WO2010013692A1 - Lead-free glass composition - Google Patents
Lead-free glass composition Download PDFInfo
- Publication number
- WO2010013692A1 WO2010013692A1 PCT/JP2009/063388 JP2009063388W WO2010013692A1 WO 2010013692 A1 WO2010013692 A1 WO 2010013692A1 JP 2009063388 W JP2009063388 W JP 2009063388W WO 2010013692 A1 WO2010013692 A1 WO 2010013692A1
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- WO
- WIPO (PCT)
- Prior art keywords
- lead
- glass
- free glass
- glass composition
- component
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2207/00—Compositions specially applicable for the manufacture of vitreous enamels
- C03C2207/08—Compositions specially applicable for the manufacture of vitreous enamels for light metals
Definitions
- the present invention relates to a lead-free glass composition.
- Glass and ceramics are usually used as an insulating material in electronic parts that require high reliability because they are less susceptible to thermal deterioration and have better electrical insulation than synthetic resins.
- glass is used for coating metal members and bonding metal members. Moreover, it is used also for uses, such as sealing of the opening part of metal members.
- glass in such applications is required to have a softening point and a thermal expansion coefficient according to the application, and to be excellent in chemical durability such as acid resistance and alkali resistance, and electrical insulation.
- the thermal expansion coefficient it is required to show a high value in consideration of firing on a metal material such as copper, copper alloy, aluminum, and aluminum alloy.
- Patent Document 1 describes a PbO-containing glass characterized by a thermal expansion coefficient in the range of 30 to 300 ° C. of 125 to 140 ⁇ 10 ⁇ 7 / ° C.
- environmental problems have been pointed out in recent years for lead, and there is an increasing demand for lead-free glass compositions that do not substantially contain lead.
- Patent Document 2 Bi 2 O 3 is used as a main component instead of PbO, and a large amount of an alkali metal oxide such as Li 2 O, Na 2 O, K 2 O or the like is contained therein.
- a glass composition for a magnetic head is described.
- the glass composition described here contains only alkali metal oxides such as Li 2 O, Na 2 O and K 2 O as components other than glass formers such as Bi 2 O 3 and SiO 2.
- Patent Document 3 listed below describes a bismuth-based glass composition suitable for bonding, sealing, coating, and the like of electronic components.
- this patent document 3 aims to provide a glass that does not have a risk of lowering electrical insulation. And the glass comprised from the composition specifically described in this patent document 3 has a low thermal expansion coefficient. Thus, a glass composition useful for forming a glass that does not contain lead and has a low softening point and has both excellent chemical durability and a high thermal expansion coefficient has not been found.
- an object of the present invention is to provide a lead-free glass composition capable of forming a glass having a high thermal expansion coefficient and excellent chemical durability while having a low softening point.
- the present inventors have found that a predetermined amount of a predetermined substance is contained as a glass component of the lead-free glass composition, and a high thermal expansion coefficient while having a low softening point. It has been found that a glass having excellent chemical durability can be formed, and the present invention has been completed. That is, according to the present invention, Bi 2 O 3 : 30 to 62%, SiO 2 : 10 to 35%, Al 2 O 3 : 0.1 to 5%, B 2 O 3 : 0.1 to 4.% by weight. 5% and TiO 2 : 0.1 to 8%, and a glass component containing a total of 10 to 25% of any one or more of Li 2 O, Na 2 O and K 2 O is included. A lead-free glass composition is provided.
- the lead-free glass composition of the present invention can form a glass having a high thermal expansion coefficient and excellent chemical durability while having a low softening point.
- the lead-free glass composition in this embodiment contains a glass component and an inorganic filler component.
- the glass component is a component for forming a portion that is normally in a glass state when lead-free glass is formed with the lead-free glass composition of the present embodiment, and the inorganic filler component is contained in the lead-free glass. Usually, it is a component contained in a crystallized state. Therefore, in the lead-free glass in which the lead-free glass composition of the present embodiment is used, the inorganic filler component is usually observed in a state of being dispersed in the form of a matrix composed of the glass component.
- the glass component contains Bi 2 O 3 , SiO 2 , Al 2 O 3 , B 2 O 3 , and TiO 2 as essential components. Further, Li 2 O, is contained in the glass component as also essential ingredient any one or more of Na 2 O and K 2 O.
- ZnO, BaO, MgO, CaO, SrO, ZrO 2 , SeO 2 , CeO 2 , Fe 2 O 3 , MnO 2 , CuO, CoO, SnO 2 , Sb 2 O 3 , V 2 O 5 , NiO, Cr 2 O 3 , TeO 2 and the like can be contained as optional components. These optional components can be contained in the glass component as long as the effects of the present invention are not significantly impaired by the addition thereof.
- Bi 2 O 3 is an effective component for making the lead-free glass composition of the present embodiment have a low softening point, and the content of the glass component in any one of the range of 30 to 62% by weight. It is taken.
- the content of Bi 2 O 3 in the glass component is any one of the above ranges. For example, if the content is less than 30%, the softening point of the lead-free glass composition increases, and the metal member This is because there is a possibility that it may be necessary to perform baking at a temperature exceeding 580 ° C., for example, in the case where it is necessary to perform baking on the substrate. That is, if firing at such a temperature is necessary, it is difficult to use an aluminum member as the metal member, which places great restrictions on the method of use.
- the content of Bi 2 O 3 in the glass component is 62% or less. If the content exceeds 62%, even if the softening point can be sufficiently reduced, for example, This is because it may be difficult to set the coefficient of thermal expansion of the glass formed by this glass component to a high value of, for example, 140 ⁇ 10 ⁇ 7 / ° C. or higher. That is, the content of Bi 2 O 3 in the glass component is 62% or less, for example, to prevent distortion from occurring during firing on a metal member.
- the content of Bi 2 O 3 in the glass component is preferably in the range of 30 to 62%, and in the range of 42 to 60%. Is more preferable.
- “thermal expansion coefficient” means an average value in the range of 50 to 250 ° C. unless otherwise specified.
- the SiO 2 is an effective component for stabilizing the formation of the glass state, and the content of the SiO 2 in the glass component is any one of 10 to 35% by weight.
- the content of SiO 2 in the glass component is any of the above ranges. For example, when the content is less than 10%, it is difficult to impart sufficient chemical durability to the lead-free glass composition. If it exceeds 35%, the firing temperature of the lead-free glass composition may exceed 580 ° C.
- the content of SiO 2 in the glass component is preferably in the range of 15 to 30%, more preferably in the range of 16 to 25%. preferable.
- the contents of Bi 2 O 3 and SiO 2 are preferably selected so that the total amount is in the range of 55 to 80% by weight. If the total amount is less than 55%, the glass becomes unstable and the chemical durability may be lowered. In this respect, the total amount of Bi 2 O 3 and SiO 2 is preferably in the range of 60 to 78%, and preferably in the range of 65 to 75%. Further preferred.
- the Al 2 O 3 is an effective component for stabilizing the formation of the glass state and making the lead-free glass composition excellent in chemical durability, and the content in the glass component is 0% by weight. .1 to 5%.
- the content of Al 2 O 3 in the glass component is any of the above ranges. For example, when the content is less than 0.1%, sufficient chemical durability is imparted to the lead-free glass composition. This is because it is difficult to do so, and if it exceeds 5%, the glass component may be destabilized, such as devitrification. Furthermore, when it exceeds 5%, the firing temperature of the lead-free glass composition may exceed 580 ° C.
- the content of Al 2 O 3 in the glass component is preferably in the range of 0.1 to 5%. Furthermore, 0.1 to 3.0% is preferable.
- the B 2 O 3 is an effective component for stabilizing the formation of the glass state and making the lead-free glass composition have a low softening point, and the content of the B 2 O 3 in the glass component is 0.1 to 4.% by weight.
- One of the ranges of 5% is used.
- the content of B 2 O 3 in the glass component is any of the above ranges because, for example, if the content is less than 0.1%, the stability in the glass state such as devitrification is reduced. This is because if the content exceeds 4.5%, it may be difficult to impart sufficient chemical durability to the lead-free glass composition.
- the content of B 2 O 3 in the glass component is preferably in the range of 2.5 to 3.7%. Furthermore, 3.0 to 3.6% is preferable.
- the TiO 2 is an effective component for making the lead-free glass composition excellent in chemical durability, and the content of the TiO 2 in the glass component is any one in the range of 0.1 to 8% by weight. It is taken.
- the content of TiO 2 in the glass component is set to any of the above ranges, for example, when the content is less than 0.1%, sufficient chemical durability is imparted to the lead-free glass composition. This is because it is difficult to cause crystallization when the content exceeds 8%.
- the content of TiO 2 in the glass component is preferably in the range of 1 to 8%, and is in the range of 1.1 to 8%. Is more preferable.
- any one or more of Li 2 O, Na 2 O and K 2 O are effective components for lowering the softening point of the lead-free glass composition as described above, and in the lead-free glass composition, It is an effective component for imparting a high thermal expansion coefficient.
- the total content of the glass components is usually in the range of 10 to 25% by weight percentage. In addition, these components should just contain any 1 type in them, and 2 types or all 3 types may contain them. The total content of these is considered to be any of the above ranges, for example, if the total content is less than 10%, the firing temperature of the lead-free glass composition may exceed 580 ° C., and exceeds 25%. This is because it may be difficult to impart sufficient chemical durability to the lead-free glass composition. In this respect, it is preferable that the total content of any one or more of Li 2 O, Na 2 O, and K 2 O is in the range of 15 to 20%.
- ZnO is an effective component for making the lead-free glass composition have a low softening point, and even if it is contained in a glass component at a content of 10% or less by weight, There is little risk of significantly impairing the effects of the invention.
- the content exceeds 10%, the glass component may be crystallized.
- the content is preferably in the range of 2 to 6%.
- BaO is an effective component for imparting a high thermal expansion coefficient to the lead-free glass composition, and is usually contained in the glass component at a content of 15% or less by weight.
- the content is preferably 10% or less, more preferably 6% or less.
- alkaline earth metal oxides other than BaO are effective components for stabilizing the formation of the glass state and effective for lowering the softening point of the lead-free glass composition.
- the effect of the present invention is not significantly impaired.
- the softening point of the lead-free glass composition may be increased, and firing at 580 ° C. or less may be difficult, and the glass component may become unstable in a glass state. There is also a risk that
- ZrO 2 is an effective component for adjusting the viscosity and thermal expansion coefficient during softening of the lead-free glass composition, and is usually contained in the glass component in an amount of 5% or less by weight.
- the content exceeds 5%, the glass component may be crystallized.
- SeO 2 , CeO 2 , Fe 2 O 3 , MnO 2 , CuO, CoO, SnO 2 , Sb 2 O 3 , V 2 O 5 , NiO, Cr 2 O 3 , TeO 2 and the like are Even if the total content is contained in the glass component in an amount of 2% or less by weight percentage, the effect of the present invention is not significantly impaired.
- the lead-free glass composition of the present invention is composed of each component.
- the composition include a) Bi 2 O 3 : 42 to 60% by weight as composition X, and b) SiO 2 : 16 to 25% by weight, c) Al 2 O 3 : 0.1 to 5% by weight, d) B 2 O 3 : 3 to 3.6% by weight, e) TiO 2 : 1.1 to 8% by weight, f ) Na 2 O: 5.0 ⁇ 10% by weight, and g) K 2 O: 5.0 include compositions containing ⁇ 10 wt%.
- composition A a) Bi 2 O 3 : 42 to 45% by weight, b) SiO 2 : 22 to 25% by weight, c) Al 2 O 3 : 0.1 to 1% by weight, d) B 2 O 3: 3 ⁇ 3.6 wt%, e) TiO 2: 5 ⁇ 8 wt%, f) Na 2 O: 7.0 ⁇ 10 wt%, g) K 2 O: 8.0 ⁇ 10 weight %) And h) a composition containing 4 to 6% by weight of BaO, or composition B: a) Bi 2 O 3 : 50 to 58% by weight, b) SiO 2 : 20 to 23% by weight, c) Al 2 O 3 D) B 2 O 3 : 3 to 3.6 wt%, e) TiO 2 : 5.1 to 8 wt%, f) Na 2 O: 5.0 to 10 wt% And g) K 2 O: A composition containing 5.0 to 10% by weight can be exemplified
- composition X, composition A, and composition B are particularly preferable in terms of water resistance, acid resistance, and thermal expansion coefficient.
- the lead-free glass composition of the present embodiment is substantially composed of only the substances specifically mentioned in the above-mentioned composition X, composition A, composition B and the like. It is preferable in that it can provide a high thermal expansion coefficient.
- the lead-free glass composition in the present embodiment contains at least one of TiO 2 , Al 2 O 3 , SiO 2 , ZrO 2 , MgO, CaF, and BaF as the inorganic filler component.
- These inorganic filler components are usually contained in the lead-free glass composition as a granular material, for example, TiO 2 particles, Al 2 O 3 particles, SiO 2 particles, ZrO 2 particles, MgO particles, CaF particles, and BaF.
- the lead-free glass composition may contain inorganic particles such as particles.
- the inorganic filler component can be contained in the form of inorganic particles, and the lead-free glass composition of the present embodiment is, for example, a mixture of glass particles (powder glass) composed of the glass components and the inorganic particles. Can be formed.
