JP5026121B2 - Antimony phosphate glass composition - Google Patents
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Description
本発明はアンチモンリン酸塩系ガラス組成物に関する。 The present invention relates to an antimony phosphate glass composition.
従来、封着用のガラス組成物は、ＰｂＯ−ＳｉＯ２−Ｂ２Ｏ３系等の鉛ガラス粉末とＰｂＴｉＯ３のようなセラミックフィラーからなるのが一般的であった。しかし近年、鉛を含むガラス及びフィラーは環境上の観点から使用が避けられ、鉛成分を含まずに低温で封着できるガラス組成物が開発されてきている。
鉛を含まない低融点ガラスとしては、ビスマス系ガラス、リン酸系ガラス、硼珪酸塩ガラス、アルカリ珪酸塩ガラスなどが知られている。
前記ビスマス系ガラスは一般に耐候性がよいが、資源量に限りがあり、また原料費が高いという問題がある。
一方、前記硼珪酸塩ガラス、アルカリ珪酸塩ガラスは低融化させるためにアルカリ金属酸化物を多く含むため、耐候性が十分ではないという問題がある。
Conventionally, a glass composition for sealing is generally composed of a lead glass powder such as a PbO—SiO 2 —B 2 O 3 system and a ceramic filler such as PbTiO 3 . However, in recent years, glass and fillers containing lead can be avoided from an environmental point of view, and glass compositions that can be sealed at low temperatures without containing lead components have been developed.
As low-melting glass not containing lead, bismuth glass, phosphate glass, borosilicate glass, alkali silicate glass, and the like are known.
The bismuth glass generally has good weather resistance, but has a problem that the amount of resources is limited and the raw material cost is high.
On the other hand, since the borosilicate glass and the alkali silicate glass contain a large amount of alkali metal oxide in order to lower the melting point, there is a problem that the weather resistance is not sufficient.
このような状況下において、リン酸塩系ガラスが着目されてきた。従来のリン酸塩系ガラスとしては下記特許文献１〜６が提供されている。
ところが上記特許文献１、２に開示されたガラスは、アルカリ金属酸化物を多く含んでいるため、低融点ではあるが、熱膨張係数が高く、また耐候性が十分ではないという問題があった。
また上記特許文献３〜５に開示されたガラスは、ＺｎＯを多く含んでいるため、軟化点を下げることができるが、耐候性が十分ではないという問題があった。
また上記特許文献６に開示されたガラスは、ＳｎＯを多く含み、耐候性に優れたものであるものの、このガラスはガラス成分のＳｎＯがＳｎＯ２になると溶け残りが発生するため、還元性雰囲気で溶解を行わねばならないという問題があった。
However, since the glasses disclosed in Patent Documents 1 and 2 contain a large amount of alkali metal oxides, they have a low melting point but a high thermal expansion coefficient and insufficient weather resistance.
Moreover, since the glass disclosed by the said patent documents 3-5 contains many ZnO, there existed a problem that a weather resistance was not enough, although a softening point could be lowered | hung.
Further, the glass disclosed in Patent Document 6 contains a lot of SnO and has excellent weather resistance. However, since this glass has an unmelted portion when SnO of the glass component becomes SnO 2 , it remains in a reducing atmosphere. There was a problem that dissolution had to be performed.
そこで本発明は上記従来のリン酸塩系ガラスの欠点を解決し、酸化鉛を含まず、低融点で耐候性がよく、通常雰囲気で溶融することができ、封着ガラスとしても有用であるアンチモンリン酸塩系ガラス組成物の提供を課題とする。 Accordingly, the present invention solves the disadvantages of the above-mentioned conventional phosphate glasses, does not contain lead oxide, has a low melting point, good weather resistance, can be melted in a normal atmosphere, and is useful as a sealing glass. It is an object to provide a phosphate glass composition.
