JP2019214494A - Glass, glass paste, and manufacturing method of glass - Google Patents

Abstract

To provide a glass and a glass paste having low melting point, and a manufacturing method of the glass capable of providing the glass having low melting point.SOLUTION: The glass contains VOand TeOas metal oxide constituting a net structure, and BiFas a halide with amount of 100 mass% or less in the outer percentage based on total amount of 100 mass% of the VOand the TeO. Since a part of metals constituting the metal oxide reacts with the halide, binding energy between the metals and oxygen as whole net structure is reduced. Thereby low melting point is achieved.SELECTED DRAWING: Figure 2

Description

  The present invention relates to glass, a glass paste, and a method for producing glass.

  BACKGROUND ART A glass paste obtained by adding a binder solution to a glass powder made of a metal oxide and kneading the same is known (for example, see Patent Document 1). The metal oxide forms an amorphous network structure in the glass powder.

  The above-mentioned glass paste is used for joining members in a manufacturing process of various electric products. Specifically, the glass paste is melted by heating while being sandwiched between the first member and the second member. Thereby, the glass paste is fused to the first member and the second member, and the first member and the second member are joined.

JP-A-2004-250276

  If the melting point of the glass paste is high, the heat for melting the glass paste may adversely affect the first member, the second member, or the electronic components held by the first member and the second member. It is feared that it will be given.

  Therefore, reducing the melting point of the glass constituting the glass paste to lower the melting point is an important research topic. Further, in applications other than the joining of the first member and the second member, there is a case where a glass having a low melting point is desired.

  An object of the present invention is to provide a glass and a glass paste with a reduced melting point, and a method for producing a glass from which a glass with a reduced melting point can be obtained.

In order to achieve the above object, the glass according to the present invention is:
A metal oxide constituting a network structure,
A halide in an amount of 100% by mass or less based on 100% by mass of the metal oxide;
including.

  The halide may be a fluoride.

The fluoride may be a BiF _3.

  The content of the halide may be not less than 5% by mass and not more than 66.7% by mass on the basis of 100% by mass of the metal oxide.

The metal oxide _may include V 2 _{O 5} and TeO _2.

In the metal oxide, a mass ratio defined by the mass of the V ₂ O ₅ / the mass of the TeO ₂ may be 1/8 or more and 5/4 or less.

Glass paste according to the present invention,
A frit made of the glass according to the present invention described above,
A binder solution;
including.

The method for producing glass according to the present invention comprises:
A raw material composition containing a metal oxide constituting a network structure and a halide in an amount of 100% by mass or less based on 100% by mass of the metal oxide is heated at a temperature of 1000 ° C. or less for 30 minutes or less. A melting step of melting by heating,
A cooling step of cooling a melt obtained by melting the raw material composition,
Have

  In the melting step, the raw material composition may be melted by heating at a temperature of 700 ° C. or less for a time of 15 minutes or less.

After the cooling step, a pulverizing step of pulverizing a glass body obtained by cooling the melt,
May be further provided.

  The melting point of the glass becomes lower as the binding energy between the metal constituting the metal oxide and oxygen is smaller. According to the present invention, since a part of the metal constituting the metal oxide is combined with the halide, the number of bonds between the metal and oxygen in the network structure is reduced. As a result, the binding energy between the metal and oxygen in the entire network structure is reduced, so that the melting point is reduced.

5 is a flowchart showing a method for producing a glass paste for bonding according to the embodiment. 3 is a triangular diagram showing a configuration of a raw material composition according to an example. 9 is a triangular diagram showing a configuration of a raw material composition according to another example. 5 is a graph showing glass transition points of glass samples according to Examples and Comparative Examples. 5 is a graph showing the thermal expansion coefficients of glass samples according to examples and comparative examples. (A)-(f) is a photograph which shows the state after the main baking of the bonding glass paste which concerns on an Example. The conceptual diagram which shows the DTA curve acquired in a differential thermal analysis. The conceptual diagram which shows the aspect of use of the glass paste for joining which concerns on an Example. 5 is a temperature profile of calcination of the bonding glass paste according to the example. The temperature profile of the main baking of the glass paste for joining which concerns on an Example.

