparatus points out the temperature (Ts) of the 4th bending point shown in FIG.
本発明の封着用ガラス組成物において、上記のようにガラス組成範囲を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、モル％を指す。 The reason why the glass composition range is limited as described above in the glass composition for sealing of the present invention will be described below. In addition, the following% display points out mol% unless there is particular notice.
ＳｉＯ2は、ガラスネットワークを形成する成分であるとともに、熱膨張係数を低下させる成分であり、その含有量は５〜３０％、好ましくは９〜２５％である。ＳｉＯ2の含有量が少ないと、ガラスの熱的安定性が低下し、レーザー光の照射時にガラスが失透しやすくなる。一方、ＳｉＯ2の含有量が多いと、ガラスの軟化点が高くなり過ぎ、レーザー光を照射しても、ガラスが軟化し難くなる。 SiO 2 is a component that forms a glass network and a component that lowers the thermal expansion coefficient, and its content is 5 to 30%, preferably 9 to 25%. When the content of SiO 2 is small, the thermal stability of the glass is lowered, and the glass tends to be devitrified when irradiated with laser light. On the other hand, if the content of SiO 2 is large, the softening point of the glass becomes too high, and the glass is difficult to soften even when irradiated with laser light.
Ｂ2Ｏ3は、ガラスネットワークを形成する成分であるとともに、ガラスの溶融温度および軟化点を下げる成分であり、その含有量は３１〜５５％、好ましくは３５〜５５％、より好ましくは４０〜５５％（但し、４０％は含まない）、更に好ましくは４１〜５０％である。Ｂ2Ｏ3の含有量が少ないと、ガラスの軟化点が高くなり過ぎ、レーザー光を照射しても、ガラスが軟化し難くなる。一方、Ｂ2Ｏ3の含有量が多いと、ガラスが分相しやすくなり、この場合、グレーズ後の焼成膜の平滑性が損なわれやすくなる。 B 2 O 3 is a component that forms a glass network and is a component that lowers the melting temperature and softening point of the glass, and its content is 31 to 55%, preferably 35 to 55%, more preferably 40 to 40%. 55% (however, 40% is not included), more preferably 41-50%. When the content of B 2 O 3 is small, the softening point of the glass becomes too high, and the glass is difficult to soften even when irradiated with laser light. On the other hand, when the content of B 2 O 3 is large, the glass tends to phase-separate, and in this case, the smoothness of the fired film after glazing tends to be impaired.
ＺｎＯは、ガラスの溶融温度や軟化点を過剰に上げることなく、熱膨張係数を下げる成分であり、その含有量は１５〜５５％、好ましくは２０〜４５％、より好ましくは２５〜３５％である。ＺｎＯの含有量が少ないと、ガラスの軟化点が高くなり過ぎ、レーザー光を照射しても、ガラスが軟化し難くなる。一方、ＺｎＯの含有量が多いと、ガラスの熱的安定性が低下し、レーザー光の照射時にガラスが失透しやすくなる。 ZnO is a component that lowers the thermal expansion coefficient without excessively increasing the melting temperature and softening point of the glass, and its content is 15 to 55%, preferably 20 to 45%, more preferably 25 to 35%. is there. When the content of ZnO is small, the softening point of the glass becomes too high, and the glass is difficult to soften even when irradiated with laser light. On the other hand, when the content of ZnO is large, the thermal stability of the glass is lowered, and the glass is easily devitrified when irradiated with laser light.
一般的に、ガラスの軟化点を下げると、ガラスネットワークが不安定になるため、ガラスの熱的安定性が低下する。よって、ガラスの低軟化特性と熱的安定性を両立させることは困難である。しかし、上記ガラス組成において、モル比ＺｎＯ／Ｂ2Ｏ3の値を１．５未満、好ましくは０．２〜１．２、より好ましくは０．５〜１に規制すると、ガラスの低軟化特性と熱的安定性を高いレベルで両立させることができる。 Generally, when the softening point of glass is lowered, the glass network becomes unstable, so that the thermal stability of the glass is lowered. Therefore, it is difficult to achieve both the low softening property and the thermal stability of the glass. However, in the above glass composition, when the molar ratio ZnO / B 2 O 3 is controlled to be less than 1.5, preferably 0.2 to 1.2, more preferably 0.5 to 1, the low softening property of the glass. And thermal stability at a high level.