本発明者らは上記課題を解決すべく鋭意研究を重ねた結果、封着用のガラスとして用いられ、また鉛フリーのガラスとして用いられるリン酸塩系ガラスとしてＳｂ２Ｏ３、Ａｌ２Ｏ３、ＭｇＯ、ＺｒＯ２、ＴｉＯ２の少なくとも１種、ＣａＯ、ＳｒＯ、ＢａＯ、ＺｎＯ、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏの少なくとも１種を、適切に含有させることにより上記の課題を解決できることを見出し、本発明を完成した。
即ち、本発明のアンチモンリン酸塩系ガラス組成物は、封着用のガラスとして用いられ、成分として鉛フリーであり、Ｐ２Ｏ５：２０〜５０重量％、Ｓｂ２Ｏ３：２０〜７０重量％、Ａｌ２Ｏ３：０．３〜５重量％、ＭｇＯ：０．５〜１５重量％、ＺｒＯ２、ＴｉＯ２の少なくとも１種：０．５〜５重量％、ＣａＯ、ＳｒＯ、ＢａＯ、ＺｎＯ、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏの少なくとも１種：２〜３０重量％を含有することを第１の特徴としている。
また本発明のアンチモンリン酸塩系ガラス組成物は、上記第１の特徴に加えて、Ｐ２Ｏ５：２０〜４０重量％、Ｓｂ２Ｏ３：４０〜６０重量％、Ａｌ２Ｏ３：０．３〜３重量％、ＭｇＯ：０．５〜５重量％、ＺｒＯ２、ＴｉＯ２の少なくとも１種：０．５〜３重量％、ＣａＯ、ＳｒＯ、ＢａＯ、ＺｎＯ、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏの少なくとも１種：５〜２０重量％を含有することを第２の特徴としている。
また本発明のアンチモンリン酸塩系ガラス組成物は、上記第１又は第２の特徴に加えて、Ｂ２Ｏ３、Ｂｉ２Ｏ３、ＴｅＯ２、Ｖ２Ｏ５の少なくとも１種を１５重量％以下含有させることを第３の特徴としている。
また本発明のアンチモンリン酸塩系ガラス組成物は、上記第１〜第３の何れかに記載の特徴に加えて、ＷＯ３、ＳｎＯ、Ａｇ２Ｏ、Ｉｎ２Ｏ３、ＣｕＯの少なくとも１種を２０重量％以下含有させることを第４の特徴としている。
また本発明のアンチモンリン酸塩系ガラス組成物は、上記第１〜第４の何れかに記載の特徴に加えて、粉末であることを第５の特徴としている。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have used Sb 2 O 3 , Al 2 O 3 , and phosphate-based glasses used as glass for sealing and used as lead-free glass . The problem described above can be solved by appropriately containing at least one of MgO, ZrO 2 and TiO 2 and at least one of CaO, SrO, BaO, ZnO, Li 2 O, Na 2 O and K 2 O. The headline and the present invention were completed.
That is, the antimony phosphate glass composition of the present invention is used as a glass for sealing and is lead-free as a component, P 2 O 5 : 20 to 50% by weight, Sb 2 O 3 : 20 to 70% by weight. %, Al 2 O 3 : 0.3 to 5% by weight, MgO: 0.5 to 15% by weight, at least one of ZrO 2 and TiO 2 : 0.5 to 5% by weight, CaO, SrO, BaO, ZnO , Li 2 O, Na 2 O, at least one of K 2 O: 2 to 30 wt% is a first feature.
The antimony phosphate type glass composition of the present invention, in addition to the first feature, P 2 O 5: 20~40 wt%, Sb 2 O 3: 40~60 wt%, Al 2 O 3: 0.3 to 3 wt%, MgO: 0.5 to 5 wt%, ZrO 2, TiO 2 of at least one: 0.5-3 wt%, CaO, SrO, BaO, ZnO, Li 2 O, Na 2 The second feature is that it contains at least one of O and K 2 O: 5 to 20% by weight.
In addition to the first or second feature, the antimony phosphate glass composition of the present invention has 15 wt.% Of at least one of B 2 O 3 , Bi 2 O 3 , TeO 2 , and V 2 O 5. The third feature is that the content is not more than%.
Moreover, the antimony phosphate glass composition of the present invention has at least one of WO 3 , SnO, Ag 2 O, In 2 O 3 , and CuO in addition to the characteristics described in any one of the first to third aspects. It is the 4th characteristic to contain 20 weight% or less.
The antimony phosphate glass composition of the present invention has a fifth feature of being a powder in addition to the features described in any one of the first to fourth aspects.
請求項１に記載のアンチモンリン酸塩系ガラス組成物によれば、そこに記載された組成としたので、得られるガラスを低融点で、耐候性がよく、通常雰囲気で溶融することができ、封着ガラスとして有用なものとすることができる。勿論、鉛を含まないので安全性も高い。 According to the antimony phosphate glass composition according to claim 1, since the composition described therein is used, the resulting glass has a low melting point, good weather resistance, and can be melted in a normal atmosphere. it can be made for organic as a sealing glass. Of course, since lead is not included, safety is also high.