  A method for manufacturing a bonding glass paste according to the embodiment will be described with reference to the flowchart shown in FIG. In the following description, what is described as "-quality raw material" represents an actual raw material that may contain unavoidable impurities, and those described with a compound name or a chemical formula represent chemical components in the raw material. Shall be.

(A) Mixing Step First, a raw material composition is obtained by mixing a metal oxide material raw material containing a metal oxide as a main component and a halide material raw material containing a halide as a main component (step S11). In the present specification, “main component” means that the purity is 90% by mass or more, preferably 95% by mass or more.

  The metal oxide plays a role in forming an amorphous network structure. In this specification, the term “metal oxide” is a concept including not only a network former (NWF) but also a network modifier (NWM) and an intermediate oxide (Intermediate).

  Note that the network-forming oxide alone can form a network structure. Although the network modifying oxide alone cannot form a network structure, it can enter the network formed by the network forming oxide and affect the properties of the network. The intermediate oxide alone cannot form a network structure, but replaces part of the network forming oxide and participates in the formation of the network.

In this specification, the term “metal” constituting a metal oxide includes not only a metal element but also a semimetal element including Te and Si. Examples of the metal oxide include TeO ₂ , V ₂ O ₅ , ZnO, BaO, P ₂ O ₅ , Fe ₂ O ₃ , Li ₂ B ₄ O ₇ , KPO ₃ , SnO, Nb ₂ O ₅ , SiO ₂ , One or more kinds selected from Al ₂ O ₃ can be used. Among _them, preferred are V 2 _{O 5} and TeO _2, in the metal _oxide, the mass ratio defined by the mass of the mass / TeO ₂ of V 2 _{O 5} is 1/8 or more, preferably 5/4 or less .

  The halide mainly serves to reduce the number of bonds between the metal and oxygen in the network structure by bonding to the metal in such a manner as to cut off the bond between the metal and oxygen in the metal oxide. As a result, the binding energy between the metal and oxygen in the entire network structure is reduced, so that the melting point is reduced. Further, the halide can also play a role of lowering the thermal expansion coefficient of the obtained glass or improving water resistance by modifying the network structure.

As the halide, for example, one or more selected from fluoride, chloride, bromide, and iodide can be used. Among them, fluoride is preferred. As the fluoride, for example, one or more selected from BiF ₃ , InF ₃ , SnF ₄ , SbF ₃ , ZnF ₂ , and AlF ₃ can be used. Among them, BiF ₃ is preferable.

  From the viewpoint of obtaining a particularly favorable effect of lowering the melting point, the content of the halide is 5% by mass or more and 100% by mass or less on the basis of 100% by mass of the metal oxide after the melting step described below. Preferably, it is 5% by mass or more and 66.7% by mass or less. After the melting step described later, the content of the halide may be 20% by mass or more or 40% by mass or more based on 100% by mass of the metal oxide. The content of the halide in the raw material composition is adjusted so that these conditions are satisfied.

(B) Melting Step Next, the raw material composition is melted (Step S12). The heating temperature for melting is preferably 1000 ° C. or less, more preferably 700 ° C. or less, from the viewpoint of stably retaining the halide in the network structure. The heating time for melting is preferably 30 minutes or less, more preferably 15 minutes or less.

(C) Cooling Step Next, a melt obtained by melting the raw material composition is poured into a mold and cooled (Step S13). The cooling method is not particularly limited. For example, by placing the melt in a temperature environment at room temperature, the melt can be cooled naturally to room temperature.

(D) Pulverizing Step Next, the glass body obtained by cooling the melt is pulverized (step S14). For the pulverization, for example, a mill, a crusher, or the like can be used. By grinding the glass body, a frit as a joining glass is obtained.

  Note that a refractory filler having a higher melting point than the frit may be added to the obtained frit for the purpose of adjusting the coefficient of thermal expansion or the like. As the refractory filler, for example, an alumina material, a mullite material, a cordierite material, or the like can be used. The amount of the refractory filler to be added is, for example, 5% by mass or more and 200% by mass or less based on 100% by mass of the frit.