ＣｕＯ＋Ｆｅ2Ｏ3＋Ｖ2Ｏ5＋ＴｉＯ2＋ＭｎＯ2は、光吸収特性を有する成分であり、レーザー光を照射すると、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０．１〜２５％、好ましくは０．２〜２０％、より好ましくは０．３〜１５％である。好ましくは０．５〜１０％である。ＣｕＯ＋Ｆｅ2Ｏ3＋Ｖ2Ｏ5＋ＴｉＯ2＋ＭｎＯ2の含有量が少ないと、光吸収特性が乏しくなり、レーザー光を照射しても、ガラスが軟化し難くなる。一方、ＣｕＯ＋Ｆｅ2Ｏ3＋Ｖ2Ｏ5＋ＴｉＯ2＋ＭｎＯ2の含有量が多いと、ガラス組成内の成分バランスが損なわれ、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 + V 2 O 5 + TiO 2 + MnO 2 is a component having light absorption characteristics, and when irradiated with laser light, it is a component that easily absorbs light and softens the glass, and its content is 0 0.1-25%, preferably 0.2-20%, more preferably 0.3-15%. Preferably it is 0.5 to 10%. If the content of CuO + Fe 2 O 3 + V 2 O 5 + TiO 2 + MnO 2 is small, the light absorption characteristics are poor, and the glass is difficult to soften even when irradiated with laser light. On the other hand, when CuO + Fe 2 O 3 + V 2 O 5 + TiO 2 + high content of MnO 2, balance of components in the glass composition is impaired, the glass is easily devitrified, the flowability of the glass is easily impaired.
ＣｕＯは、光吸収特性を有する成分であり、レーザー光を照射すると、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０〜１５％、好ましくは０．２〜１０％である。ＣｕＯの含有量が多いと、ガラス組成内の成分バランスが損なわれ、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 is a component having light absorption characteristics, and is a component that absorbs light and softens the glass when irradiated with laser light, and its content is 0 to 15%, preferably 0.2 to 10%. %. When there is much content of CuO, the component balance in a glass composition will be impaired, it will become easy to devitrify glass, and the fluidity | liquidity of glass will be easy to be impaired.
Ｆｅ2Ｏ3は、光吸収特性を有する成分であり、レーザー光を照射すると、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０〜１０％、好ましくは０．１〜５％である。Ｆｅ2Ｏ3の含有量が多いと、ガラス組成内の成分バランスが損なわれ、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。 Fe 2 O 3 is a component having light absorption characteristics, and is a component that absorbs light and softens the glass when irradiated with laser light, and its content is 0 to 10%, preferably 0.8. 1-5%. When the content of Fe 2 O 3 is large, the component balance in the glass composition is impaired, the glass is easily devitrified, the flowability 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、酸化鉄中のＦｅイオンは、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。 Although it is assumed that Fe in the glass composition exists in the form of Fe 2+ or Fe 3+ , in the present invention, Fe ions in iron oxide are either Fe 2+ or Fe 3+ . The present invention is not limited to these, and any of them may be used. Here, in the present invention, Fe 2+ is handled after being converted to Fe 2 O 3 . In particular, when using an infrared laser as a radiation beam, Fe 2+ is because it has absorption peaks in the infrared region, preferably is better to increase the proportion of Fe 2+, Fe 2+ / Fe 3+ in the iron oxide Is preferably 0.03 or more (preferably 0.08 or more).
Ｖ2Ｏ5は、光吸収特性を有する成分であり、レーザー光を照射すると、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０〜１０％、好ましくは０．１〜５％である。Ｖ2Ｏ5の含有量が多いと、レーザー光の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 is a component that absorbs light and softens the glass when irradiated with laser light, and its content is 0 to 10%, preferably 0.8. 1-5%. When the content of V 2 O 5 is large, the glass tends to be foamed when irradiated with laser light.