また請求項２に記載のアンチモンリン酸塩系ガラス組成物によれば、そこに記載された組成として、上記した請求項１に記載のアンチモンリン酸塩系ガラス組成物の各成分の含有量をより限定したことで、一層、低融点で、耐候性がよく、また封着性のよいものを提供することができる。 Moreover, according to the antimony phosphate glass composition of claim 2, the content of each component of the antimony phosphate glass composition of claim 1 described above is set as the composition described therein. By further limiting, it is possible to provide a material having a low melting point, good weather resistance, and good sealing properties.
また請求項３に記載のアンチモンリン酸塩系ガラス組成物によれば、上記請求項１又は２に記載の構成による効果に加えて、Ｂ２Ｏ３、Ｂｉ２Ｏ３、ＴｅＯ２、Ｖ２Ｏ５の少なくとも１種を１５重量％以下含有させることで、ガラスの安定性を向上させることができる。 Moreover, according to the antimony phosphate glass composition of claim 3 , in addition to the effect of the configuration of claim 1 or 2, B 2 O 3 , Bi 2 O 3 , TeO 2 , V 2 By containing at least one kind of O 5 in an amount of 15% by weight or less, the stability of the glass can be improved.
また請求項４に記載のアンチモンリン酸塩系ガラス組成物によれば、上記請求項１〜３の何れかに記載の構成による効果に加えて、ＷＯ３、ＳｎＯ、Ａｇ２Ｏ、Ｉｎ２Ｏ３、ＣｕＯの少なくとも１種を２０重量％以下含有させることで、ガラスの軟化点を一層低下させることができる。 According to the antimony phosphate glass composition of claim 4, in addition to the effect of the structure of any of claims 1 to 3, WO 3 , SnO, Ag 2 O, In 2 O 3. By containing at least one kind of CuO in an amount of 20% by weight or less, the softening point of the glass can be further reduced.
また請求項５に記載のアンチモンリン酸塩系ガラス組成物によれば、上記請求項１〜４の何れかに記載の構成による効果に加えて、粉末であることにより、封着作業の際の取り扱いが非常に容易である。 Moreover, according to the antimony phosphate glass composition of claim 5, in addition to the effect of the structure of any of claims 1 to 4, by being a powder, during the sealing operation It is very easy to handle.
本発明のアンチモンリン酸塩系ガラス組成物における成分と、その含有量について説明する。
成分Ｐ２Ｏ５は本発明の実施形態にかかるガラスの網目を形成する酸化物である。２０〜５０重量％の範囲で含有させるのが好ましい。
Ｐ２Ｏ５が２０重量％未満の場合には、軟化点が高くなり過ぎる問題がある。またガラスが得られ難くなる問題が生じる。
一方、Ｐ２Ｏ５が５０重量％を超える場合は、耐候性が悪くなる問題が生じる。
Ｐ２Ｏ５の含有量は、軟化点、耐候性等を考慮すると、２０〜４０重量％であることがより好ましい。
The components in the antimony phosphate glass composition of the present invention and the contents thereof will be described.
The component P 2 O 5 is an oxide that forms a glass network according to an embodiment of the present invention. It is preferable to make it contain in 20-50 weight%.
When P 2 O 5 is less than 20% by weight, there is a problem that the softening point becomes too high. Moreover, the problem that it becomes difficult to obtain glass arises.
On the other hand, if the P 2 O 5 exceeds 50 wt%, there is a problem that weather resistance is deteriorated.
The content of P 2 O 5 is more preferably 20 to 40% by weight in consideration of the softening point, weather resistance, and the like.
成分Ｓｂ２Ｏ３はガラスの軟化点を下げる成分であり、２０〜７０重量％の範囲で含有させるのが好ましい。
Ｓｂ２Ｏ３が２０重量％未満の場合には、軟化点が高くなり過ぎる問題がある。またガラスが得られ難くなる問題が生じる。
一方、Ｓｂ２Ｏ３が７０重量％を超えると、熱膨張係数が高くなり過ぎる問題が生じる。
Ｓｂ２Ｏ３の含有量は、ガラスの軟化点、熱膨張係数等を考慮すると、４０〜６０重量％がより好ましい。
The component Sb 2 O 3 is a component that lowers the softening point of the glass and is preferably contained in the range of 20 to 70% by weight.
When Sb 2 O 3 is less than 20% by weight, there is a problem that the softening point becomes too high. Moreover, the problem that it becomes difficult to obtain glass arises.