(E) Kneading Step Next, a binder solution is added to the above-mentioned frit or a mixture of the frit and the refractory filler and kneaded (step S15). The binder solution is obtained by dissolving a binder in a solvent. As the binder, for example, celluloses, resins, and the like can be used. As the solvent, for example, thinner, oil and the like can be used. The amount of the binder solution to be added is, for example, 5% by mass or more in an outer appearance with respect to 100% by mass of the frit.

  Thus, the bonding glass paste is completed. “For joining” means used for joining the first member and the second member. That is, the bonding glass paste is applied to the first member, and is melted while being sandwiched between the first member and the second member. Thereby, the joining glass paste is fused to the first member and the second member, and the first member and the second member are joined.

  The melting of the bonding glass paste can be performed by heating the bonding glass paste together with the first member and the second member. When the first member and the second member are glass substrates, the bonding glass paste can be melted by irradiating the bonding glass paste with laser light through the glass substrates.

  In any case, the melting point of the bonding glass paste is desired to be low in order to suppress a thermal adverse effect on the first member, the second member, or the electronic component held by the first member and the second member. . In this regard, as described above, according to the present embodiment, the halide serves to lower the melting point of the bonding glass paste.

  In addition, in order to stably maintain the bonding state between the bonding glass paste and the first member and the second member after solidifying the bonding glass paste after melting (hereinafter, referred to as a solidified body), the glass forming the bonding glass paste is It is desired that the coefficient of thermal expansion be as small as possible. In this regard, as described above, according to the present embodiment, the halide can play a role of lowering the thermal expansion coefficient of the glass constituting the bonding glass paste by modifying the network structure.

  Further, in order to prevent the solidified body of the bonding glass paste from being deteriorated by moisture, the glass constituting the bonding glass paste is required to have water resistance. When the joining is sealing, that is, the joining glass paste is applied so as to surround the electronic component held by the first member, and the first component, the second member, and the electronic component are joined by the joining glass paste. Even in the case of hermetic sealing, glass constituting the bonding glass paste is required to have water resistance in order to prevent moisture from reaching the electronic components. In this regard, as described above, according to the present embodiment, the halide can play a role of improving the water resistance of the glass by modifying the network structure.

A vanadium pentoxide raw material containing V ₂ O ₅ as a main component and a tellurium dioxide raw material containing TeO ₂ as a main component were prepared as metal oxide material raw materials. In addition, a bismuth trifluoride raw material containing BiF ₃ as a main component was prepared as a halogenated substance raw material. The purity of each raw material is 95% by mass or more.

First, as a mixing step, the above-described three types of raw materials were mixed to prepare the raw material compositions according to Examples H1 to H29. In the raw material composition according to Example _H1～H29, the content of V ₂ O 5, TeO _2, and BiF ₃ are different from each other.

FIG. 2 shows a configuration of the raw material composition according to Examples H1 to H29. The raw material composition according to each example contains V ₂ O ₅ , TeO ₂ , and BiF ₃ at a mass ratio represented by lattice points at which dashed lines provided at regular intervals in a triangular diagram intersect. However, the raw material composition according to Example H8 is composed of V ₂ O ₅ : 50% by mass, TeO ₂ : 25% by mass, and BiF ₃ : 25% by mass. Further, the raw material composition according to Example H11 was composed of V ₂ O ₅ : 45% by mass, TeO ₂ : 45% by mass, and BiF ₃ : 10% by mass.

  Next, as a melting step, each of the raw material compositions according to Examples H1 to H29 was melted to obtain a melt. Melting was performed by placing each raw material composition in a crucible and heating the entire crucible at 1000 ° C. for 20 minutes in an electric furnace.

  Next, as a cooling step, each of the melts according to Examples H1 to H29 was poured into a mold and left in the air at room temperature to be naturally cooled to room temperature. Thereby, a rod-shaped glass sample as a glass body according to Examples E1 to E29 was obtained.

  Then, the coefficient of thermal expansion of each of the glass samples according to Examples E1 to E29 was measured using a thermomechanical analyzer. In addition, a cylindrical sample having a predetermined size was cut out from each glass sample, and the cylindrical sample was measured.