ＴｉＯ2は、光吸収特性を有する成分であり、レーザー光を照射すると、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、ガラスの熱膨張係数を下げる成分であり、その含有量は０〜１０％、好ましくは０．１〜７％である。ＴｉＯ2の含有量が多いと、ガラスの軟化点が高くなり過ぎ、レーザー光を照射しても、ガラスが軟化し難くなる。 TiO 2 is a component having light absorption characteristics, and is a component that, when irradiated with laser light, absorbs light and softens the glass, and is a component that lowers the thermal expansion coefficient of the glass. Is 0 to 10%, preferably 0.1 to 7%. When the content of TiO 2 is large, the softening point of the glass becomes too high, and the glass is difficult to soften even when irradiated with laser light.
ＭｎＯ2は、光吸収特性を有する成分であり、レーザー光を照射すると、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０〜１０％、好ましくは０．１〜５％である。ＭｎＯ2の含有量が多いと、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 laser light, it is a component that absorbs light and softens the glass, and its content is 0 to 10%, preferably 0.1 to 0.1%. 5%. When the content of MnO 2 is large, the glass is easily devitrified, the flowability of the glass is easily impaired.
上記ガラス組成範囲において、上記成分以外にも、例えば、下記の成分をガラス組成中に３０％まで含有させることができる。 In the glass composition range, in addition to the above components, for example, the following components can be contained up to 30% in the glass composition.
Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏは、ガラスの軟化点を下げる成分であり、その含有量は０〜２０％、好ましくは２〜２０％、より好ましくは５〜１５％である。Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏの含有量が多いと、ガラスの熱的安定性が低下し、レーザー光の照射時にガラスが失透しやすくなる。なお、ガラスの軟化点を確実に下げるためには、ガラス組成中に、必須成分としてＬｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏを２％以上含有させればよい。 Li 2 O + Na 2 O + K 2 O is a component that lowers the softening point of glass, and its content is 0 to 20%, preferably 2 to 20%, more preferably 5 to 15%. When Li 2 O + Na 2 O + K 2 O content is large, and decreases the thermal stability of the glass, the glass tends to be devitrified during the irradiation of the laser beam. In order to reliably lower the softening point of the glass, Li 2 O + Na 2 O + K 2 O may be contained at 2% or more as an essential component in the glass composition.
Ｌｉ2Ｏは、ガラスの軟化点を下げる成分であり、その含有量は０〜１２％、好ましくは０〜１０％である。Ｌｉ2Ｏの含有量が多いと、ガラスの熱的安定性が低下し、レーザー光の照射時にガラスが失透しやすくなる。 Li 2 O is a component that lowers the softening point of the glass, and its content is 0 to 12%, preferably 0 to 10%. When Li 2 O content is large, and decreases the thermal stability of the glass, the glass tends to be devitrified during the irradiation of the laser beam.
Ｎａ2Ｏは、ガラスの軟化点を下げる成分であり、その含有量は０〜１５％、好ましくは２〜１３％である。Ｎａ2Ｏの含有量が多いと、ガラスの熱的安定性が低下し、レーザー光の照射時にガラスが失透しやすくなる。 Na 2 O is a component that lowers the softening point of glass, and its content is 0 to 15%, preferably 2 to 13%. When Na 2 O content is large, and decreases the thermal stability of the glass, the glass tends to be devitrified during the irradiation of the laser beam.
Ｋ2Ｏは、ガラスの軟化点を下げる成分であり、その含有量は０〜１０％、好ましくは０〜７％である。Ｋ2Ｏの含有量が多いと、ガラスの熱的安定性が低下し、レーザー光の照射時にガラスが失透しやすくなる。 K 2 O is a component that lowers the softening point of the glass, and its content is 0 to 10%, preferably 0 to 7%. When K 2 O content is large, and decreases the thermal stability of the glass, the glass tends to be devitrified during the irradiation of the laser beam.
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ（ＭｇＯ、ＣａＯ、ＳｒＯおよびＢａＯの合量）は、ガラスの軟化点を下げる成分であり、その含有量は０〜２５％、好ましくは０〜２０％である。ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの含有量が多いと、ガラスの熱的安定性が低下し、レーザー光の照射時にガラスが失透しやすくなる。 MgO + CaO + SrO + BaO (total amount of MgO, CaO, SrO and BaO) is a component that lowers the softening point of glass, and its content is 0 to 25%, preferably 0 to 20%. When there is much content of MgO + CaO + SrO + BaO, the thermal stability of glass will fall and it will become easy to devitrify glass at the time of laser beam irradiation.