- the inorganic filler component usually, inorganic particles having an average particle diameter (D 50 ) of 0.3 to 3.0 ⁇ m can be used.
- D 50 average particle diameter
- the ratio of the inorganic filler component to the total amount of this inorganic filler component and the said glass component is 20% or less by weight percentage.
- the lead-free glass composition of the present embodiment is used for the formation of a glass film, and when an acidic or alkaline liquid is contacted with the surface, a part of the glass component is dissolved in the liquid and the surface side Even when eroded, the inorganic particles function to protect the inner side. That is, since the lead-free glass composition of the present embodiment contains such an inorganic filler component in addition to the glass component, chemical stability is further improved. Moreover, the said inorganic filler component can also be made to act as an extender, and is useful also for adjustment of the color tone of a lead-free glass composition.
- the lead-free glass composition of the present embodiment has high chemical stability, the effect of the lead-free glass composition is more prominent when used to form the surface of a member subjected to a plating process, an etching process, or the like. Can do. Moreover, since it has a high thermal expansion coefficient, it can be suitably used not only for applications covering metal members, but also for applications such as adhesion between metal members and sealing of metal members. Moreover, since it has a low softening point, it can be fired at 580 ° C. or lower, and can be suitably used particularly in the above applications of aluminum and aluminum alloy members.
- the lead-free glass composition in the present embodiment is excellent in chemical stability, it can be said that the lead-free glass composition is suitable for a covering material for these members.
- the effect excellent also in the compounding use to conductor paste and resistor paste, such as Ag and Al, can be exhibited. Furthermore, it can be suitably used not only for metal members but also for sealing high-expansion ceramic members and for surface coating of high-expansion ceramic members. Moreover, it can be used suitably also for the adhesive use of the members made from high expansion ceramics, or the high expansion ceramics and metal members.
- the lead-free glass composition of this embodiment can be made into various forms in addition to the powder state containing glass particles and inorganic particles. Further, in the present embodiment, the lead-free glass composition is described by exemplifying the case where the glass component and the inorganic filler component are included. However, the lead-free glass composition including only the glass component exemplified above is also the intent of the present invention. It is the range to do.
- ⁇ Preparation of lead-free glass composition The blended raw materials were prepared so as to have the compositions shown in Tables 1 to 3, and after mixing, they were melted at a temperature of about 1000 to 1200 ° C. for 1 to 2 hours using a platinum crucible. The molten glass was quenched with a stainless steel cooling roll to produce glass flakes composed of a lead-free glass composition. The obtained glass flakes were further pulverized and classified by airflow, adjusted to become powdered glass having an average particle size (D 50 ) of 0.5 to 2.0 ⁇ m, and subjected to each evaluation. Further, based on the lead-free glass composition of Example 1 in Table 1 and Example 16 of Table 2, the lead-free glass compositions of Examples 9 to 13 and Examples 18 to 21 further containing an inorganic filler component were produced. did.
- a powder sample using the lead-free glass composition of each example and comparative example was used as a sample for differential thermal analysis (DTA).
- the powdery sample was press-molded and fired at (softening point + 50 ° C.) for 15 minutes, and then a rod-shaped sample having a diameter of 5 mm ⁇ length of 15 to 20 mm was prepared and used as a sample for measuring a thermal expansion coefficient. Further, the powder sample was fired to prepare a block sample having a height of 5 mm, a width of 10 mm, and a length of 15 mm, and used as a sample for evaluating chemical stability (water resistance, acid resistance).
- the lead-free glass composition of the present invention can form a glass having a high thermal expansion coefficient and excellent chemical durability while having a low softening point.
Abstract
Disclosed is a lead-free glass composition capable of forming glass that, while having a low softening point, also has a high coefficient of thermal expansion and excellent chemical durability, the lead-free glass composition including 30-62% Bi2O3, 10-35% SiO2, 0.1-5% Al2O3, 0.1-4.5% B2O3, and 0.1-8% TiO2 by weight as well as a glass component containing a total of 10-25% by weight of one or more of Li2O, Na2O, or K2O.
Description
本発明は、無鉛ガラス組成物に関する。
The present invention relates to a lead-free glass composition.
ガラスやセラミックスなどは、合成樹脂などに比べて、通常、熱劣化が少なく、電気絶縁性に優れていることから、高い信頼性の要求される電子部品における絶縁材として用いられたりしている。
この電子部品のような分野においては、ガラスは、金属製の部材に対する被覆や、金属製部材どうしの接着などに用いられている。
また、金属製部材の開口部の封着などの用途にも用いられている。
一般に、このような用途におけるガラスには、用途に応じた軟化点、熱膨張係数を有するとともに耐酸性や耐アルカリ性といった化学的耐久性や、電気絶縁性などに優れていることが要求される。特に、熱膨張係数に関しては、例えば銅、銅合金、アルミニウム、アルミニウム合金などの金属材料上での焼成を考慮して高い値を示すことが求められている。
従来、化学的耐久性に優れた低軟化点ガラスとして一般的に鉛含有ガラスが広く用いられている。例えば、下記特許文献１には、３０～３００℃の範囲における熱膨張係数が１２５～１４０×１０－７／℃であることを特徴とするＰｂＯ含有ガラスが記載されている。
しかしながら鉛に対しては、近年、環境上の問題が指摘されており、鉛を実質的に含有してない無鉛ガラス組成物に対する要望が高まっている。 Glass and ceramics are usually used as an insulating material in electronic parts that require high reliability because they are less susceptible to thermal deterioration and have better electrical insulation than synthetic resins.
In the field of electronic parts, glass is used for coating metal members and bonding metal members.
Moreover, it is used also for uses, such as sealing of the opening part of metal members.
In general, glass in such applications is required to have a softening point and a thermal expansion coefficient according to the application, and to be excellent in chemical durability such as acid resistance and alkali resistance, and electrical insulation. In particular, regarding the thermal expansion coefficient, it is required to show a high value in consideration of firing on a metal material such as copper, copper alloy, aluminum, and aluminum alloy.
Conventionally, lead-containing glass has been widely used as a low softening point glass excellent in chemical durability. For example, Patent Document 1 described below describes a PbO-containing glass characterized by a thermal expansion coefficient in the range of 30 to 300 ° C. of 125 to 140 × 10 −7 / ° C.
However, environmental problems have been pointed out in recent years for lead, and there is an increasing demand for lead-free glass compositions that do not substantially contain lead.
この電子部品のような分野においては、ガラスは、金属製の部材に対する被覆や、金属製部材どうしの接着などに用いられている。
また、金属製部材の開口部の封着などの用途にも用いられている。
一般に、このような用途におけるガラスには、用途に応じた軟化点、熱膨張係数を有するとともに耐酸性や耐アルカリ性といった化学的耐久性や、電気絶縁性などに優れていることが要求される。特に、熱膨張係数に関しては、例えば銅、銅合金、アルミニウム、アルミニウム合金などの金属材料上での焼成を考慮して高い値を示すことが求められている。
従来、化学的耐久性に優れた低軟化点ガラスとして一般的に鉛含有ガラスが広く用いられている。例えば、下記特許文献１には、３０～３００℃の範囲における熱膨張係数が１２５～１４０×１０－７／℃であることを特徴とするＰｂＯ含有ガラスが記載されている。
しかしながら鉛に対しては、近年、環境上の問題が指摘されており、鉛を実質的に含有してない無鉛ガラス組成物に対する要望が高まっている。 Glass and ceramics are usually used as an insulating material in electronic parts that require high reliability because they are less susceptible to thermal deterioration and have better electrical insulation than synthetic resins.
In the field of electronic parts, glass is used for coating metal members and bonding metal members.
Moreover, it is used also for uses, such as sealing of the opening part of metal members.
In general, glass in such applications is required to have a softening point and a thermal expansion coefficient according to the application, and to be excellent in chemical durability such as acid resistance and alkali resistance, and electrical insulation. In particular, regarding the thermal expansion coefficient, it is required to show a high value in consideration of firing on a metal material such as copper, copper alloy, aluminum, and aluminum alloy.
Conventionally, lead-containing glass has been widely used as a low softening point glass excellent in chemical durability. For example, Patent Document 1 described below describes a PbO-containing glass characterized by a thermal expansion coefficient in the range of 30 to 300 ° C. of 125 to 140 × 10 −7 / ° C.
However, environmental problems have been pointed out in recent years for lead, and there is an increasing demand for lead-free glass compositions that do not substantially contain lead.
このことに対して下記特許文献２には、ＰｂＯの代わりにＢｉ２Ｏ３を主成分とし、これにＬｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ等のアルカリ金属酸化物を多量に含有させた磁気ヘッド用のガラス組成物が記載されている。
しかしながら、ここに記載されているガラス組成物には、Ｂｉ２Ｏ３およびＳｉＯ２等のガラスフォーマー以外の成分として、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ等のアルカリ金属酸化物しか含有していないことから、高い熱膨張係数を示すと見られるものの化学的耐久性に問題を生じさせるおそれを有する。
また、下記特許文献３には、電子部品の接着、封着、被覆等に好適なビスマス系ガラス組成物が記載されている。しかし、この特許文献３は、電気絶縁性が低下するおそれが無いガラスを提供することを目的としている。
そして、この特許文献３に具体的に記載されている組成物から構成されるガラスは、その熱膨張係数が低いものである。
このように鉛を含まず、且つ低い軟化点を有しつつも、優れた化学的耐久性と高い熱膨張係数とを併せ持つガラスの形成に有用なガラス組成物は従来見出されていない。 On the other hand, in Patent Document 2 below, Bi 2 O 3 is used as a main component instead of PbO, and a large amount of an alkali metal oxide such as Li 2 O, Na 2 O, K 2 O or the like is contained therein. A glass composition for a magnetic head is described.
However, the glass composition described here contains only alkali metal oxides such as Li 2 O, Na 2 O and K 2 O as components other than glass formers such as Bi 2 O 3 and SiO 2. However, although it seems to show a high thermal expansion coefficient, it may cause a problem in chemical durability.
Patent Document 3 listed below describes a bismuth-based glass composition suitable for bonding, sealing, coating, and the like of electronic components. However, this patent document 3 aims to provide a glass that does not have a risk of lowering electrical insulation.
And the glass comprised from the composition specifically described in this patent document 3 has a low thermal expansion coefficient.
Thus, a glass composition useful for forming a glass that does not contain lead and has a low softening point and has both excellent chemical durability and a high thermal expansion coefficient has not been found.
しかしながら、ここに記載されているガラス組成物には、Ｂｉ２Ｏ３およびＳｉＯ２等のガラスフォーマー以外の成分として、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ等のアルカリ金属酸化物しか含有していないことから、高い熱膨張係数を示すと見られるものの化学的耐久性に問題を生じさせるおそれを有する。
また、下記特許文献３には、電子部品の接着、封着、被覆等に好適なビスマス系ガラス組成物が記載されている。しかし、この特許文献３は、電気絶縁性が低下するおそれが無いガラスを提供することを目的としている。
そして、この特許文献３に具体的に記載されている組成物から構成されるガラスは、その熱膨張係数が低いものである。
このように鉛を含まず、且つ低い軟化点を有しつつも、優れた化学的耐久性と高い熱膨張係数とを併せ持つガラスの形成に有用なガラス組成物は従来見出されていない。 On the other hand, in Patent Document 2 below, Bi 2 O 3 is used as a main component instead of PbO, and a large amount of an alkali metal oxide such as Li 2 O, Na 2 O, K 2 O or the like is contained therein. A glass composition for a magnetic head is described.
However, the glass composition described here contains only alkali metal oxides such as Li 2 O, Na 2 O and K 2 O as components other than glass formers such as Bi 2 O 3 and SiO 2. However, although it seems to show a high thermal expansion coefficient, it may cause a problem in chemical durability.
Patent Document 3 listed below describes a bismuth-based glass composition suitable for bonding, sealing, coating, and the like of electronic components. However, this patent document 3 aims to provide a glass that does not have a risk of lowering electrical insulation.
And the glass comprised from the composition specifically described in this patent document 3 has a low thermal expansion coefficient.
Thus, a glass composition useful for forming a glass that does not contain lead and has a low softening point and has both excellent chemical durability and a high thermal expansion coefficient has not been found.
本発明は、上記問題点に鑑み、低軟化点でありながら高い熱膨張係数と優れた化学的耐久性とを有するガラスを形成可能な無鉛ガラス組成物の提供を課題としている。
In view of the above problems, an object of the present invention is to provide a lead-free glass composition capable of forming a glass having a high thermal expansion coefficient and excellent chemical durability while having a low softening point.
本発明者らは、前記課題を解決すべく、鋭意検討を行った結果、無鉛ガラス組成物のガラス成分として所定の物質を所定量含有させることで低軟化点でありながらも高い熱膨張係数と優れた化学的耐久性とを有するガラスを形成させ得ることを見出して本発明を完成させるに至った。
すなわち、本発明は、重量百分率でＢｉ２Ｏ３：３０～６２％、ＳｉＯ２：１０～３５％、Ａｌ２Ｏ３：０．１～５％、Ｂ２Ｏ３：０．１～４．５％、及びＴｉＯ２：０．１～８％含み、さらにＬｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの何れか１種以上を合計１０～２５％含むガラス成分が含有されてなることを特徴とする無鉛ガラス組成物を提供する。 As a result of intensive studies to solve the above problems, the present inventors have found that a predetermined amount of a predetermined substance is contained as a glass component of the lead-free glass composition, and a high thermal expansion coefficient while having a low softening point. It has been found that a glass having excellent chemical durability can be formed, and the present invention has been completed.