  The water resistance of each of the glass samples according to Examples E1 to E29 was evaluated. The water resistance was evaluated based on the mass reduction rate of a sample obtained by immersing a sample of a predetermined size cut out of each glass sample in boiling distilled water for 1 hour.

  Next, as a pulverizing step, each of the glass samples according to Examples H1 to H29 was pulverized with a stamp mill and classified to obtain the frit according to Examples H1 to H29. The particle size of each frit was adjusted to less than 100 μm. In the present specification, the particle size of the particles smaller than d means that the particles have a particle size that passes through a sieve having an opening d defined in JIS-Z8801.

  Then, for each of the frits according to Examples H1 to H29, the X-ray diffraction waveform was measured using a powder X-ray diffractometer. The X-ray scanning speed was 2 ° / min.

  Further, for each of the frits according to Examples H1 to H29, a DTA (Differential Thermal Analysis) curve was obtained using a differential thermal analyzer, and a glass transition point Tg was obtained based on the DTA curve. Note that α-alumina was used as a reference material. The heating rate of the sample was 10 ° C./min.

  FIG. 7 shows a conceptual diagram of the DTA curve. The horizontal axis indicates the temperature of the frit, and the vertical axis indicates the temperature difference between the frit and the reference substance. The temperature of the shoulder closer to the origin of the first endothermic peak P1 appearing with the rise in temperature was read as the glass transition point Tg.

  The temperature at the extreme value of the endothermic peak P1 is the glass softening point Tf, and the temperature at the extreme value of the next endothermic peak P2 is the crystal precipitation point Tx. Each of the glass transition point Tg, the glass softening point Tf, and the crystal precipitation point Tx is estimated by linear approximation using nearby data.

  Next, as a kneading process, a binder solution was added to each of the frits according to Examples H1 to H29 and kneaded to obtain a bonding glass paste according to Examples H1 to H29. The binder solution used contained ethyl cellulose as a binder in an amount of 2% by mass or more and 7% by mass or less, and the balance was composed of a solvent composed of pine oil, butyl diglycol acetate, and an aromatic hydrocarbon. Each bonding glass paste is composed of 90% by mass of a frit and 10% by mass of a binder solution.

  Then, a bonding strength measurement experiment was performed on the glass paste for bonding according to Examples H1 to H29 to examine the performance of bonding members together. Hereinafter, the bonding strength measurement experiment will be specifically described.

  As shown in FIG. 8, a predetermined amount of bonding glass paste PT is uniformly applied over a predetermined area on the surface of a first glass substrate S1 as a first member. Note that the first glass substrate S1 is made of soda lime glass. In this state, the bonding glass paste PT was temporarily fired together with the first glass substrate S1. The calcination was performed in an electric furnace.

  FIG. 9 shows a temperature profile of the preliminary firing. In an electric furnace, the temperature of the first glass substrate S1 and the bonding glass paste PT is raised from room temperature to 230 ° C., and the temperature is maintained for 30 minutes to volatilize the solvent component in the binder solution.

  Next, the first glass substrate S1 and the bonding glass paste PT were heated from 230 ° C. to the glass softening point Tf of the frit constituting the bonding glass paste PT, and held for 20 minutes. Thereby, air bubbles in the bonding glass paste PT are removed. Thereafter, by stopping the heating, the inside of the electric furnace was naturally cooled to room temperature.

  Returning to FIG. 8, the description will be continued. After the calcination is performed as described above, the second glass substrate S2 as a second member is stacked on the tentatively baked bonding glass paste PT. Note that the second glass substrate S2 is also made of soda-lime glass, like the first glass substrate S1.

  Then, in a state where one of the first glass substrate S1 and the second glass substrate S2 was pressed toward the other, the bonding glass paste PT was fired together with the first glass substrate S1 and the second glass substrate S2. The main firing was also performed in an electric furnace.