ＭｇＯは、ガラスの軟化点を下げる成分であり、その含有量は０〜１０％、好ましくは０〜５％である。ＭｇＯの含有量が多いと、ガラスの熱的安定性が低下し、レーザー光の照射時にガラスが失透しやすくなる。 MgO is a component that lowers the softening point of glass, and its content is 0 to 10%, preferably 0 to 5%. When there is much content of MgO, the thermal stability of glass will fall and it will become easy to devitrify glass at the time of laser beam irradiation.
ＣａＯは、ガラスの軟化点を下げる成分であり、その含有量は０〜１０％、好ましくは０〜５％である。ＣａＯの含有量が多いと、ガラスの熱的安定性が低下し、レーザー光の照射時にガラスが失透しやすくなる。 CaO is a component that lowers the softening point of glass, and its content is 0 to 10%, preferably 0 to 5%. When there is much content of CaO, the thermal stability of glass will fall and it will become easy to devitrify glass at the time of irradiation of a laser beam.
ＳｒＯは、ガラスの軟化点を下げる成分であり、その含有量は０〜１５％、好ましくは０〜１０％である。ＳｒＯの含有量が多いと、ガラスの熱的安定性が低下し、レーザー光の照射時にガラスが失透しやすくなる。 SrO is a component that lowers the softening point of glass, and its content is 0 to 15%, preferably 0 to 10%. When the content of SrO is large, the thermal stability of the glass is lowered, and the glass is easily devitrified when irradiated with laser light.
ＢａＯは、ガラスの軟化点を下げる成分であり、またガラスの熱的安定性を向上させる成分であり、その含有量は０〜１５％、好ましくは０〜１０％である。ＢａＯの含有量が多いと、ガラスの熱膨張係数が高くなり過ぎるおそれがある。 BaO is a component that lowers the softening point of the glass and improves the thermal stability of the glass, and its content is 0 to 15%, preferably 0 to 10%. When there is much content of BaO, there exists a possibility that the thermal expansion coefficient of glass may become high too much.
Ａｌ2Ｏ3は、ガラスの分相を抑える成分であり、またガラスの耐水性を高める成分であり、その含有量は０〜７％、好ましくは０〜５％である。Ａｌ2Ｏ3の含有量が多いと、ガラスの軟化点が高くなり過ぎ、レーザー光を照射しても、ガラスが軟化し難くなる。 Al 2 O 3 is a component that suppresses the phase separation of the glass and increases the water resistance of the glass, and its content is 0 to 7%, preferably 0 to 5%. When the content of Al 2 O 3 is large, the softening point of the glass becomes too high, and the glass is difficult to soften even when irradiated with laser light.
ＮｉＯは、光吸収特性を有する成分であり、レーザー光を照射すると、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 laser light, it is a component that absorbs light and softens the glass, and its content is 0 to 7%, preferably 0 to 3%. is there. When there is much content of NiO, it will become easy to devitrify glass and the fluidity | liquidity of glass will be easy to be impaired.
ＣｏＯは、光吸収特性を有する成分であり、レーザー光を照射すると、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０〜９％、好ましくは０〜３％である。ＣｏＯの含有量が多いと、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 is a component that absorbs light and softens the glass when irradiated with laser light, and its content is 0 to 9%, preferably 0 to 3%. is there. When there is much content of CoO, it will become easy to devitrify glass and the fluidity | liquidity of glass will be easy to be impaired.
ＭｏＯ3は、光吸収特性を有する成分であり、レーザー光を照射すると、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 laser light, it is a component that absorbs light and softens the glass, and its content is 0 to 7%, preferably 0 to 3%. It is. When the content of MoO 3 is large, the glass is easily devitrified, the flowability of the glass is easily impaired.
耐水性や耐薬品性を向上させるためにＺｒＯ2を５％（好ましくは２％）まで、またガラスの熱的安定性を向上させるのためにＰ2Ｏ5または希土類酸化物を１０％まで添加してもよい。 Add ZrO 2 to 5% (preferably 2%) to improve water resistance and chemical resistance, and add P 2 O 5 or rare earth oxide to 10% to improve the thermal stability of glass. May be.