That is, according to the present invention, Bi 2 O 3 : 30 to 62%, SiO 2 : 10 to 35%, Al 2 O 3 : 0.1 to 5%, B 2 O 3 : 0.1 to 4.% by weight. 5% and TiO 2 : 0.1 to 8%, and a glass component containing a total of 10 to 25% of any one or more of Li 2 O, Na 2 O and K 2 O is included. A lead-free glass composition is provided.
すなわち、本発明は、重量百分率でＢｉ２Ｏ３：３０～６２％、ＳｉＯ２：１０～３５％、Ａｌ２Ｏ３：０．１～５％、Ｂ２Ｏ３：０．１～４．５％、及びＴｉＯ２：０．１～８％含み、さらにＬｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの何れか１種以上を合計１０～２５％含むガラス成分が含有されてなることを特徴とする無鉛ガラス組成物を提供する。 As a result of intensive studies to solve the above problems, the present inventors have found that a predetermined amount of a predetermined substance is contained as a glass component of the lead-free glass composition, and a high thermal expansion coefficient while having a low softening point. It has been found that a glass having excellent chemical durability can be formed, and the present invention has been completed.
That is, according to the present invention, Bi 2 O 3 : 30 to 62%, SiO 2 : 10 to 35%, Al 2 O 3 : 0.1 to 5%, B 2 O 3 : 0.1 to 4.% by weight. 5% and TiO 2 : 0.1 to 8%, and a glass component containing a total of 10 to 25% of any one or more of Li 2 O, Na 2 O and K 2 O is included. A lead-free glass composition is provided.
本発明の無鉛ガラス組成物は、低軟化点でありながらも高い熱膨張係数と優れた化学的耐久性とを有するガラスを形成させ得る。
The lead-free glass composition of the present invention can form a glass having a high thermal expansion coefficient and excellent chemical durability while having a low softening point.
以下に、本発明の好ましい実施の形態について説明する。
本実施形態における無鉛ガラス組成物には、ガラス成分と無機フィラー成分とが含有されている。
前記ガラス成分は、通常、本実施形態の無鉛ガラス組成物で無鉛ガラスを形成させた場合にガラス状態となっている部分を構成させるための成分であり、前記無機フィラー成分は、無鉛ガラス中に、通常、結晶化した状態で含有される成分である。
したがって、本実施形態の無鉛ガラス組成物が用いられてなる無鉛ガラスには、通常、ガラス成分からなるマトリックス中に無機フィラー成分が粒子状に分散された状態となって観察される。 The preferred embodiments of the present invention will be described below.
The lead-free glass composition in this embodiment contains a glass component and an inorganic filler component.
The glass component is a component for forming a portion that is normally in a glass state when lead-free glass is formed with the lead-free glass composition of the present embodiment, and the inorganic filler component is contained in the lead-free glass. Usually, it is a component contained in a crystallized state.
Therefore, in the lead-free glass in which the lead-free glass composition of the present embodiment is used, the inorganic filler component is usually observed in a state of being dispersed in the form of a matrix composed of the glass component.
本実施形態における無鉛ガラス組成物には、ガラス成分と無機フィラー成分とが含有されている。
前記ガラス成分は、通常、本実施形態の無鉛ガラス組成物で無鉛ガラスを形成させた場合にガラス状態となっている部分を構成させるための成分であり、前記無機フィラー成分は、無鉛ガラス中に、通常、結晶化した状態で含有される成分である。
したがって、本実施形態の無鉛ガラス組成物が用いられてなる無鉛ガラスには、通常、ガラス成分からなるマトリックス中に無機フィラー成分が粒子状に分散された状態となって観察される。 The preferred embodiments of the present invention will be described below.
The lead-free glass composition in this embodiment contains a glass component and an inorganic filler component.
The glass component is a component for forming a portion that is normally in a glass state when lead-free glass is formed with the lead-free glass composition of the present embodiment, and the inorganic filler component is contained in the lead-free glass. Usually, it is a component contained in a crystallized state.
Therefore, in the lead-free glass in which the lead-free glass composition of the present embodiment is used, the inorganic filler component is usually observed in a state of being dispersed in the form of a matrix composed of the glass component.
前記ガラス成分には、Ｂｉ２Ｏ３、ＳｉＯ２、Ａｌ２Ｏ３、Ｂ２Ｏ３、及びＴｉＯ２が必須成分として含有されている。
また、Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの何れか１種以上も必須成分としてガラス成分中に含有されている。
さらに、これらの必須成分に加えて、ＺｎＯ、ＢａＯ、ＭｇＯ、ＣａＯ、ＳｒＯ、ＺｒＯ２、ＳｅＯ２、ＣｅＯ２、Ｆｅ２Ｏ３、ＭｎＯ２、ＣｕＯ、ＣｏＯ、ＳｎＯ２、Ｓｂ２Ｏ３、Ｖ２Ｏ５、ＮｉＯ、Ｃｒ２Ｏ３、ＴｅＯ２などを任意成分として含有させることができる。
これらの任意成分は、その添加によって本発明の効果を著しく損ねない範囲において前記ガラス成分中に含有させることができる。 The glass component contains Bi 2 O 3 , SiO 2 , Al 2 O 3 , B 2 O 3 , and TiO 2 as essential components.
Further, Li 2 O, is contained in the glass component as also essential ingredient any one or more of Na 2 O and K 2 O.
In addition to these essential components, ZnO, BaO, MgO, CaO, SrO, ZrO 2 , SeO 2 , CeO 2 , Fe 2 O 3 , MnO 2 , CuO, CoO, SnO 2 , Sb 2 O 3 , V 2 O 5 , NiO, Cr 2 O 3 , TeO 2 and the like can be contained as optional components.
These optional components can be contained in the glass component as long as the effects of the present invention are not significantly impaired by the addition thereof.
また、Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの何れか１種以上も必須成分としてガラス成分中に含有されている。
さらに、これらの必須成分に加えて、ＺｎＯ、ＢａＯ、ＭｇＯ、ＣａＯ、ＳｒＯ、ＺｒＯ２、ＳｅＯ２、ＣｅＯ２、Ｆｅ２Ｏ３、ＭｎＯ２、ＣｕＯ、ＣｏＯ、ＳｎＯ２、Ｓｂ２Ｏ３、Ｖ２Ｏ５、ＮｉＯ、Ｃｒ２Ｏ３、ＴｅＯ２などを任意成分として含有させることができる。
これらの任意成分は、その添加によって本発明の効果を著しく損ねない範囲において前記ガラス成分中に含有させることができる。 The glass component contains Bi 2 O 3 , SiO 2 , Al 2 O 3 , B 2 O 3 , and TiO 2 as essential components.
Further, Li 2 O, is contained in the glass component as also essential ingredient any one or more of Na 2 O and K 2 O.
In addition to these essential components, ZnO, BaO, MgO, CaO, SrO, ZrO 2 , SeO 2 , CeO 2 , Fe 2 O 3 , MnO 2 , CuO, CoO, SnO 2 , Sb 2 O 3 , V 2 O 5 , NiO, Cr 2 O 3 , TeO 2 and the like can be contained as optional components.
These optional components can be contained in the glass component as long as the effects of the present invention are not significantly impaired by the addition thereof.
前記Ｂｉ２Ｏ３は、本実施形態の無鉛ガラス組成物を低軟化点とするために有効な成分であり、ガラス成分に占める含有量は、重量百分率で３０～６２％の範囲の内の何れかとされる。
Ｂｉ２Ｏ３のガラス成分に占める含有量が上記範囲の内の何れかとされるのは、例えば、その含有量が３０％未満では、無鉛ガラス組成物の軟化点が上昇し、金属製の部材の上で焼成しなければならない場合などにおいて、５８０℃を超える温度で焼成する必要が生じるおそれを有するためである。
すなわち、このような温度での焼成が必要になると、前記金属製部材としてアルミニウム製の部材を用いることが困難となるなどその使用方法に大きな制約が加えられるためである。
一方で、Ｂｉ２Ｏ３のガラス成分に占める含有量が６２％以下とされているのは、６２％を超える含有量とされた場合には、軟化点を十分低減できたとしても、例えば、このガラス成分によって形成されるガラスの熱膨張係数を、例えば、１４０×１０－７／℃以上の高い値とすることが困難となるおそれを有するためである。
すなわち、Ｂｉ２Ｏ３のガラス成分に占める含有量が６２％以下とされているのは、例えば、金属製部材上での焼成時に歪が生じることを防止するためである。
このような点において、Ｂｉ２Ｏ３のガラス成分に占める含有量は、３０～６２％の範囲の内の何れかであることが好ましく、４２～６０％の範囲の内の何れかであることがさらに好ましい。なお、本明細書中における“熱膨張係数”は、特段の記載がない限りにおいては５０～２５０℃の範囲における平均値を意味する。 Bi 2 O 3 is an effective component for making the lead-free glass composition of the present embodiment have a low softening point, and the content of the glass component in any one of the range of 30 to 62% by weight. It is taken.
The content of Bi 2 O 3 in the glass component is any one of the above ranges. For example, if the content is less than 30%, the softening point of the lead-free glass composition increases, and the metal member This is because there is a possibility that it may be necessary to perform baking at a temperature exceeding 580 ° C., for example, in the case where it is necessary to perform baking on the substrate.
That is, if firing at such a temperature is necessary, it is difficult to use an aluminum member as the metal member, which places great restrictions on the method of use.
On the other hand, the content of Bi 2 O 3 in the glass component is 62% or less. If the content exceeds 62%, even if the softening point can be sufficiently reduced, for example, This is because it may be difficult to set the coefficient of thermal expansion of the glass formed by this glass component to a high value of, for example, 140 × 10 −7 / ° C. or higher.
That is, the content of Bi 2 O 3 in the glass component is 62% or less, for example, to prevent distortion from occurring during firing on a metal member.
In this respect, the content of Bi 2 O 3 in the glass component is preferably in the range of 30 to 62%, and in the range of 42 to 60%. Is more preferable. In the present specification, “thermal expansion coefficient” means an average value in the range of 50 to 250 ° C. unless otherwise specified.
Ｂｉ２Ｏ３のガラス成分に占める含有量が上記範囲の内の何れかとされるのは、例えば、その含有量が３０％未満では、無鉛ガラス組成物の軟化点が上昇し、金属製の部材の上で焼成しなければならない場合などにおいて、５８０℃を超える温度で焼成する必要が生じるおそれを有するためである。
すなわち、このような温度での焼成が必要になると、前記金属製部材としてアルミニウム製の部材を用いることが困難となるなどその使用方法に大きな制約が加えられるためである。
一方で、Ｂｉ２Ｏ３のガラス成分に占める含有量が６２％以下とされているのは、６２％を超える含有量とされた場合には、軟化点を十分低減できたとしても、例えば、このガラス成分によって形成されるガラスの熱膨張係数を、例えば、１４０×１０－７／℃以上の高い値とすることが困難となるおそれを有するためである。
すなわち、Ｂｉ２Ｏ３のガラス成分に占める含有量が６２％以下とされているのは、例えば、金属製部材上での焼成時に歪が生じることを防止するためである。
このような点において、Ｂｉ２Ｏ３のガラス成分に占める含有量は、３０～６２％の範囲の内の何れかであることが好ましく、４２～６０％の範囲の内の何れかであることがさらに好ましい。なお、本明細書中における“熱膨張係数”は、特段の記載がない限りにおいては５０～２５０℃の範囲における平均値を意味する。 Bi 2 O 3 is an effective component for making the lead-free glass composition of the present embodiment have a low softening point, and the content of the glass component in any one of the range of 30 to 62% by weight. It is taken.
The content of Bi 2 O 3 in the glass component is any one of the above ranges. For example, if the content is less than 30%, the softening point of the lead-free glass composition increases, and the metal member This is because there is a possibility that it may be necessary to perform baking at a temperature exceeding 580 ° C., for example, in the case where it is necessary to perform baking on the substrate.
That is, if firing at such a temperature is necessary, it is difficult to use an aluminum member as the metal member, which places great restrictions on the method of use.
On the other hand, the content of Bi 2 O 3 in the glass component is 62% or less. If the content exceeds 62%, even if the softening point can be sufficiently reduced, for example, This is because it may be difficult to set the coefficient of thermal expansion of the glass formed by this glass component to a high value of, for example, 140 × 10 −7 / ° C. or higher.
That is, the content of Bi 2 O 3 in the glass component is 62% or less, for example, to prevent distortion from occurring during firing on a metal member.
In this respect, the content of Bi 2 O 3 in the glass component is preferably in the range of 30 to 62%, and in the range of 42 to 60%. Is more preferable. In the present specification, “thermal expansion coefficient” means an average value in the range of 50 to 250 ° C. unless otherwise specified.