On the other hand, when Sb 2 O 3 exceeds 70% by weight, there arises a problem that the thermal expansion coefficient becomes too high.
The content of Sb 2 O 3 is more preferably 40 to 60% by weight in consideration of the softening point of glass, the thermal expansion coefficient, and the like.
成分Ａｌ２Ｏ３は熱膨張係数を下げ、且つ耐候性を向上させる作用がある。このＡｌ２Ｏ３は０．３〜５重量％の範囲で含有させるのが好ましい。
０．３重量％未満の場合には、熱膨張係数が高くなる問題が生じ、或いは耐候性が悪くなる問題が生じる。
また５重量％を超える場合には、ガラスが得られなくなるおそれが生じる。
成分Ａｌ２Ｏ３の含有量は、熱膨張係数、耐候性を考慮すると、０．３〜３重量％であることがより好ましい。
The component Al 2 O 3 has the effect of lowering the thermal expansion coefficient and improving the weather resistance. This Al 2 O 3 is preferably contained in the range of 0.3 to 5% by weight.
When the amount is less than 0.3% by weight, there is a problem that the thermal expansion coefficient is increased or a weather resistance is deteriorated.
Moreover, when it exceeds 5 weight%, there exists a possibility that glass may not be obtained.
The content of the component Al 2 O 3 is more preferably 0.3 to 3% by weight in consideration of the thermal expansion coefficient and weather resistance.
ＭｇＯは熱膨張係数を下げ、ガラスの成形性を向上させる成分であり、０．５〜１５重量％の範囲で含有させることが好ましい。
ＭｇＯが０．５重量％未満の場合には、熱膨張係数が高くなり過ぎる問題が生じる。
またＭｇＯが１５重量％を超える場合には、軟化点が高くなり過ぎるおそれがある。
ＭｇＯの含有量は、熱膨張係数、ガラスの成形性等を考慮すると、０．５〜５重量％であることがより好ましい。
MgO is a component that lowers the thermal expansion coefficient and improves the moldability of the glass, and is preferably contained in the range of 0.5 to 15% by weight.
When MgO is less than 0.5% by weight, there arises a problem that the thermal expansion coefficient becomes too high.
If MgO exceeds 15% by weight, the softening point may be too high.
The content of MgO is more preferably 0.5 to 5% by weight in consideration of the thermal expansion coefficient, glass moldability, and the like.
成分ＺｒＯ２、ＴｉＯ２はガラスの耐候性を向上させ、Ａｌ２Ｏ３と同様に熱膨張係数を下げる作用がある。このＺｒＯ２、ＴｉＯ２は、その少なくとも１種を０．５〜５重量％の範囲で含有させるのが好ましい。
合計量で０．５重量％未満の場合には、ガラスの耐候性を向上させる効果がでない。
５重量％を超える場合には、溶液中で溶け残るおそれが生じる。
成分ＺｒＯ２、ＴｉＯ２の含有量は、ガラスの耐候性、成形性等を考慮すると、０．５〜３重量％とすることがより好ましい。
Components ZrO 2 and TiO 2 have the effect of improving the weather resistance of the glass and lowering the thermal expansion coefficient in the same manner as Al 2 O 3 . It is preferable that at least one of these ZrO 2 and TiO 2 is contained in the range of 0.5 to 5% by weight.
When the total amount is less than 0.5% by weight, there is no effect of improving the weather resistance of the glass.
If it exceeds 5% by weight, there is a risk that it will remain undissolved in the solution.
The content of the components ZrO 2 and TiO 2 is more preferably 0.5 to 3% by weight in consideration of the weather resistance, moldability, and the like of the glass.
ＣａＯ、ＳｒＯ、ＢａＯ、ＺｎＯは、熱膨張係数を下げ、ガラスの成形性を向上させる作用がある。一方、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏは熱膨張係数を上げる成分であるが、ガラスの成形性を向上させる作用がある。
これらＣａＯ、ＳｒＯ、ＢａＯ、ＺｎＯ、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏは、少なくとも１種を２〜３０重量％の範囲で含有させることが好ましい。
合計量が２重量％未満の場合には、ガラスの成形性を向上させる効果を奏さない。
また３０重量％を超える場合には、軟化点が高くなり過ぎ、熱膨張係数が上がり過ぎ、耐候性が低下する問題が生じる。
成分ＣａＯ、ＳｒＯ、ＢａＯ、ＺｎＯ、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏの含有量は、ガラスの成形性を考慮すると５〜２０重量％であることがより好ましい。
CaO, SrO, BaO and ZnO have the effect of lowering the coefficient of thermal expansion and improving the moldability of the glass. On the other hand, Li 2 O, Na 2 O, and K 2 O are components that increase the coefficient of thermal expansion, but have the effect of improving the moldability of the glass.
These CaO, SrO, BaO, ZnO, Li 2 O, Na 2 O, and K 2 O are preferably contained in the range of 2 to 30% by weight.
When the total amount is less than 2% by weight, the effect of improving the moldability of the glass is not achieved.
On the other hand, if it exceeds 30% by weight, the softening point becomes too high, the thermal expansion coefficient becomes too high, and the weather resistance deteriorates.
The content of the components CaO, SrO, BaO, ZnO, Li 2 O, Na 2 O, and K 2 O is more preferably 5 to 20% by weight in view of the moldability of the glass.
上記の成分の他に、Ｂ２Ｏ３、Ｂｉ２Ｏ３、ＴｅＯ２、Ｖ２Ｏ５の少なくとも１種を１５重量％以下含有させることができる。
これらの成分を合計量で１５重量％以下含有させることにより、ガラスの安定性を向上させることができる。
より好ましくは１０重量％以下で含有させるのがよい。
In addition to the above components, at least one of B 2 O 3 , Bi 2 O 3 , TeO 2 , and V 2 O 5 can be contained in an amount of 15% by weight or less.
By containing these components in a total amount of 15% by weight or less, the stability of the glass can be improved.
More preferably, the content is 10% by weight or less.
また上記成分の他に、ＷＯ３、ＳｎＯ、Ａｇ２Ｏ、Ｉｎ２Ｏ３、ＣｕＯの少なくとも１種を２０重量％以下含有させることができる。
合計量で２０重量％以下含有させることにより、ガラスの軟化点を低下させることができる。
より好ましくは１０重量％以下含有させるのがよい。
In addition to the above components, at least one of WO 3 , SnO, Ag 2 O, In 2 O 3 and CuO can be contained in an amount of 20% by weight or less.
By containing 20% by weight or less in the total amount, the softening point of the glass can be lowered.
More preferably, it is 10% by weight or less.
ガラスよりも熱膨張係数の低い基材との接合、例えば封着や接着を行う場合には、上記したガラス組成に耐火物フィラーを混合して、熱膨張係数を低下させる必要がある。
前記耐火物フィラーは、セラミックフィラーと石英ガラスフィラーとの少なくとも１種を３５重量％以下添加することで、基材との熱膨張係数を合わせる。３５重量％を超えると接着がなされない問題が生じる。
前記セラミックフィラーとしては、コージェライト、β−ユークリプタイト、チタン酸アルミニウム、ジルコン、ムライト、β−スポジュメン、アルミナ、ウィレマイト、リン酸ジルコニウム、ニオブリン酸ジルコニウム、α−クォーツのうちの少なくとも１種を用いることが好ましい。
これらのフィラーを用いることにより、種々の基材に対して十分な封着を行うことができる。
When joining with a base material having a lower thermal expansion coefficient than glass, for example, sealing or bonding, it is necessary to mix the above-described glass composition with a refractory filler to lower the thermal expansion coefficient.
The refractory filler is added with at least one of a ceramic filler and a quartz glass filler in an amount of 35% by weight or less, thereby matching the thermal expansion coefficient with the substrate. If it exceeds 35% by weight, there is a problem that adhesion is not achieved.
As the ceramic filler, at least one of cordierite, β-eucryptite, aluminum titanate, zircon, mullite, β-spodumene, alumina, willemite, zirconium phosphate, zirconium niobate, and α-quartz is used. It is preferable.
By using these fillers, sufficient sealing can be performed on various substrates.
上記した成分によるガラスの製造と封着について説明する。
先ず所定の成分組成となるように各成分原料を混合してバッチ原料とする。
次にこれを１０００〜１１００℃で、白金ルツボ内で１時間溶融し、その後、双ロール法で急冷してガラスフレークを得る。得られたフレークをアルミナ製ボールミルで粉砕して粉末とする。
粉末となったガラスは封着材料として単独でも使用できるが、基材との熱膨張係数を合わせる場合には、耐火物フィラーを添加する。
作製した封着材料は有機系ビヒクル等でペースト化して、基材の接着表面に塗布し、ガラスが軟化する温度まで加熱して使用する。
前記基材はガラス板、ステンレス、アルミナ基板等である。
The production and sealing of the glass using the above components will be described.
First, each component raw material is mixed so as to have a predetermined component composition to obtain a batch raw material.
Next, it is melted at 1000 to 1100 ° C. in a platinum crucible for 1 hour, and then rapidly cooled by a twin roll method to obtain glass flakes. The obtained flakes are pulverized with an alumina ball mill to form a powder.
Although the powdered glass can be used alone as a sealing material, a refractory filler is added to match the thermal expansion coefficient with the base material.
The produced sealing material is made into a paste with an organic vehicle or the like, applied to the adhesive surface of the substrate, and heated to a temperature at which the glass is softened.
The substrate is a glass plate, stainless steel, alumina substrate or the like.
以下に、実施例を挙げて本発明を更に説明する。しかしながら本発明は、これらの実施例により何ら限定されるものではない。
下記表１〜表６に示す成分組成となるように、実施例１〜４１について原料を調合して混合し、これを白金ルツボに入れて、電気炉中で１０００℃、１時間溶融する。その後、双ロール法で急冷してガラスフレークを得ると共に、予め加熱しておいた鉄板に流し出してガラスブロックを作製した。
前記ガラスブロックは予想されるガラス転移温度より約５０℃高い温度に設定した電気炉に入れ、徐冷を行った後、切り出して研磨し、熱膨張係数、軟化点を測定するサンプルとした。また別のガラスブロックを切り出し、０．３〜０．５ｍｍの厚さになるまで鏡面研磨し、その試料を使用して耐候性試験のサンプルとした。
また前記ガラスフレークを用いて、これをアルミナ製ボールミルで粉砕して粉末とし、ガラス転移温度の測定、フロー試験のサンプルとした。
同様にして、Ｓｂ２Ｏ５、ＭｇＯ等、本発明の成分組成を含有しない、Ｐ２Ｏ５−ＺｎＯ系ガラスである比較例１、２について上記と同様の測定、試験のサンプルとした。
The present invention will be further described below with reference to examples. However, the present invention is not limited to these examples.
The raw materials were prepared and mixed for Examples 1 to 41 so as to have the component compositions shown in Tables 1 to 6 below, put in a platinum crucible, and melted in an electric furnace at 1000 ° C. for 1 hour. Thereafter, the glass flakes were obtained by quenching by a twin roll method, and poured into a preheated iron plate to produce a glass block.
The glass block was put in an electric furnace set to a temperature about 50 ° C. higher than the expected glass transition temperature, slowly cooled, cut out, polished, and used as a sample for measuring the thermal expansion coefficient and softening point. Another glass block was cut out and mirror-polished to a thickness of 0.3 to 0.5 mm, and the sample was used as a sample for a weather resistance test.
The glass flakes were pulverized with an alumina ball mill to form a powder, which was used as a sample for measurement of the glass transition temperature and flow test.
Similarly, the samples of Comparative Examples 1 and 2 which are P 2 O 5 —ZnO-based glasses that do not contain the component composition of the present invention, such as Sb 2 O 5 and MgO, were used as measurement and test samples similar to the above.
実施例、比較例に供した原料は、Ｈ３ＰＯ４、Ｓｂ２Ｏ３、Ａｌ（ＰＯ３）３、Ａｌ２Ｏ３、Ａｌ（ＯＨ）３、Ｍｇ（ＰＯ３）２、Ｍｇ（ＯＨ）２、ＺｒＯ２、ＴｉＯ２、Ｃａ（ＰＯ３）２、Ｓｒ（ＰＯ３）２、Ｂａ（ＰＯ３）２、Ｚｎ（ＰＯ３）２、ＣａＣＯ３、ＳｒＣＯ３、ＢａＣＯ３、ＺｎＯ、ＬｉＰＯ３、ＮａＰＯ３、ＫＰＯ３、Ｌｉ２ＣＯ３、Ｎａ２ＣＯ３、Ｋ２ＣＯ３、Ｈ３ＢＯ３、Ｂｉ２Ｏ３、ＴｅＯ２、Ｖ２Ｏ５、ＷＯ３、ＳｎＯ、ＡｇＮＯ３、Ｉｎ２Ｏ３、ＣｕＯである。 The raw materials used in Examples and Comparative Examples were H 3 PO 4 , Sb 2 O 3 , Al (PO 3 ) 3 , Al 2 O 3 , Al (OH) 3 , Mg (PO 3 ) 2 , Mg (OH) 2 , ZrO 2 , TiO 2 , Ca (PO 3 ) 2 , Sr (PO 3 ) 2 , Ba (PO 3 ) 2 , Zn (PO 3 ) 2 , CaCO 3 , SrCO 3 , BaCO 3 , ZnO, LiPO 3 , NaPO 3, KPO 3, Li 2 CO 3, Na 2 CO 3, K 2 CO 3, H 3 BO 3, Bi 2 O 3, TeO 2, V 2 O 5, WO 3, SnO, AgNO 3, In 2 O 3 and CuO.
また実施例、比較例において、ガラス転移点（Ｔｇ）、熱膨張係数（α）、軟化点（Ｔｄ）、耐候性、フロー温度を測定した。各測定の方法は次の通りである。
（１）ガラス転移温度（Ｔｇ）
１００メッシュを通過したガラス粉末、約５０ｍｇを白金セルに入れ、示差熱分析装置（ＤＴＡ、理学電機製ＴＧ８１１０）を用いて、アルミナ粉末を標準試料として室温から２０Ｋ／ｍｉｎで昇温して得られたＤＴＡ曲線より、最初の吸熱の開始点（外挿点）の温度をガラス転移温度とした。
（２）熱膨張係数（α）、軟化点（Ｔｄ）
ガラス或いはフロー後の試料を用い、直径約５ｍｍ、長さ１５〜２０ｍｍのロッド状に加工し、熱機械分析装置（ＴＭＡ、理学電機製ＴＭ８１４０）を用い、荷重を１０ｇ、石英ガラスを標準試料とし、室温から１０Ｋ／ｍｉｎで昇温して得られた熱膨張曲線より５０〜２５０℃の平均値の線熱膨張係数を求めた。またガラス単独の場合、熱膨張曲線の最大長さとなったときの温度を軟化点（Ｔｄ）とした。
（３）耐候性（時間）
得られたガラスブロックを０．３〜０．５ｍｍの厚さになるまで鏡面研磨した試料を約６０℃、９５％相対湿度の恒温恒湿機内で保持し、一定時間毎にその表面状態を観察し、ガラス表面が曇り、斑点が観察される時間により評価した。
（４）フロー温度（℃）
ガラス粉末と耐火物フィラーを所定の割合で混合し、その混合粉末を直径約１０ｍｍ、長さ１２〜１５ｍｍのロッドになるようにプレス成形する。このロッドをアルミナ板上にのせ、所定温度へ上昇させる。ロッドが変形、屈曲してアルミナ板上に倒れたときの温度をフロー温度とした。
In Examples and Comparative Examples, glass transition point (Tg), thermal expansion coefficient (α), softening point (Td), weather resistance, and flow temperature were measured. Each measurement method is as follows.
(1) Glass transition temperature (Tg)
About 50 mg of glass powder that has passed 100 mesh is placed in a platinum cell, and is obtained by using a differential thermal analyzer (DTA, TG8110 manufactured by Rigaku Corporation) and increasing the temperature from room temperature to 20 K / min using alumina powder as a standard sample. From the DTA curve, the temperature of the first endothermic end point (extrapolated point) was defined as the glass transition temperature.
(2) Thermal expansion coefficient (α), softening point (Td)
Using glass or a sample after flow, it is processed into a rod shape with a diameter of about 5 mm and a length of 15 to 20 mm. Using a thermomechanical analyzer (TMA, TM8140 manufactured by Rigaku Corporation), the load is 10 g and quartz glass is the standard sample. From the thermal expansion curve obtained by raising the temperature from room temperature at 10 K / min, an average linear thermal expansion coefficient of 50 to 250 ° C. was determined. In the case of glass alone, the temperature at which the maximum length of the thermal expansion curve was reached was defined as the softening point (Td).
(3) Weather resistance (time)
A sample obtained by mirror polishing the obtained glass block to a thickness of 0.3 to 0.5 mm is held in a constant temperature and humidity chamber at about 60 ° C. and 95% relative humidity, and the surface state is observed at regular intervals. Then, the glass surface was cloudy, and the evaluation was based on the time when the spots were observed.
(4) Flow temperature (° C)
Glass powder and refractory filler are mixed at a predetermined ratio, and the mixed powder is press-molded so as to be a rod having a diameter of about 10 mm and a length of 12 to 15 mm. This rod is placed on an alumina plate and raised to a predetermined temperature. The temperature when the rod was deformed and bent and fell on the alumina plate was defined as the flow temperature.
実施例１〜４１及び比較例１、２の測定結果を表１〜表６に示す。
なお表１に示すように、耐候性（時間）は実施例１と比較例１、２において測定した。
また表５〜表６に示すように、実施例２７〜２９は実施例１のガラス粉末に、実施例３０〜４１は実施例１３のガラス粉末に、それぞれ耐火物フィラーを混合した例で、フロー試験を行い、封着材料としてのフロー温度（℃）及び熱膨張係数（α）を測定している。
The measurement results of Examples 1 to 41 and Comparative Examples 1 and 2 are shown in Tables 1 to 6.
As shown in Table 1, weather resistance (time) was measured in Example 1 and Comparative Examples 1 and 2.
As shown in Tables 5 to 6, Examples 27 to 29 are examples in which refractory fillers are mixed with the glass powder of Example 1 and Examples 30 to 41 are mixed with the glass powder of Example 13, respectively. A test is conducted to measure the flow temperature (° C.) and the thermal expansion coefficient (α) as a sealing material.
実施例１では耐候性が２８８時間で、比較例１では耐候性が９６時間、比較例２では耐候性が１４４時間であって、本発明の組成でＰ２Ｏ５−ＺｎＯ系ガラスに比べて耐候性が十分に向上していることが判る。
また本発明の実施例では、転移温度（Ｔｇ）、軟化点（Ｔｄ）が低く、熱膨張係数（α５０−２５０）が小さくて低く、比較例１、２のＰ２Ｏ５−ＺｎＯ系ガラスと同程度であることが判る。
また耐火物フィラーを混合した実施例２７〜４１において、フロー温度が低く、熱膨張係数が小さく、封着材料に適していることが判る。
In Example 1, the weather resistance was 288 hours, in Comparative Example 1, the weather resistance was 96 hours, in Comparative Example 2, the weather resistance was 144 hours, and compared with the P 2 O 5 —ZnO-based glass in the composition of the present invention. It can be seen that the weather resistance is sufficiently improved.
In the examples of the present invention, the transition temperature (Tg) and the softening point (Td) are low, the thermal expansion coefficient (α50-250) is small and low, and the P 2 O 5 —ZnO-based glasses of Comparative Examples 1 and 2 It turns out that it is comparable.
Moreover, in Examples 27-41 which mixed the refractory filler, it turns out that a flow temperature is low and a thermal expansion coefficient is small, and it is suitable for a sealing material.
Claims (5)
Ｐ２Ｏ５ ：２０〜５０重量％
Ｓｂ２Ｏ３ ：２０〜７０重量％
Ａｌ２Ｏ３ ：０．３〜５重量％
ＭｇＯ ：０．５〜１５重量％
ＺｒＯ２、ＴｉＯ２の少なくとも１種：０．５〜５重量％
ＣａＯ、ＳｒＯ、ＢａＯ、ＺｎＯ、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏの少なくとも１種
：２〜３０重量％
を含有することを特徴とするアンチモンリン酸塩系ガラス組成物。 Used as glass for sealing, lead-free as a component,
P 2 O 5 : 20 to 50% by weight
Sb 2 O 3: 20~70 weight%
Al 2 O 3 : 0.3 to 5% by weight
MgO: 0.5 to 15% by weight
At least one of ZrO 2 and TiO 2 : 0.5 to 5% by weight
At least one of CaO, SrO, BaO, ZnO, Li 2 O, Na 2 O, K 2 O
: 2 to 30% by weight
An antimony phosphate glass composition comprising:
Ｓｂ２Ｏ３ ：４０〜６０重量％
Ａｌ２Ｏ３ ：０．３〜３重量％
ＭｇＯ ：０．５〜５重量％
ＺｒＯ２、ＴｉＯ２の少なくとも１種：０．５〜３重量％
ＣａＯ、ＳｒＯ、ＢａＯ、ＺｎＯ、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏの少なくとも１種
：５〜２０重量％
を含有することを特徴とする請求項１に記載のアンチモンリン酸塩系ガラス組成物。 P 2 O 5: 20~40 weight%
Sb 2 O 3 : 40 to 60% by weight
Al 2 O 3 : 0.3 to 3 % by weight
MgO: 0.5 to 5% by weight
At least one of ZrO 2 and TiO 2 : 0.5 to 3% by weight
At least one of CaO, SrO, BaO, ZnO, Li 2 O, Na 2 O, K 2 O
: 5 to 20% by weight
The antimony phosphate glass composition according to claim 1, comprising:
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