  FIG. 10 shows a temperature profile of the main firing. In an electric furnace, the first glass substrate S1, the second glass substrate S2, and the bonding glass paste PT were heated from room temperature to the crystal precipitation point Tx of the frit constituting the bonding glass paste PT, and held for 20 minutes. . Thereafter, by stopping the heating, the inside of the electric furnace was naturally cooled to room temperature.

  Next, a tensile strength test for separating the bonded first glass substrate S1 and the second glass substrate S2 from each other is performed, and a unit area per unit area required to separate the first glass substrate S1 and the second glass substrate S2 from each other is performed. Force (hereinafter referred to as bonding strength) was measured.

  Hereinafter, the results of the above-described various evaluations will be described.

  In FIG. 2, among Examples H1 to H29, those which were confirmed to be amorphous in the X-ray diffraction pattern were plotted with circles. Also, those which were within the allowable range but were slightly crystallized were plotted with triangles. Here, "slightly crystallized" means that, in the X-ray diffraction pattern, a part that rises in a mountain shape, although it is sufficiently gentle, is confirmed.

As shown in FIG. 2, crystallization was observed in Examples H10, H15, H16, and H21 in which the BiF ₃ content was 40% by mass or more. In addition, the degree of crystallization was stronger as the BiF ₃ content was larger.

Glass crystallization can be a factor in raising the melting point. Therefore, in order to obtain the effect of lowering the melting point particularly favorably, it is considered that the content of BiF ₃ is preferably 40% by mass or less, and more preferably less than 40% by mass. In other words, the content of BiF ₃ is preferably not more than 66.7% by mass, and more preferably less than 66.7% by mass, based on the total amount of V ₂ O ₅ and TeO ₂ of 100% by mass. More preferred.

  Further, in FIG. 2, in the bonding strength measurement experiment described above, the bonding strength is equal to or more than a threshold value indicating that the first glass substrate S1 and the second glass substrate S2 are sufficiently firmly bonded. Was surrounded by a thick solid line.

From these results, in order to obtain particularly good bonding strength, it is considered that the content of TeO _{2 in} the glass is preferably more than 20% by mass, and more preferably 30% by mass or more. Further, the content of V ₂ O _{5 in} the glass is preferably less than 60% by mass, more preferably less than 50% by mass, and even more preferably 45% by mass or less.

Focusing on the mass ratio defined by the mass of V ₂ O ₅ / the mass of TeO ₂ , in order to obtain a particularly good bonding strength, the value of this mass ratio should be 1/8 or more and 5/4 or less. It is considered preferable.

  Next, the same raw material compositions as those of Examples H6, H12 to H15, H17 to H20, H22 to H25, and H26 to H29 shown in FIG. Under the same manufacturing conditions as in Examples H1 to H29, the bonding glass pastes according to Examples L6, L12 to L15, L17 to L20, L22 to L25, and L26 to L29 were manufactured.

  FIG. 3 shows the configurations of the raw material compositions according to Examples L6, L12 to L15, L17 to L20, L22 to L25, and L26 to L29. In the melting step according to these examples, the raw material composition was melted by heating at 700 ° C. for 10 minutes.

  In FIG. 3, similarly to FIG. 2, those which were confirmed to be amorphous in the X-ray diffraction pattern were plotted with circles and, although within an allowable range, slightly crystallized. Those are plotted with triangles.

As shown in FIG. 3, crystallization was observed in Examples L15 and L29 in which the BiF ₃ content was 40% by mass or more. In addition, the degree of crystallization was stronger as the BiF ₃ content was larger. Therefore, it is considered preferable that the content of BiF ₃ is less than 40% by mass. This is the same as the result shown in FIG.

  Also, in FIG. 3, as in FIG. 2, in the bonding strength measurement experiment described above, the bonding strength is equal to or larger than a threshold value indicating that the first glass substrate S1 and the second glass substrate S2 are bonded sufficiently firmly. Was surrounded by a thick solid line.

From this result, it is considered that the content of V ₂ O _{5 in} the glass is preferably 40% by mass or less in order to obtain particularly good bonding strength. Further, it is considered that the content of TeO _{2 in} the glass is preferably 30% by mass or more. Focusing on the mass ratio defined by the mass of V ₂ O ₅ / the mass of TeO ₂ , it is considered that the value of this mass ratio is preferably 1/8 or more and 4/5 or less.