前記ＳｉＯ２は、ガラス状態の形成を安定化させるために有効な成分でありガラス成分に占める含有量は、重量百分率で１０～３５％の範囲の内の何れかとされる。
ＳｉＯ２のガラス成分に占める含有量が上記範囲の内の何れかとされるのは、例えば、その含有量が１０％未満では、無鉛ガラス組成物に十分な化学的耐久性を付与することが困難となり、３５％を超えると無鉛ガラス組成物の焼成温度が５８０℃を超えるおそれがあるためである。
このような点において、ＳｉＯ２のガラス成分に占める含有量は、１５～３０％の範囲の内の何れかであることが好ましく、１６～２５％の範囲の内の何れかであることがさらに好ましい。 The SiO 2 is an effective component for stabilizing the formation of the glass state, and the content of the SiO 2 in the glass component is any one of 10 to 35% by weight.
The content of SiO 2 in the glass component is any of the above ranges. For example, when the content is less than 10%, it is difficult to impart sufficient chemical durability to the lead-free glass composition. If it exceeds 35%, the firing temperature of the lead-free glass composition may exceed 580 ° C.
In this respect, the content of SiO 2 in the glass component is preferably in the range of 15 to 30%, more preferably in the range of 16 to 25%. preferable.
ＳｉＯ２のガラス成分に占める含有量が上記範囲の内の何れかとされるのは、例えば、その含有量が１０％未満では、無鉛ガラス組成物に十分な化学的耐久性を付与することが困難となり、３５％を超えると無鉛ガラス組成物の焼成温度が５８０℃を超えるおそれがあるためである。
このような点において、ＳｉＯ２のガラス成分に占める含有量は、１５～３０％の範囲の内の何れかであることが好ましく、１６～２５％の範囲の内の何れかであることがさらに好ましい。 The SiO 2 is an effective component for stabilizing the formation of the glass state, and the content of the SiO 2 in the glass component is any one of 10 to 35% by weight.
The content of SiO 2 in the glass component is any of the above ranges. For example, when the content is less than 10%, it is difficult to impart sufficient chemical durability to the lead-free glass composition. If it exceeds 35%, the firing temperature of the lead-free glass composition may exceed 580 ° C.
In this respect, the content of SiO 2 in the glass component is preferably in the range of 15 to 30%, more preferably in the range of 16 to 25%. preferable.
なお、このＢｉ２Ｏ３とＳｉＯ２とは、その合計量が、重量百分率で５５～８０％の範囲の内の何れかとなるようにそれぞれの含有量が選択されることが好ましい。
なお、これらの合計量が５５％未満では、ガラスとして不安定になり、化学的耐久性も低下させるおそれを有する。
このような点においてＢｉ２Ｏ３とＳｉＯ２との合計量は、６０～７８％の範囲の内の何れかであることが好ましく、６５～７５％の範囲の内の何れかであることがさらに好ましい。 The contents of Bi 2 O 3 and SiO 2 are preferably selected so that the total amount is in the range of 55 to 80% by weight.
If the total amount is less than 55%, the glass becomes unstable and the chemical durability may be lowered.
In this respect, the total amount of Bi 2 O 3 and SiO 2 is preferably in the range of 60 to 78%, and preferably in the range of 65 to 75%. Further preferred.
なお、これらの合計量が５５％未満では、ガラスとして不安定になり、化学的耐久性も低下させるおそれを有する。
このような点においてＢｉ２Ｏ３とＳｉＯ２との合計量は、６０～７８％の範囲の内の何れかであることが好ましく、６５～７５％の範囲の内の何れかであることがさらに好ましい。 The contents of Bi 2 O 3 and SiO 2 are preferably selected so that the total amount is in the range of 55 to 80% by weight.
If the total amount is less than 55%, the glass becomes unstable and the chemical durability may be lowered.
In this respect, the total amount of Bi 2 O 3 and SiO 2 is preferably in the range of 60 to 78%, and preferably in the range of 65 to 75%. Further preferred.
前記Ａｌ２Ｏ３は、ガラス状態の形成を安定化させるとともに無鉛ガラス組成物を化学的耐久性に優れたものとするために有効な成分でありガラス成分に占める含有量は、重量百分率で０．１～５％の範囲の内の何れかとされる。
Ａｌ２Ｏ３のガラス成分に占める含有量が上記範囲の内の何れかとされるのは、例えば、その含有量が０．１％未満では、無鉛ガラス組成物に十分な化学的耐久性を付与することが困難となり、５％を超えると、失透するなどガラス成分を不安定化させるおそれがあるためである。
さらには、５％を超えると、無鉛ガラス組成物の焼成温度が５８０℃を超えるおそれもある。
このような点において、Ａｌ２Ｏ３のガラス成分に占める含有量は、０．１～５％の範囲の内の何れかであることが好ましい。さらに０．１～３．０％が好ましい。 The Al 2 O 3 is an effective component for stabilizing the formation of the glass state and making the lead-free glass composition excellent in chemical durability, and the content in the glass component is 0% by weight. .1 to 5%.
The content of Al 2 O 3 in the glass component is any of the above ranges. For example, when the content is less than 0.1%, sufficient chemical durability is imparted to the lead-free glass composition. This is because it is difficult to do so, and if it exceeds 5%, the glass component may be destabilized, such as devitrification.
Furthermore, when it exceeds 5%, the firing temperature of the lead-free glass composition may exceed 580 ° C.
In this respect, the content of Al 2 O 3 in the glass component is preferably in the range of 0.1 to 5%. Furthermore, 0.1 to 3.0% is preferable.
Ａｌ２Ｏ３のガラス成分に占める含有量が上記範囲の内の何れかとされるのは、例えば、その含有量が０．１％未満では、無鉛ガラス組成物に十分な化学的耐久性を付与することが困難となり、５％を超えると、失透するなどガラス成分を不安定化させるおそれがあるためである。
さらには、５％を超えると、無鉛ガラス組成物の焼成温度が５８０℃を超えるおそれもある。
このような点において、Ａｌ２Ｏ３のガラス成分に占める含有量は、０．１～５％の範囲の内の何れかであることが好ましい。さらに０．１～３．０％が好ましい。 The Al 2 O 3 is an effective component for stabilizing the formation of the glass state and making the lead-free glass composition excellent in chemical durability, and the content in the glass component is 0% by weight. .1 to 5%.
The content of Al 2 O 3 in the glass component is any of the above ranges. For example, when the content is less than 0.1%, sufficient chemical durability is imparted to the lead-free glass composition. This is because it is difficult to do so, and if it exceeds 5%, the glass component may be destabilized, such as devitrification.
Furthermore, when it exceeds 5%, the firing temperature of the lead-free glass composition may exceed 580 ° C.
In this respect, the content of Al 2 O 3 in the glass component is preferably in the range of 0.1 to 5%. Furthermore, 0.1 to 3.0% is preferable.
前記Ｂ２Ｏ３は、ガラス状態の形成を安定化させるとともに無鉛ガラス組成物を低軟化点とするために有効な成分でありガラス成分に占める含有量は、重量百分率で０．１～４．５％の範囲の内の何れかとされる。
Ｂ２Ｏ３のガラス成分に占める含有量が上記範囲の内の何れかとされるのは、例えば、その含有量が０．１％未満では、失透するなどガラス状態での安定性を低下させるおそれがあり、４．５％を超える含有量とすると無鉛ガラス組成物に十分な化学的耐久性を付与することが困難となるおそれを有するためである。
このような点において、Ｂ２Ｏ３のガラス成分に占める含有量は、２．５～３．７％の範囲の内の何れかであることが好ましい。さらに３．０～３．６％が好ましい。 The B 2 O 3 is an effective component for stabilizing the formation of the glass state and making the lead-free glass composition have a low softening point, and the content of the B 2 O 3 in the glass component is 0.1 to 4.% by weight. One of the ranges of 5% is used.
The content of B 2 O 3 in the glass component is any of the above ranges because, for example, if the content is less than 0.1%, the stability in the glass state such as devitrification is reduced. This is because if the content exceeds 4.5%, it may be difficult to impart sufficient chemical durability to the lead-free glass composition.
In this respect, the content of B 2 O 3 in the glass component is preferably in the range of 2.5 to 3.7%. Furthermore, 3.0 to 3.6% is preferable.
Ｂ２Ｏ３のガラス成分に占める含有量が上記範囲の内の何れかとされるのは、例えば、その含有量が０．１％未満では、失透するなどガラス状態での安定性を低下させるおそれがあり、４．５％を超える含有量とすると無鉛ガラス組成物に十分な化学的耐久性を付与することが困難となるおそれを有するためである。
このような点において、Ｂ２Ｏ３のガラス成分に占める含有量は、２．５～３．７％の範囲の内の何れかであることが好ましい。さらに３．０～３．６％が好ましい。 The B 2 O 3 is an effective component for stabilizing the formation of the glass state and making the lead-free glass composition have a low softening point, and the content of the B 2 O 3 in the glass component is 0.1 to 4.% by weight. One of the ranges of 5% is used.
The content of B 2 O 3 in the glass component is any of the above ranges because, for example, if the content is less than 0.1%, the stability in the glass state such as devitrification is reduced. This is because if the content exceeds 4.5%, it may be difficult to impart sufficient chemical durability to the lead-free glass composition.
In this respect, the content of B 2 O 3 in the glass component is preferably in the range of 2.5 to 3.7%. Furthermore, 3.0 to 3.6% is preferable.
前記ＴｉＯ２は、無鉛ガラス組成物を化学的耐久性に優れたものとするために有効な成分でありガラス成分に占める含有量は、重量百分率で０．１～８％の範囲の内の何れかとされる。
ＴｉＯ２のガラス成分に占める含有量が上記範囲の内の何れかとされるのは、例えば、その含有量が０．１％未満では、無鉛ガラス組成物に十分な化学的耐久性を付与することが困難となり、８％を超えると、結晶化を起こしやすくなるおそれがあるためである。
このような点において、ＴｉＯ２のガラス成分に占める含有量は、１～８％の範囲の内の何れかであることが好ましく、１．１～８％の範囲の内の何れかであることがさらに好ましい。 The TiO 2 is an effective component for making the lead-free glass composition excellent in chemical durability, and the content of the TiO 2 in the glass component is any one in the range of 0.1 to 8% by weight. It is taken.
The content of TiO 2 in the glass component is set to any of the above ranges, for example, when the content is less than 0.1%, sufficient chemical durability is imparted to the lead-free glass composition. This is because it is difficult to cause crystallization when the content exceeds 8%.
In this respect, the content of TiO 2 in the glass component is preferably in the range of 1 to 8%, and is in the range of 1.1 to 8%. Is more preferable.
ＴｉＯ２のガラス成分に占める含有量が上記範囲の内の何れかとされるのは、例えば、その含有量が０．１％未満では、無鉛ガラス組成物に十分な化学的耐久性を付与することが困難となり、８％を超えると、結晶化を起こしやすくなるおそれがあるためである。
このような点において、ＴｉＯ２のガラス成分に占める含有量は、１～８％の範囲の内の何れかであることが好ましく、１．１～８％の範囲の内の何れかであることがさらに好ましい。 The TiO 2 is an effective component for making the lead-free glass composition excellent in chemical durability, and the content of the TiO 2 in the glass component is any one in the range of 0.1 to 8% by weight. It is taken.
The content of TiO 2 in the glass component is set to any of the above ranges, for example, when the content is less than 0.1%, sufficient chemical durability is imparted to the lead-free glass composition. This is because it is difficult to cause crystallization when the content exceeds 8%.
In this respect, the content of TiO 2 in the glass component is preferably in the range of 1 to 8%, and is in the range of 1.1 to 8%. Is more preferable.
Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの何れか１種以上は、先にも述べたように無鉛ガラス組成物を低軟化点化するのに有効な成分であるとともに、無鉛ガラス組成物に高い熱膨張係数を付与するために有効な成分である。
そして、ガラス成分に占めるこれらの合計含有量は、通常、重量百分率で１０～２５％の範囲の内の何れかとされる。
なお、これらの成分は、その内の何れか１種が含まれていればよく、２種又は３種全てが含有されていてもよい。
これらの合計含有量が上記範囲の内の何れかとされるのは、例えば、その合計含有量が１０％未満では、無鉛ガラス組成物の焼成温度が５８０℃を超えるおそれがあり、２５％を超えると、無鉛ガラス組成物に十分な化学的耐久性を付与することが困難となるおそれがあるためである。
このような点において、Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの何れか１種以上は、その合計含有量が、１５～２０％の範囲の内の何れかであることが好ましい。 Any one or more of Li 2 O, Na 2 O and K 2 O are effective components for lowering the softening point of the lead-free glass composition as described above, and in the lead-free glass composition, It is an effective component for imparting a high thermal expansion coefficient.
The total content of the glass components is usually in the range of 10 to 25% by weight percentage.
In addition, these components should just contain any 1 type in them, and 2 types or all 3 types may contain them.
The total content of these is considered to be any of the above ranges, for example, if the total content is less than 10%, the firing temperature of the lead-free glass composition may exceed 580 ° C., and exceeds 25%. This is because it may be difficult to impart sufficient chemical durability to the lead-free glass composition.
In this respect, it is preferable that the total content of any one or more of Li 2 O, Na 2 O, and K 2 O is in the range of 15 to 20%.
そして、ガラス成分に占めるこれらの合計含有量は、通常、重量百分率で１０～２５％の範囲の内の何れかとされる。
なお、これらの成分は、その内の何れか１種が含まれていればよく、２種又は３種全てが含有されていてもよい。
これらの合計含有量が上記範囲の内の何れかとされるのは、例えば、その合計含有量が１０％未満では、無鉛ガラス組成物の焼成温度が５８０℃を超えるおそれがあり、２５％を超えると、無鉛ガラス組成物に十分な化学的耐久性を付与することが困難となるおそれがあるためである。
このような点において、Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの何れか１種以上は、その合計含有量が、１５～２０％の範囲の内の何れかであることが好ましい。 Any one or more of Li 2 O, Na 2 O and K 2 O are effective components for lowering the softening point of the lead-free glass composition as described above, and in the lead-free glass composition, It is an effective component for imparting a high thermal expansion coefficient.
The total content of the glass components is usually in the range of 10 to 25% by weight percentage.
In addition, these components should just contain any 1 type in them, and 2 types or all 3 types may contain them.
The total content of these is considered to be any of the above ranges, for example, if the total content is less than 10%, the firing temperature of the lead-free glass composition may exceed 580 ° C., and exceeds 25%. This is because it may be difficult to impart sufficient chemical durability to the lead-free glass composition.
In this respect, it is preferable that the total content of any one or more of Li 2 O, Na 2 O, and K 2 O is in the range of 15 to 20%.
前記任意成分の内、ＺｎＯは、無鉛ガラス組成物を低軟化点とするために有効な成分であり、通常、ガラス成分中に重量百分率で１０％以下となる含有量で含有させても、本発明の効果を著しく損ねるおそれは低い。
一方で、１０％を超える含有量とするとガラス成分を結晶化させるおそれを有する。
このようなことからＺｎＯをガラス成分に含有させる場合には、その含有量が２～６％の範囲の内の何れかとすることが好ましい。 Among the optional components, ZnO is an effective component for making the lead-free glass composition have a low softening point, and even if it is contained in a glass component at a content of 10% or less by weight, There is little risk of significantly impairing the effects of the invention.
On the other hand, if the content exceeds 10%, the glass component may be crystallized.
For this reason, when ZnO is contained in the glass component, the content is preferably in the range of 2 to 6%.
一方で、１０％を超える含有量とするとガラス成分を結晶化させるおそれを有する。
このようなことからＺｎＯをガラス成分に含有させる場合には、その含有量が２～６％の範囲の内の何れかとすることが好ましい。 Among the optional components, ZnO is an effective component for making the lead-free glass composition have a low softening point, and even if it is contained in a glass component at a content of 10% or less by weight, There is little risk of significantly impairing the effects of the invention.
On the other hand, if the content exceeds 10%, the glass component may be crystallized.
For this reason, when ZnO is contained in the glass component, the content is preferably in the range of 2 to 6%.
前記任意成分の内、ＢａＯは、無鉛ガラス組成物に対して高い熱膨張係数を付与させるために有効な成分であり、通常、ガラス成分中に重量百分率で１５％以下となる含有量で含有させても、本発明の効果を著しく損ねるおそれは低い。
一方で、１５％を超える含有量とすると無鉛ガラス組成物の化学的耐久性、特に、耐酸性を大きく低下させるおそれがある。
したがって、ＢａＯをガラス成分に含有させる場合には、１０％以下の何れか、更に好ましくは６％以下の含有量とすることが好ましい。 Among the optional components, BaO is an effective component for imparting a high thermal expansion coefficient to the lead-free glass composition, and is usually contained in the glass component at a content of 15% or less by weight. However, there is a low possibility that the effects of the present invention will be significantly impaired.
On the other hand, if the content exceeds 15%, the chemical durability, particularly acid resistance, of the lead-free glass composition may be greatly reduced.
Therefore, when BaO is contained in the glass component, the content is preferably 10% or less, more preferably 6% or less.
一方で、１５％を超える含有量とすると無鉛ガラス組成物の化学的耐久性、特に、耐酸性を大きく低下させるおそれがある。
したがって、ＢａＯをガラス成分に含有させる場合には、１０％以下の何れか、更に好ましくは６％以下の含有量とすることが好ましい。 Among the optional components, BaO is an effective component for imparting a high thermal expansion coefficient to the lead-free glass composition, and is usually contained in the glass component at a content of 15% or less by weight. However, there is a low possibility that the effects of the present invention will be significantly impaired.
On the other hand, if the content exceeds 15%, the chemical durability, particularly acid resistance, of the lead-free glass composition may be greatly reduced.
Therefore, when BaO is contained in the glass component, the content is preferably 10% or less, more preferably 6% or less.
前記任意成分の内、ＭｇＯ、ＣａＯ、ＳｒＯなどのＢａＯ以外のアルカリ土類金属酸化物は、ガラス状態の形成を安定化させる効果を奏するとともに無鉛ガラス組成物の低軟化点化に有効な成分であり、通常、その合計含有量がガラス成分中に重量百分率で１０％以下となる量で含有させても、本発明の効果を著しく損ねるおそれは低い。
一方で、１０％を超える合計含有量とすると無鉛ガラス組成物の軟化点を上昇させるおそれがあり５８０℃以下での焼成を困難にさせるおそれがあるとともにガラス成分がガラス状態となるのを不安定化させるおそれもある。 Among the optional components, alkaline earth metal oxides other than BaO, such as MgO, CaO, and SrO, are effective components for stabilizing the formation of the glass state and effective for lowering the softening point of the lead-free glass composition. In general, even if the total content is 10% or less by weight in the glass component, the effect of the present invention is not significantly impaired.
On the other hand, if the total content exceeds 10%, the softening point of the lead-free glass composition may be increased, and firing at 580 ° C. or less may be difficult, and the glass component may become unstable in a glass state. There is also a risk that
一方で、１０％を超える合計含有量とすると無鉛ガラス組成物の軟化点を上昇させるおそれがあり５８０℃以下での焼成を困難にさせるおそれがあるとともにガラス成分がガラス状態となるのを不安定化させるおそれもある。 Among the optional components, alkaline earth metal oxides other than BaO, such as MgO, CaO, and SrO, are effective components for stabilizing the formation of the glass state and effective for lowering the softening point of the lead-free glass composition. In general, even if the total content is 10% or less by weight in the glass component, the effect of the present invention is not significantly impaired.
On the other hand, if the total content exceeds 10%, the softening point of the lead-free glass composition may be increased, and firing at 580 ° C. or less may be difficult, and the glass component may become unstable in a glass state. There is also a risk that
前記任意成分の内、ＺｒＯ２は、無鉛ガラス組成物の軟化時の粘性や熱膨張係数の調整に有効な成分であり、通常、ガラス成分中に重量百分率で５％以下となる量で含有させても本発明の効果を著しく損ねるおそれは低い。
一方で、５％を超える含有量とするとガラス成分を結晶化させるおそれがある。 Among the optional components, ZrO 2 is an effective component for adjusting the viscosity and thermal expansion coefficient during softening of the lead-free glass composition, and is usually contained in the glass component in an amount of 5% or less by weight. However, there is a low possibility that the effects of the present invention will be significantly impaired.
On the other hand, if the content exceeds 5%, the glass component may be crystallized.
一方で、５％を超える含有量とするとガラス成分を結晶化させるおそれがある。 Among the optional components, ZrO 2 is an effective component for adjusting the viscosity and thermal expansion coefficient during softening of the lead-free glass composition, and is usually contained in the glass component in an amount of 5% or less by weight. However, there is a low possibility that the effects of the present invention will be significantly impaired.
On the other hand, if the content exceeds 5%, the glass component may be crystallized.
さらに、前記任意成分の内、ＳｅＯ２、ＣｅＯ２、Ｆｅ２Ｏ３、ＭｎＯ２、ＣｕＯ、ＣｏＯ、ＳｎＯ２、Ｓｂ２Ｏ３、Ｖ２Ｏ５、ＮｉＯ、Ｃｒ２Ｏ３、ＴｅＯ２などは、その合計含有量が、ガラス成分中に重量百分率で２％以下となる量で含有させても本発明の効果を著しく損ねるおそれは低い。
Further, among the optional components, SeO 2 , CeO 2 , Fe 2 O 3 , MnO 2 , CuO, CoO, SnO 2 , Sb 2 O 3 , V 2 O 5 , NiO, Cr 2 O 3 , TeO 2 and the like are Even if the total content is contained in the glass component in an amount of 2% or less by weight percentage, the effect of the present invention is not significantly impaired.
なお、上記に例示の範囲内であっても、これら任意成分は、その全ての合計量が、ガラス成分中に重量百分率で２０％を超える場合には、本発明の効果を損ねるおそれが高くなることから２０％以下とされることが好ましい。
In addition, even if it is in the range illustrated above, when these total components exceed 20% by weight percentage in the glass component, there is a high possibility that the effect of the present invention will be impaired. Therefore, it is preferably 20% or less.
このように、本発明の無鉛ガラス組成物は各成分から構成されるが、具体的な組成としては、例えば、組成Ｘとしてａ）Ｂｉ２Ｏ３：４２～６０重量％、ｂ）ＳｉＯ２：１６～２５重量％、ｃ）Ａｌ２Ｏ３：０．１～５重量％、ｄ）Ｂ２Ｏ３：３～３．６重量％、ｅ）ＴｉＯ２：１．１～８重量％、ｆ)Ｎａ２Ｏ：５．０～１０重量％、及びｇ）Ｋ２Ｏ：５．０～１０重量％を含有する組成が挙げられる。
より具体的には、組成Ａとしてａ）Ｂｉ２Ｏ３：４２～４５重量％、ｂ）ＳｉＯ２：２２～２５重量％、ｃ）Ａｌ２Ｏ３：０．１～１重量％、ｄ）Ｂ２Ｏ３：３～３．６重量％、ｅ）ＴｉＯ２：５～８重量％、ｆ)Ｎａ２Ｏ：７．０～１０重量％、ｇ）Ｋ２Ｏ：８．０～１０重量％及びｈ）ＢａＯを４～６重量％含有する組成や、組成Ｂとして、ａ）Ｂｉ２Ｏ３：５０～５８重量％、ｂ）ＳｉＯ２：２０～２３重量％、ｃ）Ａｌ２Ｏ３：０．１～２重量％、ｄ）Ｂ２Ｏ３：３～３．６重量％、ｅ）ＴｉＯ２：５．１～８重量％、ｆ)Ｎａ２Ｏ：５．０～１０重量％、及びｇ）Ｋ２Ｏ：５．０～１０重量％を含有する組成が好ましい組成として例示することができる。
なお、上記組成Ｘ、組成Ａ、組成Ｂは、特に耐水性、耐酸性、熱膨張係数の点において好ましい組成である。
特に、本実施形態の無鉛ガラス組成物を、実質上、上記組成Ｘや組成Ａ、組成Ｂなどに具体的に挙げている物質のみで構成させることが、得られるガラスに優れた耐水性、耐酸性、並びに、高い熱膨張係数を付与し得る点において好適である。 Thus, the lead-free glass composition of the present invention is composed of each component. Specific examples of the composition include a) Bi 2 O 3 : 42 to 60% by weight as composition X, and b) SiO 2 : 16 to 25% by weight, c) Al 2 O 3 : 0.1 to 5% by weight, d) B 2 O 3 : 3 to 3.6% by weight, e) TiO 2 : 1.1 to 8% by weight, f ) Na 2 O: 5.0 ~ 10% by weight, and g) K 2 O: 5.0 include compositions containing ~ 10 wt%.
More specifically, as composition A, a) Bi 2 O 3 : 42 to 45% by weight, b) SiO 2 : 22 to 25% by weight, c) Al 2 O 3 : 0.1 to 1% by weight, d) B 2 O 3: 3 ~ 3.6 wt%, e) TiO 2: 5 ~ 8 wt%, f) Na 2 O: 7.0 ~ 10 wt%, g) K 2 O: 8.0 ~ 10 weight %) And h) a composition containing 4 to 6% by weight of BaO, or composition B: a) Bi 2 O 3 : 50 to 58% by weight, b) SiO 2 : 20 to 23% by weight, c) Al 2 O 3 D) B 2 O 3 : 3 to 3.6 wt%, e) TiO 2 : 5.1 to 8 wt%, f) Na 2 O: 5.0 to 10 wt% And g) K 2 O: A composition containing 5.0 to 10% by weight can be exemplified as a preferred composition.
The above composition X, composition A, and composition B are particularly preferable in terms of water resistance, acid resistance, and thermal expansion coefficient.
In particular, the lead-free glass composition of the present embodiment is substantially composed of only the substances specifically mentioned in the above-mentioned composition X, composition A, composition B and the like. It is preferable in that it can provide a high thermal expansion coefficient.
より具体的には、組成Ａとしてａ）Ｂｉ２Ｏ３：４２～４５重量％、ｂ）ＳｉＯ２：２２～２５重量％、ｃ）Ａｌ２Ｏ３：０．１～１重量％、ｄ）Ｂ２Ｏ３：３～３．６重量％、ｅ）ＴｉＯ２：５～８重量％、ｆ)Ｎａ２Ｏ：７．０～１０重量％、ｇ）Ｋ２Ｏ：８．０～１０重量％及びｈ）ＢａＯを４～６重量％含有する組成や、組成Ｂとして、ａ）Ｂｉ２Ｏ３：５０～５８重量％、ｂ）ＳｉＯ２：２０～２３重量％、ｃ）Ａｌ２Ｏ３：０．１～２重量％、ｄ）Ｂ２Ｏ３：３～３．６重量％、ｅ）ＴｉＯ２：５．１～８重量％、ｆ)Ｎａ２Ｏ：５．０～１０重量％、及びｇ）Ｋ２Ｏ：５．０～１０重量％を含有する組成が好ましい組成として例示することができる。
なお、上記組成Ｘ、組成Ａ、組成Ｂは、特に耐水性、耐酸性、熱膨張係数の点において好ましい組成である。
特に、本実施形態の無鉛ガラス組成物を、実質上、上記組成Ｘや組成Ａ、組成Ｂなどに具体的に挙げている物質のみで構成させることが、得られるガラスに優れた耐水性、耐酸性、並びに、高い熱膨張係数を付与し得る点において好適である。 Thus, the lead-free glass composition of the present invention is composed of each component. Specific examples of the composition include a) Bi 2 O 3 : 42 to 60% by weight as composition X, and b) SiO 2 : 16 to 25% by weight, c) Al 2 O 3 : 0.1 to 5% by weight, d) B 2 O 3 : 3 to 3.6% by weight, e) TiO 2 : 1.1 to 8% by weight, f ) Na 2 O: 5.0 ~ 10% by weight, and g) K 2 O: 5.0 include compositions containing ~ 10 wt%.
More specifically, as composition A, a) Bi 2 O 3 : 42 to 45% by weight, b) SiO 2 : 22 to 25% by weight, c) Al 2 O 3 : 0.1 to 1% by weight, d) B 2 O 3: 3 ~ 3.6 wt%, e) TiO 2: 5 ~ 8 wt%, f) Na 2 O: 7.0 ~ 10 wt%, g) K 2 O: 8.0 ~ 10 weight %) And h) a composition containing 4 to 6% by weight of BaO, or composition B: a) Bi 2 O 3 : 50 to 58% by weight, b) SiO 2 : 20 to 23% by weight, c) Al 2 O 3 D) B 2 O 3 : 3 to 3.6 wt%, e) TiO 2 : 5.1 to 8 wt%, f) Na 2 O: 5.0 to 10 wt% And g) K 2 O: A composition containing 5.0 to 10% by weight can be exemplified as a preferred composition.
The above composition X, composition A, and composition B are particularly preferable in terms of water resistance, acid resistance, and thermal expansion coefficient.
In particular, the lead-free glass composition of the present embodiment is substantially composed of only the substances specifically mentioned in the above-mentioned composition X, composition A, composition B and the like. It is preferable in that it can provide a high thermal expansion coefficient.
本実施形態における無鉛ガラス組成物には、前記無機フィラー成分として、ＴｉＯ２、Ａｌ２Ｏ３、ＳｉＯ２、ＺｒＯ２、ＭｇＯ、ＣａＦ、及びＢａＦの何れか１種以上が含まれている。
これらの無機フィラー成分は、通常、粒状物として無鉛ガラス組成物に含有されており、例えば、ＴｉＯ２粒子、Ａｌ２Ｏ３粒子、ＳｉＯ２粒子、ＺｒＯ２粒子、ＭｇＯ粒子、ＣａＦ粒子、及びＢａＦ粒子などの無機物粒子として無鉛ガラス組成物に含有させうる。 The lead-free glass composition in the present embodiment contains at least one of TiO 2 , Al 2 O 3 , SiO 2 , ZrO 2 , MgO, CaF, and BaF as the inorganic filler component.
These inorganic filler components are usually contained in the lead-free glass composition as a granular material, for example, TiO 2 particles, Al 2 O 3 particles, SiO 2 particles, ZrO 2 particles, MgO particles, CaF particles, and BaF. The lead-free glass composition may contain inorganic particles such as particles.
これらの無機フィラー成分は、通常、粒状物として無鉛ガラス組成物に含有されており、例えば、ＴｉＯ２粒子、Ａｌ２Ｏ３粒子、ＳｉＯ２粒子、ＺｒＯ２粒子、ＭｇＯ粒子、ＣａＦ粒子、及びＢａＦ粒子などの無機物粒子として無鉛ガラス組成物に含有させうる。 The lead-free glass composition in the present embodiment contains at least one of TiO 2 , Al 2 O 3 , SiO 2 , ZrO 2 , MgO, CaF, and BaF as the inorganic filler component.
These inorganic filler components are usually contained in the lead-free glass composition as a granular material, for example, TiO 2 particles, Al 2 O 3 particles, SiO 2 particles, ZrO 2 particles, MgO particles, CaF particles, and BaF. The lead-free glass composition may contain inorganic particles such as particles.
上記のごとく無機フィラー成分は、無機物粒子の状態で含有させることができ、本実施形態の無鉛ガラス組成物は、例えば、前記ガラス成分からなるガラス粒子（粉末ガラス）と、上記無機物粒子とを混合して形成させることができる。
この無機フィラー成分には、通常、平均粒径（Ｄ５０）が０．３～３．０μｍの無機物粒子を用いることができる。
なお、該無機フィラー成分と前記ガラス成分との合計量に占める無機フィラー成分の割合は、重量百分率で２０％以下であることが好ましい。 As described above, the inorganic filler component can be contained in the form of inorganic particles, and the lead-free glass composition of the present embodiment is, for example, a mixture of glass particles (powder glass) composed of the glass components and the inorganic particles. Can be formed.
As the inorganic filler component, usually, inorganic particles having an average particle diameter (D 50 ) of 0.3 to 3.0 μm can be used.
In addition, it is preferable that the ratio of the inorganic filler component to the total amount of this inorganic filler component and the said glass component is 20% or less by weight percentage.
この無機フィラー成分には、通常、平均粒径（Ｄ５０）が０．３～３．０μｍの無機物粒子を用いることができる。
なお、該無機フィラー成分と前記ガラス成分との合計量に占める無機フィラー成分の割合は、重量百分率で２０％以下であることが好ましい。 As described above, the inorganic filler component can be contained in the form of inorganic particles, and the lead-free glass composition of the present embodiment is, for example, a mixture of glass particles (powder glass) composed of the glass components and the inorganic particles. Can be formed.
As the inorganic filler component, usually, inorganic particles having an average particle diameter (D 50 ) of 0.3 to 3.0 μm can be used.
In addition, it is preferable that the ratio of the inorganic filler component to the total amount of this inorganic filler component and the said glass component is 20% or less by weight percentage.
本実施形態の無鉛ガラス組成物は、ガラス被膜の形成などに用いられて、その表面に酸性又はアルカリ性の液体などが接触された際において、当該液体にガラス成分の一部が溶解されて表面側から侵食を受けたとしてもこの無機物粒子がその内部側を保護すべく機能する。
すなわち、本実施形態の無鉛ガラス組成物は、このような無機フィラー成分を前記ガラス成分に加えて含有していることから化学的安定性がより向上されている。
また、前記無機フィラー成分は、体質顔料として作用させることもでき、無鉛ガラス組成物の色調の調整にも有用である。 The lead-free glass composition of the present embodiment is used for the formation of a glass film, and when an acidic or alkaline liquid is contacted with the surface, a part of the glass component is dissolved in the liquid and the surface side Even when eroded, the inorganic particles function to protect the inner side.
That is, since the lead-free glass composition of the present embodiment contains such an inorganic filler component in addition to the glass component, chemical stability is further improved.
Moreover, the said inorganic filler component can also be made to act as an extender, and is useful also for adjustment of the color tone of a lead-free glass composition.
すなわち、本実施形態の無鉛ガラス組成物は、このような無機フィラー成分を前記ガラス成分に加えて含有していることから化学的安定性がより向上されている。
また、前記無機フィラー成分は、体質顔料として作用させることもでき、無鉛ガラス組成物の色調の調整にも有用である。 The lead-free glass composition of the present embodiment is used for the formation of a glass film, and when an acidic or alkaline liquid is contacted with the surface, a part of the glass component is dissolved in the liquid and the surface side Even when eroded, the inorganic particles function to protect the inner side.
That is, since the lead-free glass composition of the present embodiment contains such an inorganic filler component in addition to the glass component, chemical stability is further improved.
Moreover, the said inorganic filler component can also be made to act as an extender, and is useful also for adjustment of the color tone of a lead-free glass composition.
本実施形態の無鉛ガラス組成物は、化学的安定性が高いことから、メッキ工程やエッチング工程などが施される部材の表面を構成すべく用いられる場合などにおいてその効果をより顕著に発揮させることができる。
また、高い熱膨張係数を有することから、金属製の部材を被覆する用途に限らず、金属製部材どうしの接着や、金属製部材の封着などといった用途においても好適に用いられうる。
また、低い軟化点を有することから、５８０℃以下で焼成することができ、特にアルミニウム、アルミニウム合金の部材の上記用途において好適に用いられうる。
特に、アルミニウムは両性金属であることから、アルミニウムやその合金によって形成された部材は、酸性液体のみならずアルカリ性の液体に接液した場合でも腐食されるおそれを有する。
その点、本実施形態における無鉛ガラス組成物は、化学的安定性にも優れていることから、これらの部材の被覆材などに好適なものであるといえる。 Since the lead-free glass composition of the present embodiment has high chemical stability, the effect of the lead-free glass composition is more prominent when used to form the surface of a member subjected to a plating process, an etching process, or the like. Can do.
Moreover, since it has a high thermal expansion coefficient, it can be suitably used not only for applications covering metal members, but also for applications such as adhesion between metal members and sealing of metal members.
Moreover, since it has a low softening point, it can be fired at 580 ° C. or lower, and can be suitably used particularly in the above applications of aluminum and aluminum alloy members.
In particular, since aluminum is an amphoteric metal, a member formed of aluminum or an alloy thereof may be corroded even when it comes into contact with an alkaline liquid as well as an acidic liquid.
In that respect, since the lead-free glass composition in the present embodiment is excellent in chemical stability, it can be said that the lead-free glass composition is suitable for a covering material for these members.
また、高い熱膨張係数を有することから、金属製の部材を被覆する用途に限らず、金属製部材どうしの接着や、金属製部材の封着などといった用途においても好適に用いられうる。
また、低い軟化点を有することから、５８０℃以下で焼成することができ、特にアルミニウム、アルミニウム合金の部材の上記用途において好適に用いられうる。
特に、アルミニウムは両性金属であることから、アルミニウムやその合金によって形成された部材は、酸性液体のみならずアルカリ性の液体に接液した場合でも腐食されるおそれを有する。
その点、本実施形態における無鉛ガラス組成物は、化学的安定性にも優れていることから、これらの部材の被覆材などに好適なものであるといえる。 Since the lead-free glass composition of the present embodiment has high chemical stability, the effect of the lead-free glass composition is more prominent when used to form the surface of a member subjected to a plating process, an etching process, or the like. Can do.
Moreover, since it has a high thermal expansion coefficient, it can be suitably used not only for applications covering metal members, but also for applications such as adhesion between metal members and sealing of metal members.
Moreover, since it has a low softening point, it can be fired at 580 ° C. or lower, and can be suitably used particularly in the above applications of aluminum and aluminum alloy members.
In particular, since aluminum is an amphoteric metal, a member formed of aluminum or an alloy thereof may be corroded even when it comes into contact with an alkaline liquid as well as an acidic liquid.
In that respect, since the lead-free glass composition in the present embodiment is excellent in chemical stability, it can be said that the lead-free glass composition is suitable for a covering material for these members.
また、ＡｇやＡｌなどの導体ペーストや抵抗体ペーストへの配合用途などにも優れた効果を発揮させ得る。
さらには、金属製部材のみならず、高膨張セラミックス製部材の封着や、高膨張セラミックス製部材の表面被覆用途においても好適に用いられうる。
また、高膨張セラミックス製部材どうし、又は高膨張セラミックスと金属製部材との接着用途などにも好適に用いられうる。 Moreover, the effect excellent also in the compounding use to conductor paste and resistor paste, such as Ag and Al, can be exhibited.
Furthermore, it can be suitably used not only for metal members but also for sealing high-expansion ceramic members and for surface coating of high-expansion ceramic members.
Moreover, it can be used suitably also for the adhesive use of the members made from high expansion ceramics, or the high expansion ceramics and metal members.
さらには、金属製部材のみならず、高膨張セラミックス製部材の封着や、高膨張セラミックス製部材の表面被覆用途においても好適に用いられうる。
また、高膨張セラミックス製部材どうし、又は高膨張セラミックスと金属製部材との接着用途などにも好適に用いられうる。 Moreover, the effect excellent also in the compounding use to conductor paste and resistor paste, such as Ag and Al, can be exhibited.
Furthermore, it can be suitably used not only for metal members but also for sealing high-expansion ceramic members and for surface coating of high-expansion ceramic members.
Moreover, it can be used suitably also for the adhesive use of the members made from high expansion ceramics, or the high expansion ceramics and metal members.
なお、本実施形態の無鉛ガラス組成物は、その形態をガラス粒子と無機物粒子とを含んだ粉末状態以外に種々の形態とされうるものである。
また、本実施形態においては、無鉛ガラス組成物をガラス成分と無機フィラー成分とを含む場合を例示して説明しているが、上記例示のガラス成分のみを含む無鉛ガラス組成物も本発明の意図する範囲である。 In addition, the lead-free glass composition of this embodiment can be made into various forms in addition to the powder state containing glass particles and inorganic particles.
Further, in the present embodiment, the lead-free glass composition is described by exemplifying the case where the glass component and the inorganic filler component are included. However, the lead-free glass composition including only the glass component exemplified above is also the intent of the present invention. It is the range to do.
また、本実施形態においては、無鉛ガラス組成物をガラス成分と無機フィラー成分とを含む場合を例示して説明しているが、上記例示のガラス成分のみを含む無鉛ガラス組成物も本発明の意図する範囲である。 In addition, the lead-free glass composition of this embodiment can be made into various forms in addition to the powder state containing glass particles and inorganic particles.
Further, in the present embodiment, the lead-free glass composition is described by exemplifying the case where the glass component and the inorganic filler component are included. However, the lead-free glass composition including only the glass component exemplified above is also the intent of the present invention. It is the range to do.
次に実施例を挙げて本発明をさらに詳しく説明するが、本発明はこれらに限定されるものではない。
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
＜無鉛ガラス組成物の作製＞
表１～３に示す組成となるように配合原料を調合し、混合の後、白金ルツボを用いて約１０００～１２００℃の温度で１～２時間溶融した。該溶融したガラスをステンレス製の冷却ロールにて急冷し、無鉛ガラス組成物によって構成されたガラスフレークを作製した。
得られたガラスフレークは、さらに粉砕した後に気流分級して平均粒径（Ｄ５０）が０．５～２．０μｍの粉末ガラスとなるように調整して各評価に供した。
また、表１の実施例１、表２の実施例１６の無鉛ガラス組成物をベースに、さらに、無機フィラー成分を含有する実施例９～１３、実施例１８～２１の無鉛ガラス組成物を作製した。 <Preparation of lead-free glass composition>
The blended raw materials were prepared so as to have the compositions shown in Tables 1 to 3, and after mixing, they were melted at a temperature of about 1000 to 1200 ° C. for 1 to 2 hours using a platinum crucible. The molten glass was quenched with a stainless steel cooling roll to produce glass flakes composed of a lead-free glass composition.
The obtained glass flakes were further pulverized and classified by airflow, adjusted to become powdered glass having an average particle size (D 50 ) of 0.5 to 2.0 μm, and subjected to each evaluation.
Further, based on the lead-free glass composition of Example 1 in Table 1 and Example 16 of Table 2, the lead-free glass compositions of Examples 9 to 13 and Examples 18 to 21 further containing an inorganic filler component were produced. did.
表１～３に示す組成となるように配合原料を調合し、混合の後、白金ルツボを用いて約１０００～１２００℃の温度で１～２時間溶融した。該溶融したガラスをステンレス製の冷却ロールにて急冷し、無鉛ガラス組成物によって構成されたガラスフレークを作製した。
得られたガラスフレークは、さらに粉砕した後に気流分級して平均粒径（Ｄ５０）が０．５～２．０μｍの粉末ガラスとなるように調整して各評価に供した。
また、表１の実施例１、表２の実施例１６の無鉛ガラス組成物をベースに、さらに、無機フィラー成分を含有する実施例９～１３、実施例１８～２１の無鉛ガラス組成物を作製した。 <Preparation of lead-free glass composition>
The blended raw materials were prepared so as to have the compositions shown in Tables 1 to 3, and after mixing, they were melted at a temperature of about 1000 to 1200 ° C. for 1 to 2 hours using a platinum crucible. The molten glass was quenched with a stainless steel cooling roll to produce glass flakes composed of a lead-free glass composition.
The obtained glass flakes were further pulverized and classified by airflow, adjusted to become powdered glass having an average particle size (D 50 ) of 0.5 to 2.0 μm, and subjected to each evaluation.
Further, based on the lead-free glass composition of Example 1 in Table 1 and Example 16 of Table 2, the lead-free glass compositions of Examples 9 to 13 and Examples 18 to 21 further containing an inorganic filler component were produced. did.
＜評価試料の作製＞
各実施例、比較例の無鉛ガラス組成物が用いられた粉末状試料をそのまま示差熱分析（ＤＴＡ）用試料とした。
また、上記粉末状試料をプレス成型し、（軟化点＋５０℃）で１５分間焼成した後、直径５ｍｍ×長さ１５～２０ｍｍのロッド状試料を作製し、熱膨張係数測定用試料とした。
また、上記粉末状試料を焼成して、高さ５ｍｍ×幅１０ｍｍ×長さ１５ｍｍのブロック状試料を作製し化学的安定性（耐水性、耐酸性）評価用試料とした。 <Production of evaluation sample>
A powder sample using the lead-free glass composition of each example and comparative example was used as a sample for differential thermal analysis (DTA).
The powdery sample was press-molded and fired at (softening point + 50 ° C.) for 15 minutes, and then a rod-shaped sample having a diameter of 5 mm × length of 15 to 20 mm was prepared and used as a sample for measuring a thermal expansion coefficient.
Further, the powder sample was fired to prepare a block sample having a height of 5 mm, a width of 10 mm, and a length of 15 mm, and used as a sample for evaluating chemical stability (water resistance, acid resistance).
各実施例、比較例の無鉛ガラス組成物が用いられた粉末状試料をそのまま示差熱分析（ＤＴＡ）用試料とした。
また、上記粉末状試料をプレス成型し、（軟化点＋５０℃）で１５分間焼成した後、直径５ｍｍ×長さ１５～２０ｍｍのロッド状試料を作製し、熱膨張係数測定用試料とした。
また、上記粉末状試料を焼成して、高さ５ｍｍ×幅１０ｍｍ×長さ１５ｍｍのブロック状試料を作製し化学的安定性（耐水性、耐酸性）評価用試料とした。 <Production of evaluation sample>
A powder sample using the lead-free glass composition of each example and comparative example was used as a sample for differential thermal analysis (DTA).
The powdery sample was press-molded and fired at (softening point + 50 ° C.) for 15 minutes, and then a rod-shaped sample having a diameter of 5 mm × length of 15 to 20 mm was prepared and used as a sample for measuring a thermal expansion coefficient.
Further, the powder sample was fired to prepare a block sample having a height of 5 mm, a width of 10 mm, and a length of 15 mm, and used as a sample for evaluating chemical stability (water resistance, acid resistance).
（評価）
１）軟化点
各実施例、比較例の無鉛ガラス組成物が用いられた粉末状試料約５０ｍｇを白金セルに入れ、アルミナ粉末を用いたリファレンスとともにＤＴＡ装置にセットし室温から２０℃／ｍｉｎの昇温速度で昇温させ、得られたＤＴＡ曲線における吸熱開始点（外挿点）の温度をガラス転移点（Ｔｇ）、吸熱終了点（外挿点）の温度を軟化点（Ｔｓ）とした。
得られた結果を、表１～３に併せて示す。
２）熱膨張係数
各実施例、比較例の無鉛ガラス組成物が用いられたロッド状試料と石英ガラスにより形成された標準試料とを、熱機械分析装置（ＴＭＡ）を用いて、室温から１０℃／ｍｉｎで昇温して熱膨張曲線の測定を行い、５０℃から２５０℃までに観測される熱膨張係数の値を平均して各実施例、比較例の無鉛ガラス組成物によって形成されるガラスの熱膨張係数を求めた。結果を、表１～３に併せて示す。
３）化学的耐久性
３－１）耐水性（Ａ）
各実施例、比較例の無鉛ガラス組成物が用いられたブロック状試料の重量を精秤して初期重量（Ｗ０）を測定した後に５０℃のイオン交換水中に２４時間浸漬させ、再び、このブロック状試料の重量を精秤して試験後重量（Ｗ１）を求め、初期重量に対する重量減少率（〔Ｗ０－Ｗ１〕／Ｗ０×１００％）を計算して重量減少率が０．０５％以下の場合を“○”として判定し、０．０５％を超える重量減少率が見られたものを“×”として判定した。結果を、表１～３に併せて示す。
３－２）耐水性（Ｂ）
各実施例、比較例の無鉛ガラス組成物が用いられたブロック状試料の重量を精秤して初期重量（Ｗ０）を測定した後に１２１℃、１００％ＲＨ、２ａｔｍ雰囲気に４８時間暴露させ、再び、このブロック状試料の重量を精秤して試験後重量（Ｗ１）を求め、初期重量に対する重量減少率（〔Ｗ０－Ｗ１〕／Ｗ０×１００％）を計算して重量減少率が０．０５％以下の場合を“◎”として判定し、０．０５％を超える重量減少率が見られたものを“△”として判定した。結果を、表１～３に併せて示す。
３－３）耐酸性
イオン交換水中に代えて０．１Ｎの硝酸水溶液を用いたこと以外は、耐水性（Ａ）と同様に評価した。
すなわち、各実施例、比較例の無鉛ガラス組成物が用いられたブロック状試料の重量を精秤して初期重量（Ｗ０）を測定した後に５０℃の０．１Ｎ硝酸水溶液中に３０分浸漬させ、再び、このブロック状試料の重量を精秤して試験後重量（Ｗ１）を求め、初期重量に対する重量減少率（〔Ｗ０－Ｗ１〕／Ｗ０×１００％）を計算した。
なお、判定基準については、重量減少率が０．１％未満を“☆”、０．１～０．５％の場合を“◎”、０．５％を超え、２％以下の場合を“○”とし、２％を超える重量減少率が見られたものを“×”とた。結果を、表１～３に併せて示す。 (Evaluation)
1) Softening point Approximately 50 mg of a powder sample using the lead-free glass composition of each example and comparative example was placed in a platinum cell, set in a DTA apparatus together with a reference using alumina powder, and increased from room temperature to 20 ° C / min. The temperature was increased at a temperature rate, and the temperature at the endothermic start point (extrapolation point) in the obtained DTA curve was defined as the glass transition point (Tg), and the temperature at the endotherm end point (extrapolation point) was defined as the softening point (Ts).
The obtained results are also shown in Tables 1 to 3.
2) Thermal expansion coefficient A rod-shaped sample using the lead-free glass composition of each Example and Comparative Example and a standard sample formed of quartz glass were used at room temperature to 10 ° C. using a thermomechanical analyzer (TMA). The glass formed by the lead-free glass composition of each Example and Comparative Example by measuring the thermal expansion curve by raising the temperature at / min and averaging the values of the thermal expansion coefficients observed from 50 ° C. to 250 ° C. The thermal expansion coefficient of was determined. The results are also shown in Tables 1 to 3.
3) Chemical durability 3-1) Water resistance (A)
The weight of the block-like sample using the lead-free glass composition of each Example and Comparative Example was precisely weighed and the initial weight (W 0 ) was measured, and then immersed in ion exchange water at 50 ° C. for 24 hours. The weight of the block sample is precisely weighed to determine the weight (W 1 ) after the test, and the weight reduction rate with respect to the initial weight ([W 0 -W 1 ] / W 0 × 100%) is calculated, and the weight reduction rate is 0. A case of 0.05% or less was judged as “◯”, and a case where a weight reduction rate exceeding 0.05% was seen was judged as “x”. The results are also shown in Tables 1 to 3.
3-2) Water resistance (B)
After precisely weighing the weight of the block-shaped sample using the lead-free glass composition of each Example and Comparative Example and measuring the initial weight (W 0 ), it was exposed to 121 ° C., 100% RH, 2 atm atmosphere for 48 hours, Again, the weight of this block sample is precisely weighed to determine the weight (W 1 ) after the test, and the weight reduction rate ([W 0 −W 1 ] / W 0 × 100%) relative to the initial weight is calculated to reduce the weight. A case where the rate was 0.05% or less was determined as “◎”, and a case where a weight reduction rate exceeding 0.05% was observed was determined as “Δ”. The results are also shown in Tables 1 to 3.
3-3) Acid resistance The evaluation was the same as the water resistance (A) except that a 0.1 N aqueous nitric acid solution was used instead of ion-exchanged water.
That is, the weight of a block-like sample using the lead-free glass composition of each Example and Comparative Example was precisely weighed and the initial weight (W 0 ) was measured, and then immersed in a 0.1N nitric acid aqueous solution at 50 ° C. for 30 minutes Again, the weight of this block-like sample was precisely weighed to determine the weight after the test (W 1 ), and the weight reduction rate ([W 0 −W 1 ] / W 0 × 100%) with respect to the initial weight was calculated.
Regarding the judgment criteria, “☆” indicates that the weight reduction rate is less than 0.1%, “◎” indicates that the weight reduction rate is 0.1 to 0.5%, and “ “○” means that the rate of weight loss exceeding 2% was seen as “×”. The results are also shown in Tables 1 to 3.