上記の成分以外にも、他の成分をガラス組成中に１０％まで添加することができる。なお、環境的観点から、ＰｂＯを実質的に含有しないことが好ましい。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（質量）以下の場合を指す。 In addition to the above components, other components can be added up to 10% during the glass composition. From an environmental viewpoint, it is preferable that PbO is not substantially contained. Here, “substantially no PbO” refers to the case where the content of PbO in the glass composition is 1000 ppm (mass) or less.
本発明の封着材料は、上記の封着用ガラス組成物からなるガラス粉末を６５〜１００体積％、好ましくは８５〜１００体積％、より好ましくは９５〜１００体積％、特に好ましくは９８〜１００体積％含有する。ガラス粉末の含有量が少ないと、封着材料の流動性が乏しくなり、ガラス基板同士の封着強度を高めることが困難になる。 The sealing material of the present invention contains 65 to 100% by volume, preferably 85 to 100% by volume, more preferably 95 to 100% by volume, and particularly preferably 98 to 100% by volume of the glass powder composed of the above glass composition for sealing. %contains. When there is little content of glass powder, the fluidity | liquidity of a sealing material will become scarce and it will become difficult to raise the sealing strength of glass substrates.
本発明の封着材料において、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。ガラス粉末の平均粒子径Ｄ50を１５μｍ未満にすると、有機ＥＬディスプレイにおいて、ガラス基板間のギャップを狭小化しやすくなり、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。ここで、「平均粒子径Ｄ50」はレーザー回折法で測定した値を指す。 In the sealing material of the present invention, the average particle diameter D 50 of the 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 glass powder is less than 15 μm, it becomes easy to narrow the gap between the glass substrates in the organic EL display. In such a case, the difference in the thermal expansion coefficient between the glass substrate and the sealing material is large. In addition, cracks and the like are less likely to occur in the glass substrate and the sealing portion, and the time required for sealing can be shortened. Here, “average particle diameter D 50 ” refers to a value measured by a laser diffraction method.
本発明の封着材料において、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。ガラス粉末の平均粒子径Ｄmaxを３０μｍ以下にすると、有機ＥＬディスプレイにおいて、ガラス基板間のギャップを狭小化しやすくなり、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。ここで、「最大粒子径Ｄmax」はレーザー回折法で測定した値を指し、積算粒子径が９９％の粒子径（体積）を指す。 In the sealing material of the present invention, the maximum particle diameter D max of the 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 glass powder is 30 μm or less, the gap between the glass substrates is easily narrowed in the organic EL display. In such a case, the difference in the thermal expansion coefficient between the glass substrate and the sealing material is large. In addition, cracks and the like are less likely to occur in the glass substrate and the sealing portion, and the time required for sealing can be shortened. Here, “maximum particle diameter D max ” refers to a value measured by a laser diffraction method, and refers to a particle diameter (volume) with an integrated particle diameter of 99%.
上記封着用ガラス組成物からなるガラス粉末は、熱膨張係数が低いため、被封着物の熱膨張係数に整合させるために、必ずしも耐火性フィラー粉末を添加する必要はないが、被封着物の熱膨張係数に整合させるために、耐火性フィラー粉末を添加することも可能である（しかし、耐火性フィラー粉末を添加すると、既述の不具合が生じる可能性がある）。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４５体積％まで、好ましくは３０体積％まで含有させることができる。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被封着物の熱膨張係数に整合させることができ、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。耐火性フィラー粉末は、ジルコン、ジルコニア、酸化錫、チタン酸アルミニウム、β−スポジュメン、ムライト、チタニア、石英ガラス、β−石英、ウイレマイト、リン酸ジルコニウム化合物（例えば、リン酸ジルコニウム、リン酸タングステン酸ジルコニウム等）、タングステン酸ジルコニウムおよびＮＺＰ型結晶（例えば、ＮｂＺｒ（ＰＯ4）3、 [ＡＢ2（ＭＯ4）3]の基本構造をもつ結晶物、
Ａ：Ｌｉ、Ｎａ、Ｋ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｃｕ、Ｎｉ、Ｍｎ等
Ｂ：Ｚｒ、Ｔｉ、Ｓｎ、Ｎｂ、Ａｌ、Ｓｃ、Ｙ等
Ｍ：Ｐ、Ｓｉ、Ｗ、Ｍｏ等）若しくはこれらの固溶体が使用可能である。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、β−ユークリプタイト等を添加することもできる。
Since the glass powder made of the glass composition for sealing has a low coefficient of thermal expansion, it is not always necessary to add a refractory filler powder to match the coefficient of thermal expansion of the object to be sealed. In order to match the expansion coefficient, it is also possible to add a refractory filler powder (but the addition of the refractory filler powder may cause the above-mentioned problems). The sealing material for organic EL displays of the present invention can contain refractory filler powder up to 45% by volume, preferably up to 30% by volume. If the refractory filler powder is added, the thermal expansion coefficient of the sealing material can be matched with the thermal expansion coefficient of the object to be sealed, and as a result, it is possible to prevent a situation in which undue stress remains in the sealing portion. it can. The refractory filler powder is composed of zircon, zirconia, tin oxide, aluminum titanate, β-spodumene, mullite, titania, quartz glass, β-quartz, willemite, zirconium phosphate compounds (for example, zirconium phosphate, zirconium tungstate phosphate). Etc.), zirconium tungstate and NZP type crystals (for example, crystals having a basic structure of NbZr (PO 4 ) 3 , [AB 2 (MO 4 ) 3 ],
A: Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cu, Ni, Mn etc. B: Zr, Ti, Sn, Nb, Al, Sc, Y etc. M: P, Si, W, Mo etc. ) Or a solid solution thereof can be used. In addition to the above refractory filler powder, β-eucryptite and the like can be added for adjusting the thermal expansion coefficient of the sealing material, adjusting the fluidity, and improving the mechanical strength.
本発明の封着材料において、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、有機ＥＬディスプレイにおいて、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、有機ＥＬディスプレイにおいて、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 of the present invention, the average particle diameter D 50 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 15 μm or more, the sealing part is likely to be thick, and in the organic EL display, the gap between the glass substrates is increased, making it difficult to reduce the thickness of the organic EL display. Further, when the average particle diameter D 50 of the refractory filler powder is less than 15 μm, the gap between the glass substrates can be reduced in the organic EL display. In such a case, the thermal expansion coefficient of the glass substrate and the sealing material is reduced. Even if the difference is large, 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、有機ＥＬディスプレイにおいて、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、有機ＥＬディスプレイにおいて、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 of the present invention, the maximum particle diameter D max 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. When the maximum particle diameter D max of the refractory filler powder is larger than 30 μm, a portion having a thickness of 30 μm or more is generated in the sealing portion. Therefore, in the organic EL display, the gap between the glass substrates becomes non-uniform and organic It becomes difficult to make the EL display thinner. Further, when the average particle diameter D max of the refractory filler powder is 30 μm or less, the gap between the glass substrates can be reduced in the organic EL display. In such a case, the thermal expansion coefficient between the glass substrate and the sealing material Even if the difference is large, cracks and the like hardly occur in the glass substrate and the sealing part.
本発明の封着材料は、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２０体積％まで含有させてもよい。また、本発明の封着材料は、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１５体積％まで含有させてもよい。 The sealing material of the present invention may further contain glass fiber, glass beads, silica beads, resin beads, etc. up to 20% by volume as a spacer in order to make the thickness of the sealing part uniform. Further, the sealing material of the present invention may further contain up to 15% by volume of transition metal powder such as Cu, Fe, Mn, and Co in order to promote light absorption.
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、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、封着材料の熱膨張係数をできるだけ小さくすることは重要であり、具体的には、封着材料の熱膨張係数を８５×１０-7／℃以下（好ましくは８０×１０-7／℃以下、より好ましくは７５×１０-7／℃以下）にすることが望ましい。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。 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 with the thermal expansion coefficient of the alkali-free glass. However, it is important to make the thermal expansion coefficient of the sealing material as small as possible. Specifically, the thermal expansion coefficient of the sealing material is 85 × 10 −7 / ° C. or less (preferably 80 × 10 −7 / ° C. In the following, it is desirable to set it to 75 × 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.
本発明の封着材料において、軟化点は６００℃以下が好ましく、５８０℃以下がより好ましく、５６０℃以下が更に好ましい。軟化点が６００℃より高いと、レーザー光を照射しても、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。 In the sealing material of the present invention, the softening point is preferably 600 ° C. or less, more preferably 580 ° C. or less, and further preferably 560 ° C. or less. When the softening point is higher than 600 ° C., the glass tends to be difficult to soften even when irradiated with laser light. In order to increase the sealing strength between the glass substrates, it is necessary to increase the output of the laser light. 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.
本発明の封着材料は、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 of the present invention may be used as it is in powder form, but 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は、本発明の実施例（試料Ｎｏ．１〜５）および比較例（試料Ｎｏ．６）を示している。 Table 1 shows Examples (Sample Nos. 1 to 5) and Comparative Examples (Sample No. 6) of the present invention.
表１に記載の各試料は次のようにして調製した。まず、表中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１２５０℃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２０μｍの各ガラス粉末を得た。 Each sample described in Table 1 was prepared as follows. First, a glass batch in which raw materials such as various oxides and carbonates were prepared so as to have the glass composition shown in the table was prepared, and this was put in a platinum crucible and melted at 1250 ° C. for 1 hour. Next, the molten glass was formed into a thin piece with a water-cooled roller. Finally, the glass flakes were pulverized by a ball mill and classified by air to obtain glass powders having an average particle diameter D 50 of 2.5 μm and a maximum particle diameter D max of 20 μm.
試料Ｎｏ．１〜６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。 Sample No. About 1-6, 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.
ガラス転移点および軟化点は、ＤＴＡ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 DTA apparatus. The measurement was performed in the atmosphere at a temperature rising rate of 10 ° C./min, and the measurement was started from room temperature.
熱膨張係数は、ＴＭＡ装置で求めた。測定温度範囲は３０〜３８０℃とした。 The thermal expansion coefficient was determined with a TMA apparatus. The measurement temperature range was 30 to 380 ° 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.
封着強度は、次のようにして評価した。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、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、ガラス基板を５５０℃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、焼成膜が形成されたガラス基板の上に、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、焼成膜に沿って、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、封着部位が両ガラス基板から剥離しなかったものを「○」、封着部位が両ガラス基板から剥離したものを「×」として評価した。 The sealing strength was evaluated as follows. First, each sample and vehicle (acrylic resin-containing α-terpineol) were uniformly kneaded with a three-roll mill and made into a paste, and then a glass substrate (OA-10, Nippon Electric Glass Co., Ltd., □ 100 mm × 0.5 mm) (Thickness) was coated linearly (30 μm thick) at 150 ° C. for 10 minutes in a drying oven. Next, the temperature was raised from room temperature at 10 ° C./minute, and the glass substrate was baked at 550 ° C. for 20 minutes, and then the temperature was lowered to room temperature at 10 ° C./minute to perform a binder removal treatment. Next, a glass substrate (OA-10 manufactured by Nippon Electric Glass Co., Ltd., □ 100 mm × 0.5 mm thickness) is accurately stacked on the glass substrate on which the fired film is formed, and then the wavelength along the fired film. A 1060 nm YAG laser (output 600 mW, power density 5 kW / cm 2 ) was irradiated to seal both glass substrates. Both glass substrates after sealing are dropped onto the concrete from 1 m above, “○” indicates that the sealing part is not peeled off from both glass substrates, and “×” indicates that the sealing part is peeled off from both glass substrates. As evaluated.
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 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 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から明らかなように、試料Ｎｏ．１〜５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ディスプレイの封着に好適であると判断できる。表３から明らかなように、試料Ｎｏ．６は、ガラス組成中にＣｕＯ＋Ｆｅ2Ｏ3＋Ｖ2Ｏ5＋ＴｉＯ2＋ＭｎＯ2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。 As is clear from Table 1, sample No. Nos. 1 to 5 have good evaluation of fluidity, sealing strength, foamability and devitrification state, and can be determined to be suitable for sealing an organic EL display. As apparent from Table 3, the sample No. Since No. 6 did not contain CuO + Fe 2 O 3 + V 2 O 5 + TiO 2 + MnO 2 in the glass composition, the evaluation of fluidity and sealing strength was poor.
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