FIG. 4 shows the glass transition point Tg of the frit according to Examples H12 to H14 and L12 to L14 described above as a representative. FIG. 4 also shows, as Comparative Example CE1, the glass transition point Tg of a known frit made of V ₂ O ₅ , ZnO, BaO, and TeO ₂ .

  As shown in FIG. 4, the glass transition point Tg of the frit according to Examples H12 to H14 and L12 to L14 is sufficiently lower than the glass transition point Tg of the frit according to Comparative Example CE1. That is, the frit according to Examples H12 to H14 and L12 to L14 has a low melting point. Further, although not shown in FIG. 4, it was confirmed that the frit according to the other example had a lower melting point than the comparative example CE1.

This is because, in the process of manufacturing the frit, BiF ₃ bonds with metal in a form that cuts off the bond between oxygen, which is V or Te, and the number of bonds between metal and oxygen in the network structure. Is reduced. That is, as a result of a decrease in the binding energy between metal and oxygen in the entire network structure, the melting point was reduced.

Conventionally, in the glass technical field, the effect of reducing the melting point of an alkali metal is known. However, according to the above-described embodiments, the melting point can be reduced by adding BiF ₃ without adding an alkali metal. It was planned. Since the frit according to each of the above embodiments does not contain an alkali metal, the harmful effect of adding an alkali metal, specifically, the harmful effect that the chemical durability of glass tends to decrease due to elution of an alkali component is avoided. Is done.

In each of the above embodiments, BiF ₃ was used as the substance that reduces the binding energy between metal and oxygen. However, it is considered that the same effect can be obtained even when another halide is used. . In other words, since the halide is highly reactive, the number of bonds between the metal and oxygen in the entire network structure is reduced by cutting the bond between the metal and oxygen and bonding to the metal in preference to oxygen. Can be reduced.

Further, as shown in FIG. 4, Examples L12 to L14 have a lower glass transition point Tg than Examples H12 to H14. This is because embodiments L12~L14 is than Example H12～14, the heating temperature is low in the raw material composition in the melting process, and because the heating time is short, volatilization of BiF ₃ is suppressed, the BiF ₃ It is considered that the effect of lowering the melting point by the addition was fully exhibited. For this reason, the heating temperature of the raw material composition in the melting step is preferably as low as possible, and the heating time is preferably as short as possible.

Note that even after the melting step, the amount of loss of the metal oxide is negligible. Therefore, the mass ratio defined by the mass of V ₂ O ₅ / the mass of TeO _{2 in} the glass body or the frit is shown in FIGS. 3 is maintained at the value read.

In FIGS. 2 and 3, the lower limit of the BiF ₃ content is 10% by mass. Even volatilized at BiF ₃ has lost part of the melting step, BiF ₃ in the glass sample or fritted _is outside over the total amount 100 mass% of V 2 _{O 5} and TeO _2, or 5 wt% when residual Conceivable.

FIG. 5 shows the thermal expansion coefficients α of the glass samples according to Examples H12 to H14 and L12 to L14 described above as representatives. FIG. 5 also shows the thermal expansion coefficient α of a known glass sample made of V ₂ O ₅ , Li ₂ O, and TeO ₂ as Comparative Example CE2. As shown in FIG. 5, the thermal expansion coefficients α of the glass samples according to Examples H12 to H14 and L12 to L14 are lower than the thermal expansion coefficient α of the glass sample according to Comparative Example CE2.

Glass sample according to the comparative example CE2 is free of BiF _3. Thus, glass samples according to Examples H12~14 and L12~L14 is, the exhibited thermal expansion coefficient α less than the glass sample according to the comparative example CE2 is in the process of manufacturing the glass sample, BiF ₃ is mesh It is thought to be due to the modification of the structure.

However, Examples L12 to L14 have a larger coefficient of thermal expansion α than Examples H12 to H14. As described above, the residual amount of BiF ₃ in the glass sample, there are more examples L12~L14 than Example H12～14. Therefore, from the viewpoint of obtaining a smaller thermal expansion coefficient α, it is considered that the smaller the amount of BiF ₃ added to the metal oxide, the better.