１）軟化点
各実施例、比較例の無鉛ガラス組成物が用いられた粉末状試料約５０ｍｇを白金セルに入れ、アルミナ粉末を用いたリファレンスとともにＤＴＡ装置にセットし室温から２０℃／ｍｉｎの昇温速度で昇温させ、得られたＤＴＡ曲線における吸熱開始点（外挿点）の温度をガラス転移点（Ｔｇ）、吸熱終了点（外挿点）の温度を軟化点（Ｔｓ）とした。
得られた結果を、表１～３に併せて示す。
２）熱膨張係数
各実施例、比較例の無鉛ガラス組成物が用いられたロッド状試料と石英ガラスにより形成された標準試料とを、熱機械分析装置（ＴＭＡ）を用いて、室温から１０℃／ｍｉｎで昇温して熱膨張曲線の測定を行い、５０℃から２５０℃までに観測される熱膨張係数の値を平均して各実施例、比較例の無鉛ガラス組成物によって形成されるガラスの熱膨張係数を求めた。結果を、表１～３に併せて示す。
３）化学的耐久性
３－１）耐水性（Ａ）
各実施例、比較例の無鉛ガラス組成物が用いられたブロック状試料の重量を精秤して初期重量（Ｗ０）を測定した後に５０℃のイオン交換水中に２４時間浸漬させ、再び、このブロック状試料の重量を精秤して試験後重量（Ｗ１）を求め、初期重量に対する重量減少率（〔Ｗ０－Ｗ１〕／Ｗ０×１００％）を計算して重量減少率が０．０５％以下の場合を“○”として判定し、０．０５％を超える重量減少率が見られたものを“×”として判定した。結果を、表１～３に併せて示す。
３－２）耐水性（Ｂ）
各実施例、比較例の無鉛ガラス組成物が用いられたブロック状試料の重量を精秤して初期重量（Ｗ０）を測定した後に１２１℃、１００％ＲＨ、２ａｔｍ雰囲気に４８時間暴露させ、再び、このブロック状試料の重量を精秤して試験後重量（Ｗ１）を求め、初期重量に対する重量減少率（〔Ｗ０－Ｗ１〕／Ｗ０×１００％）を計算して重量減少率が０．０５％以下の場合を“◎”として判定し、０．０５％を超える重量減少率が見られたものを“△”として判定した。結果を、表１～３に併せて示す。
３－３）耐酸性
イオン交換水中に代えて０．１Ｎの硝酸水溶液を用いたこと以外は、耐水性（Ａ）と同様に評価した。
すなわち、各実施例、比較例の無鉛ガラス組成物が用いられたブロック状試料の重量を精秤して初期重量（Ｗ０）を測定した後に５０℃の０．１Ｎ硝酸水溶液中に３０分浸漬させ、再び、このブロック状試料の重量を精秤して試験後重量（Ｗ１）を求め、初期重量に対する重量減少率（〔Ｗ０－Ｗ１〕／Ｗ０×１００％）を計算した。
なお、判定基準については、重量減少率が０．１％未満を“☆”、０．１～０．５％の場合を“◎”、０．５％を超え、２％以下の場合を“○”とし、２％を超える重量減少率が見られたものを“×”とた。結果を、表１～３に併せて示す。 (Evaluation)
1) Softening point Approximately 50 mg of a powder sample using the lead-free glass composition of each example and comparative example was placed in a platinum cell, set in a DTA apparatus together with a reference using alumina powder, and increased from room temperature to 20 ° C / min. The temperature was increased at a temperature rate, and the temperature at the endothermic start point (extrapolation point) in the obtained DTA curve was defined as the glass transition point (Tg), and the temperature at the endotherm end point (extrapolation point) was defined as the softening point (Ts).
The obtained results are also shown in Tables 1 to 3.
2) Thermal expansion coefficient A rod-shaped sample using the lead-free glass composition of each Example and Comparative Example and a standard sample formed of quartz glass were used at room temperature to 10 ° C. using a thermomechanical analyzer (TMA). The glass formed by the lead-free glass composition of each Example and Comparative Example by measuring the thermal expansion curve by raising the temperature at / min and averaging the values of the thermal expansion coefficients observed from 50 ° C. to 250 ° C. The thermal expansion coefficient of was determined. The results are also shown in Tables 1 to 3.
3) Chemical durability 3-1) Water resistance (A)
The weight of the block-like sample using the lead-free glass composition of each Example and Comparative Example was precisely weighed and the initial weight (W 0 ) was measured, and then immersed in ion exchange water at 50 ° C. for 24 hours. The weight of the block sample is precisely weighed to determine the weight (W 1 ) after the test, and the weight reduction rate with respect to the initial weight ([W 0 -W 1 ] / W 0 × 100%) is calculated, and the weight reduction rate is 0. A case of 0.05% or less was judged as “◯”, and a case where a weight reduction rate exceeding 0.05% was seen was judged as “x”. The results are also shown in Tables 1 to 3.
3-2) Water resistance (B)
After precisely weighing the weight of the block-shaped sample using the lead-free glass composition of each Example and Comparative Example and measuring the initial weight (W 0 ), it was exposed to 121 ° C., 100% RH, 2 atm atmosphere for 48 hours, Again, the weight of this block sample is precisely weighed to determine the weight (W 1 ) after the test, and the weight reduction rate ([W 0 −W 1 ] / W 0 × 100%) relative to the initial weight is calculated to reduce the weight. A case where the rate was 0.05% or less was determined as “◎”, and a case where a weight reduction rate exceeding 0.05% was observed was determined as “Δ”. The results are also shown in Tables 1 to 3.
3-3) Acid resistance The evaluation was the same as the water resistance (A) except that a 0.1 N aqueous nitric acid solution was used instead of ion-exchanged water.
That is, the weight of a block-like sample using the lead-free glass composition of each Example and Comparative Example was precisely weighed and the initial weight (W 0 ) was measured, and then immersed in a 0.1N nitric acid aqueous solution at 50 ° C. for 30 minutes Again, the weight of this block-like sample was precisely weighed to determine the weight after the test (W 1 ), and the weight reduction rate ([W 0 −W 1 ] / W 0 × 100%) with respect to the initial weight was calculated.
Regarding the judgment criteria, “☆” indicates that the weight reduction rate is less than 0.1%, “◎” indicates that the weight reduction rate is 0.1 to 0.5%, and “ “○” means that the rate of weight loss exceeding 2% was seen as “×”. The results are also shown in Tables 1 to 3.
これらの表に示された結果からも、本発明の無鉛ガラス組成物は、低軟化点でありながらも高い熱膨張係数と優れた化学的耐久性とを有するガラスを形成させ得ることがわかる。
From the results shown in these tables, it can be seen that the lead-free glass composition of the present invention can form a glass having a high thermal expansion coefficient and excellent chemical durability while having a low softening point.
Claims (7)
- 重量百分率でＢｉ２Ｏ３：３０～６２％、ＳｉＯ２：１０～３５％、Ａｌ２Ｏ３：０．１～５％、Ｂ２Ｏ３：０．１～４．５％、及びＴｉＯ２：０．１～８％含み、さらに、Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの何れか１種以上を合計１０～２５％含むガラス成分が含有されてなることを特徴とする無鉛ガラス組成物。 Bi 2 O 3 : 30 to 62% by weight percentage, SiO 2 : 10 to 35%, Al 2 O 3 : 0.1 to 5%, B 2 O 3 : 0.1 to 4.5%, and TiO 2 A lead-free glass composition characterized by containing a glass component containing 0.1 to 8% and further containing at least one of Li 2 O, Na 2 O and K 2 O in a total of 10 to 25% object.
- 前記ガラス成分が、重量百分率でＢｉ２Ｏ３：４２～６０％、ＳｉＯ２：１６～２５％、Ａｌ２Ｏ３：０．１～５％、Ｂ２Ｏ３：３～３．６％、及びＴｉＯ２：１．１～８％含み、Ｎａ２Ｏ：５．０～１０％、及びＫ２Ｏ：５．０～１０％を含有する請求項１記載の無鉛ガラス組成物。 The glass component is, by weight percentage, Bi 2 O 3 : 42 to 60%, SiO 2 : 16 to 25%, Al 2 O 3 : 0.1 to 5%, B 2 O 3 : 3 to 3.6%, And TiO 2 : 1.1 to 8%, Na 2 O: 5.0 to 10%, and K 2 O: 5.0 to 10%.
- 前記ガラス成分が、重量百分率でＢｉ２Ｏ３：４２～４５％、ＳｉＯ２：２２～２５％、Ａｌ２Ｏ３：０．１～１％、Ｂ２Ｏ３：３～３．６％、及びＴｉＯ２：５～８％含み、さらに、Ｎａ２Ｏ：７．０～１０％、Ｋ２Ｏ：８．０～１０％、及びＢａＯ：４～６％含有する請求項１記載の無鉛ガラス組成物。 The glass component contains Bi 2 O 3 : 42 to 45%, SiO 2 : 22 to 25%, Al 2 O 3 : 0.1 to 1%, B 2 O 3 : 3 to 3.6% by weight percentage, And TiO 2 : 5 to 8%, and further containing Na 2 O: 7.0 to 10%, K 2 O: 8.0 to 10%, and BaO: 4 to 6%. Composition.
- 前記ガラス成分が、重量百分率でＢｉ２Ｏ３：５０～５８％、ＳｉＯ２：２０～２３％、Ａｌ２Ｏ３：０．１～２％、Ｂ２Ｏ３：３～３．６％、及びＴｉＯ２：５．１～８％含み、さらに、Ｎａ２Ｏ：５．０～１０％、及びＫ２Ｏ：５．０～１０％を含有する請求項１記載の無鉛ガラス組成物。 The glass component is, by weight percentage, Bi 2 O 3 : 50 to 58%, SiO 2 : 20 to 23%, Al 2 O 3 : 0.1 to 2%, B 2 O 3 : 3 to 3.6%, And TiO 2 : 5.1 to 8%, and further containing Na 2 O: 5.0 to 10% and K 2 O: 5.0 to 10%.
- 前記ガラス成分の軟化点が５２０℃以下であり、且つ、前記ガラス成分の５０～２５０℃の熱膨張係数が１４０×１０－７／℃以上である請求項１に記載の無鉛ガラス組成物。 2. The lead-free glass composition according to claim 1, wherein the glass component has a softening point of 520 ° C. or lower, and the glass component has a thermal expansion coefficient of 50 to 250 ° C. of 140 × 10 −7 / ° C. or higher.
- ＴｉＯ２、Ａｌ２Ｏ３、ＳｉＯ２、ＺｒＯ２、及びＭｇＯの何れか１種以上を含む無機フィラー成分が前記ガラス成分とともに含まれている請求項１に記載の無鉛ガラス組成物。 TiO 2, Al 2 O 3, SiO 2, ZrO 2, and either lead-free glass composition according to claim 1, the inorganic filler component is contained together with the glass component comprising one or more MgO.
- アルミニウム、又はアルミニウム合金製の部材上で焼成されるべく用いられる請求項１に記載の無鉛ガラス組成物。 The lead-free glass composition according to claim 1, which is used to be fired on a member made of aluminum or an aluminum alloy.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2010522717A JPWO2010013692A1 (en) | 2008-07-28 | 2009-07-28 | Lead-free glass composition |
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| JP2008193689 | 2008-07-28 | ||
| JP2008-193689 | 2008-07-28 |
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| PCT/JP2009/063388 WO2010013692A1 (en) | 2008-07-28 | 2009-07-28 | Lead-free glass composition |
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| WO (1) | WO2010013692A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011178574A (en) * | 2010-02-26 | 2011-09-15 | Tokan Material Technology Co Ltd | Glass composition for high acid resistant coating firable at low temperature and the glass composition paste |
| JP2011213526A (en) * | 2010-03-31 | 2011-10-27 | Nihon Yamamura Glass Co Ltd | Glass composition |
| JP2016119492A (en) * | 2011-03-07 | 2016-06-30 | ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ | housing |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06234547A (en) * | 1992-12-18 | 1994-08-23 | Asahi Glass Co Ltd | Ceramic color composition and production of curved glass plate using the same |
| JPH09227214A (en) * | 1996-02-22 | 1997-09-02 | Asahi Glass Co Ltd | Ceramic color composition |
| JPH09278483A (en) * | 1996-04-05 | 1997-10-28 | Nippon Electric Glass Co Ltd | Bismuth based glass composition |
| JPH11343141A (en) * | 1998-04-27 | 1999-12-14 | Cerdec Ag Keramische Farben | Low melting lead-free glass-and enamel composition having high bismuth content |
-
2009
- 2009-07-28 WO PCT/JP2009/063388 patent/WO2010013692A1/en active Application Filing
- 2009-07-28 JP JP2010522717A patent/JPWO2010013692A1/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06234547A (en) * | 1992-12-18 | 1994-08-23 | Asahi Glass Co Ltd | Ceramic color composition and production of curved glass plate using the same |
| JPH09227214A (en) * | 1996-02-22 | 1997-09-02 | Asahi Glass Co Ltd | Ceramic color composition |
| JPH09278483A (en) * | 1996-04-05 | 1997-10-28 | Nippon Electric Glass Co Ltd | Bismuth based glass composition |
| JPH11343141A (en) * | 1998-04-27 | 1999-12-14 | Cerdec Ag Keramische Farben | Low melting lead-free glass-and enamel composition having high bismuth content |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011178574A (en) * | 2010-02-26 | 2011-09-15 | Tokan Material Technology Co Ltd | Glass composition for high acid resistant coating firable at low temperature and the glass composition paste |
| JP2011213526A (en) * | 2010-03-31 | 2011-10-27 | Nihon Yamamura Glass Co Ltd | Glass composition |
| JP2016119492A (en) * | 2011-03-07 | 2016-06-30 | ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ | housing |
| US9807897B2 (en) | 2011-03-07 | 2017-10-31 | Schott Ag | Glass system for hermetically joining Cu components, and housing for electronic components |
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| JPWO2010013692A1 (en) | 2012-01-12 |
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