The thermal expansion coefficient of the solidified body of the bonding glass paste PT alpha is, since it depends on the content of BiF _3, the content of BiF _3, the alpha coefficient of thermal expansion of the solidified body of the bonding glass paste PT, the The thermal expansion coefficients of the first member and the second member can be approximated.

  In Table 1 below, the mass reduction rates as the evaluation results of the water resistance of the glass samples according to Examples H12 to H14 and L12 to L14 and Comparative Examples CE1 and CE2 are shown. The lower the mass reduction rate, the lower the solubility in water, indicating higher water resistance.

As shown in Table 1, in each of Examples H12 to H14 and L12 to L14, the mass reduction rate was sufficiently lower than that of Comparative Examples CE1 and CE2, that is, sufficiently high water resistance was exhibited. Glass sample according to Comparative Example CE1 and CE2 contains no BiF _3. For this reason, it is considered that the reason why the sufficiently high water resistance was obtained is that BiF ₃ modified the network structure in the process of producing the glass sample.

  FIGS. 6A to 6F show, at an equal magnification, the state after the main firing of the bonding glass paste PT according to Examples H12 to H14 and L12 to L14. As shown in FIGS. 6 (a) to 6 (f), all the examples showed sufficient fluidity.

Further, Examples H12, H13, L12 and L13 show higher fluidity than Examples H14 and L14. The coagulated bodies according to Examples H12, H13, L12, and L13 contain more BiF ₃ than the coagulated bodies according to Examples H14 and L14.

From this, it is considered that the fluidity during firing of the bonding glass paste PT can be adjusted by the content of BiF ₃ . That is, when high fluidity is desired, the content of BiF ₃ is preferably high, and when it is desired to suppress fluidity, the content of BiF ₃ may be reduced.

  The embodiments and examples have been described above, but the present invention is not limited to these. The above embodiments and examples are for explaining the present invention, and do not limit the scope of the present invention. The scope of the invention is indicated by the claims. Various modifications made within the scope of the claims and equivalents thereto are considered to be within the scope of the present invention.

  The glass and glass paste according to the present invention are particularly suitable for use in joining a first member and a second member. However, the uses of the glass and the glass paste according to the present invention are not limited to bonding. The glass and the glass paste according to the present invention can be used for all applications that require a low melting point.

P1, P2 ... endothermic peak,
PT… Glass paste for bonding (glass paste),
S1: first glass substrate (first member),
S2: Second glass substrate (second member).

Claims (10)

A metal oxide constituting a network structure,
A halide in an amount of 100% by mass or less based on 100% by mass of the metal oxide;
Including, glass. The halide is a fluoride,
The glass according to claim 1. The fluoride is BiF ₃ ;
The glass according to claim 2. The content of the halide is not less than 5% by mass and not more than 66.7% by mass in an outer appearance with respect to 100% by mass of the metal oxide.
The glass according to any one of claims 1 to 3. The metal oxide comprises V ₂ O ₅ and TeO ₂ ;
The glass according to any one of claims 1 to 4. In the metal oxide, the mass ratio defined by the mass of the V ₂ O ₅ / the mass of the TeO ₂ is 1/8 or more and 5/4 or less.
The glass according to claim 5. A frit made of the glass according to any one of claims 1 to 6,
A binder solution;
Containing, glass paste. A raw material composition containing a metal oxide constituting a network structure and a halide in an amount of 100% by mass or less based on 100% by mass of the metal oxide is heated at a temperature of 1000 ° C. or less for 30 minutes or less. A melting step of melting by heating,
A cooling step of cooling a melt obtained by melting the raw material composition,
A method for producing glass, comprising: In the melting step, the raw material composition is melted by heating at a temperature of 700 ° C or less for a time of 15 minutes or less,
A method for producing the glass according to claim 8. After the cooling step, a pulverizing step of pulverizing a glass body obtained by cooling the melt,
The method for producing glass according to claim 8, further comprising: