JP2015166289A - glass or crystallized glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass that has a low mean linear expansion coefficient.SOLUTION: Provided is a glass containing, in mole %, POconstituent by 16% or more and 50% or less, one or more constituent among NbOconstituent and TiOconstituent in sum by 10% or more and 70% or less, and a RO constituent in sum by 1% or more and 55% or less, and having a mean linear expansion coefficient at -30°C to 70°C of 80×10/°C or less, per glass total material amount in terms of oxide converted composition (here, R is one or more selected from a group consisting of Zn, Mg, Ca, Sr and Ba.).

Description

  The present invention relates to a glass or crystallized glass having a low average linear expansion coefficient.

  Glass having a low average linear expansion coefficient (also referred to as expansion coefficient in the present specification) is used for decoration, insulation, and prevention of various base materials such as substrate materials, heat-resistant glass, metals and ceramics in the field of precision equipment. It is used in a wide range of fields such as coating materials for imparting various functions such as rust.

As glass having a low expansion coefficient, silicate glass mainly containing a large amount of SiO ₂ component is known. The SiO ₂ component is a component that contributes to low expansion of the glass. For example, the glass for tungsten sealing described in Patent Document 1, the glass for display having heat resistance described in Patent Document 2, and the glass for anodic bonding disclosed in Patent Documents 3 and 4 can be mentioned. These glasses have an average coefficient of linear expansion from 30 to 380 ° C. or from room temperature to 300 ° C. of 40 × 10 ⁻⁷ / ° C. or less, but contain a large amount of SiO ₂ component that increases the melting temperature of the glass as 50 wt% or more. Yes. Therefore, the viscosity of the glass in the liquid phase in the production process is increased, and the melting temperature needs to be increased to 1500 ° C. or higher in order to homogenize the glass. Therefore, the production of these glasses is difficult and the production cost tends to increase.
In addition, since these glasses have a high softening point, there is also a problem that they are not suitable for applications that require a low working temperature such as coating and sealing.

JP 2007-39334 A JP 2000-44278 A JP-A-7-53235 JP 2001-72433 A

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a glass or crystallized glass that can be melted at a relatively low temperature and has a low average linear expansion coefficient.

As a result of intensive studies in view of the above problems, the present inventor has prescribed the content range of the specific component not by the existing silicate glass composition but by the phosphate glass composition. The present invention has been completed by finding out to solve the problems, and the specific configuration thereof is as follows.
That is, the present invention resides in the following (1) to (9).
(1) 16% or more and 50% or less of the P ₂ O ₅ component, and one or more components among the Nb ₂ O ₅ component and the TiO ₂ component in mol% with respect to the total amount of glass in the oxide conversion composition. Glass (R is at least one selected from the group consisting of Zn, Mg, Ca, Sr and Ba) containing 10% or more and 70% or less in total, and containing RO component in 1% or more and 55% or less in total ).
(2) With respect to the total amount of glass in an oxide conversion composition, the total amount of one or more of the SiO ₂ component, B ₂ O ₃ component and Al ₂ O ₃ component is 0% or more and 20% in mol%. % Glass or less according to (1).
(3) With respect to the total amount of glass in an oxide conversion composition, the total amount of one or more of TiO ₂ component, ZrO ₂ component, SnO ₂ component and WO ₃ component is 0% or more and 60% in mol%. % Or less of the glass according to (1) or (2).
(4) The glass according to any one of (1) to (3), containing 0% to 30% of the total amount of the Rn ₂ O component in mol% with respect to the total amount of the glass having an oxide equivalent composition. (Rn is one or more selected from the group consisting of Li, Na, K, Rb and Cs).
(5) Containing 3% or more and 50% or less of the total amount of one or more of the ZnO component and the MgO component in mol% with respect to the total amount of glass in the oxide conversion composition (4) ).
(6) Crystallized glass produced by heat-treating the glass according to any one of (1) to (5).
(7) Glass or crystallized glass in any one of (1) to (6) whose average linear expansion coefficient in -30 degreeC-70 degreeC is 80x10 < ^-7 > / degrees C or less.
(8) A filler containing the glass or crystallized glass according to any one of (1) to (7).
(9) A sealing composition containing the glass or crystallized glass according to any one of (1) to (7).

According to the present invention, it is possible to obtain a phosphate-based glass or crystallized glass having a low average linear expansion coefficient that is 80 × 10 ⁻⁷ / ° C. or lower at −30 ° C. to 70 ° C. In addition, the present invention can be produced at low cost because the melting temperature is much lower than that of existing silicate glass having low expansion.
Since the glass or crystallized glass of the present invention has a low average linear expansion coefficient, for example, precision equipment, fillers for adjusting the average linear expansion coefficient of sealing materials, fire protection glass, top plates of electric ranges, and gas ranges. It can be used for products that require heat resistance, such as top plates, anodic bonding materials, and sealing materials for electronic materials.
The glass or crystallized glass of the present invention can be used for applications that do not necessarily require low expansion, such as optical glass, and can be used for a wide range of applications other than optical glass, such as photocatalytic materials. it can.

It is the figure which showed the change of the average linear expansion coefficient at the time of changing the compounding quantity of the glass of this Example 4 when the glass of Example 4 of this invention is used as a filler.

Hereinafter, embodiments of the present invention will be described in detail.
[About components contained in glass or crystallized glass of the present invention]
In the present specification, unless otherwise specified, the content of each component constituting the glass is all expressed as “mol% with respect to the total substance amount of the oxide equivalent composition”. Here, the “oxide equivalent composition” means that the oxide, composite salt, metal fluoride, etc. used as a raw material for the glass constituting the glass or crystallized glass of the present invention are all decomposed when melted. When the total amount of the generated oxide is assumed to be 100 mol%, it is a composition describing each component contained in the glass.

The P ₂ O ₅ component is a glass forming component and an essential component that lowers the melting temperature of the glass. In particular, by setting the content ratio of the P ₂ O ₅ component to 16% or more, devitrification resistance is improved, and a highly stable glass can be easily obtained. Therefore, the content of the P ₂ O ₅ component is preferably 16%, more preferably 18%, and still more preferably 20%.
On the other hand, if the content of P ₂ O ₅ exceeds 50%, the expansion coefficient increases and exceeds the desired range. Therefore, the content of the P ₂ O ₅ component is preferably 50%, more preferably 45%, more preferably 40%, and still more preferably 35%.
As the P ₂ O ₅ component, for example, Al (PO ₃ ) ₃ , Ca (PO ₃ ) ₂ , Ba (PO ₃ ) ₂ , NaPO ₃ , BPO ₄ , H ₃ PO ₄ or the like can be used as a raw material.

Of the Nb ₂ O ₅ component and the TiO ₂ component, one or more components are preferably contained in a total amount of 10% to 70%.
In particular, when the total amount is 10% or more, vitrification is facilitated and the expansion coefficient is reduced. Therefore, the total amount (Nb ₂ O ₅ + TiO ₂ ) is preferably 10%, more preferably 15%, still more preferably 20%, and most preferably 22%.
On the other hand, by making this total amount 70% or less, it becomes easy to suppress the deterioration of the stability of the glass. Therefore, the total amount (Nb ₂ O ₅ + TiO ₂ ) is preferably 70%, more preferably 65%, and still more preferably 60%.

The Nb ₂ O ₅ component is a component that increases the meltability, stability, and chemical durability of the glass and decreases the expansion coefficient. The Nb ₂ O ₅ component is a component that can be optionally contained on condition that the range of the total amount (Nb ₂ O ₅ + TiO ₂ ) is satisfied. In particular, when the Nb ₂ O ₅ component is contained, the content of the Nb ₂ O ₅ component is preferably 0.1%, more preferably 1%, more preferably 2%, and still more preferably 20%.
On the other hand, when the content of the Nb ₂ O ₅ component exceeds 60%, the stability of the glass is remarkably deteriorated. Therefore, when the Nb ₂ O ₅ component is contained, the content of the Nb ₂ O ₅ component is preferably 60%, more preferably 50%, and further preferably 45%.
As the Nb ₂ O ₅ component, for example, Nb ₂ O ₅ can be used as a raw material.

The TiO ₂ component is a component that increases the meltability, stability, and chemical durability of the glass and decreases the expansion coefficient. The TiO ₂ component is a component that can be optionally contained on condition that the range of the total amount (Nb ₂ O ₅ + TiO ₂ ) is satisfied. In particular, when a TiO ₂ component is contained, the content of the TiO ₂ component is preferably 0.1%, more preferably 1%, still more preferably 3%, and most preferably 5%.
On the other hand, if the content of the TiO ₂ component exceeds 60%, vitrification becomes very difficult. Accordingly, when the TiO ₂ component is contained, the content of the TiO ₂ component is preferably 60%, more preferably 55%, and still more preferably 52%.
As the TiO ₂ component, for example, TiO ₂ or the like can be used as a raw material.

The RO (wherein R is one or more selected from the group consisting of Zn, Mg, Ca, Sr and Ba) is a component that improves the meltability and stability of the glass. In order to express the effect, the total amount of RO components is preferably 1%, more preferably 3%, and still more preferably 5%.
On the other hand, the stability of glass can be maintained by making the total amount of RO components 55% or less. Therefore, when the RO component is contained, the total amount of the RO component is preferably 55%, more preferably 50%, and still more preferably 45%.

A ZnO component is a component which improves the meltability and stability of glass, and makes an expansion coefficient small, and is a component which can be contained arbitrarily. When the ZnO component is contained, the content of the ZnO component is preferably 1%, more preferably 3%, and still more preferably 5%.
On the other hand, if the content of the ZnO component exceeds 50%, the stability of the glass is impaired and vitrification becomes difficult. Therefore, when the ZnO component is contained, the content of the ZnO component is preferably 50%, more preferably 45%, and still more preferably 40%.
For the ZnO component, for example, ZnO, Zn (PO ₃ ) ₂ , ZnSO ₄ , ZnF ₂ or the like can be used as a raw material.

The MgO component is a component that improves the meltability and stability of the glass and decreases the expansion coefficient, and can be optionally contained. When the MgO component is contained, the content of the MgO component is preferably 1%, more preferably 3%, and still more preferably 5%.
On the other hand, if the content of the MgO component exceeds 50%, the stability of the glass deteriorates. Therefore, when the MgO component is contained, the content of the MgO component is preferably 50%, more preferably 45%, and still more preferably 40%.
As the MgO component, for example, MgO, Mg (PO ₃ ) ₂ , MgCO ₃ , MgF ₂ or the like can be used as a raw material.

In the glass or crystallized glass of the present invention, since both the ZnO component and the MgO component are optional components, the total amount of these one or more components (ZnO + MgO) may be 0%, but this total amount is 3% If it is above, it will become easy to obtain a low expansion coefficient. Accordingly, when one or more of the ZnO component and the MgO component are contained, the total amount (ZnO + MgO) is preferably 3%, more preferably 5%, and even more preferably 7%.
On the other hand, if the total amount exceeds 50%, it becomes difficult to obtain glass. Accordingly, when one or more of the ZnO component and the MgO component are contained, the total amount (ZnO + MgO) is preferably 50%, more preferably 45%, more preferably 43%, still more preferably 35% (provided that 35% is excluded).

A CaO component is a component which improves the meltability and stability of glass, and is a component which can be contained arbitrarily. However, if the content of the CaO component exceeds 30%, the stability of the glass deteriorates. Therefore, when it contains a CaO component, the content of the CaO component is preferably 30%, more preferably 27%, and even more preferably 25%. As the CaO component, for example, CaCO ₃ , Ca (PO ₃ ) ₂ , CaF ₂ or the like can be used as a raw material.

A SrO component is a component which improves the meltability and stability of glass, and is a component which can be contained arbitrarily. However, when the content of the SrO component exceeds 30%, the stability of the glass is deteriorated. Therefore, when the SrO component is contained, the content of the SrO component is preferably 30%, more preferably 27%, and further preferably 25%. For the SrO component, for example, Sr (NO ₃ ) ₂ , SrF ₂ or the like can be used as a raw material.

A BaO component is a component which improves the meltability and stability of glass, and is a component which can be contained arbitrarily. However, if the content of the BaO component exceeds 30%, the stability of the glass deteriorates. Therefore, when it contains a BaO component, the content of the BaO component is preferably 30%, more preferably 27%, and even more preferably 25%. For the BaO component, for example, BaCO ₃ , Ba (PO ₃ ) ₂ , Ba (NO ₃ ) ₂ , BaSO ₄ , BaF _{2 and the} like can be used as a raw material.

SiO ₂ component constitutes the network structure of the glass, or to enhance resistance to devitrification and chemical durability of the glass and is a component which can contain arbitrarily. When the SiO ₂ component is contained, the content of the SiO ₂ component is preferably more than 0%, more preferably 0.1%, and still more preferably 0.3%.
On the other hand, when the content of the SiO ₂ component exceeds 20%, the meltability of the glass deteriorates. Accordingly, when the SiO ₂ component is contained, the content of the SiO ₂ component is preferably 20%, more preferably 15%, and still more preferably 10%.
For the SiO ₂ component, for example, SiO ₂ , K ₂ SiF ₆ , Na ₂ SiF ₆ or the like can be used as a raw material.

B ₂ O ₃ component constitutes the network structure of the glass, or to enhance the meltability and stability of glass and is a component which can contain arbitrarily. However, when the content exceeds 20%, the stability of the glass is lowered. Therefore, when it contains a B ₂ O ₃ component, the content of the B ₂ O ₃ component is preferably 20%, more preferably 10%, and even more preferably 5%. For the B ₂ O ₃ component, for example, H ₃ BO ₃ , Na ₂ B ₄ O ₇ , Na ₂ B ₄ O ₇ .10H ₂ O, BPO ₄ or the like can be used as a raw material.

The Al ₂ O ₃ component is a component that enhances the meltability and stability of the glass, and can be optionally contained. When the Al ₂ O ₃ component is contained, the content is preferably 0.1%, more preferably 0.5%, and even more preferably 1%, in order to express the effect of the component.
On the other hand, if the content exceeds 20%, the devitrification resistance of the glass is lowered and vitrification becomes difficult. Therefore, when it contains an Al ₂ O ₃ component, the content of the Al ₂ O ₃ component is preferably 20%, more preferably 15%, and even more preferably 10%.
On the other hand, for the Al ₂ O ₃ component, for example, Al ₂ O ₃ , Al (OH) ₃ , AlF ₃ or the like can be used as a raw material.

In the glass or crystallized glass of the present invention, all of the SiO ₂ component, the B ₂ O ₃ component and the Al ₂ O ₃ component are optional components, so the total amount of these one or more components (SiO ₂ + B ₂ O ₃ + Al ₂ O ₃ ) may be 0%, but by setting the total amount to 0.1% or more, devitrification resistance can be improved and glass can be easily obtained. Of the SiO ₂ component, the B ₂ O ₃ component, and the Al ₂ O ₃ component, the SiO ₂ component is a component that improves devitrification resistance, and therefore is used in combination with the B ₂ O ₃ component and the Al ₂ O ₃ component. As a result, the effect is more prominently exhibited. Therefore, when it contains one or more components among SiO ₂ component, B ₂ O ₃ component and Al ₂ O ₃ component, the total amount (SiO ₂ + B ₂ O ₃ + Al ₂ O ₃ ) is preferably 0.1. %, More preferably 0.3%, still more preferably 0.5%, and most preferably 1%.
On the other hand, if the total amount exceeds 20%, it becomes difficult to obtain glass. Therefore, when it contains one or more components among SiO ₂ component, B ₂ O ₃ component and Al ₂ O ₃ component, the total amount (SiO ₂ + B ₂ O ₃ + Al ₂ O ₃ ) is preferably 20%, The upper limit is more preferably 15%, and still more preferably 10%.

The ZrO ₂ component is a component that increases the meltability, devitrification resistance, and chemical durability of the glass and decreases the expansion coefficient, and can be optionally contained. However, if the content of the ZrO ₂ component exceeds 15%, vitrification becomes difficult. Therefore, when the ZrO ₂ component is contained, the content of the ZrO ₂ component is preferably 15%, more preferably 10%, and still more preferably 8%. For the ZrO ₂ component, for example, ZrO ₂ , ZrF ₄ or the like can be used as a raw material.

The SnO ₂ component is a component that increases the meltability, devitrification resistance and chemical durability of the glass and decreases the expansion coefficient, and can be optionally contained. However, when the content of these components exceeds 15%, vitrification becomes difficult. Therefore, when the SnO ₂ component is contained, the content of the SnO ₂ component is preferably 15%, more preferably 10%, and still more preferably 8%. For the SnO ₂ component, for example, SnO, SnO ₂ , SnO ₃ or the like can be used as a raw material.

The WO ₃ component is a component that increases the meltability, devitrification resistance, and chemical durability of the glass and decreases the expansion coefficient, and can be optionally contained. However, when the content of these components exceeds 20%, vitrification becomes difficult. Therefore, when the WO ₃ component is contained, the content of the WO ₃ component is preferably 20%, more preferably 10%, and still more preferably 8%.

In the glass or crystallized glass of the present invention, since any of TiO ₂ component, ZrO ₂ component, SnO ₂ component and WO ₃ is an optional component, the total amount of these one or more components (TiO ₂ + ZrO ₂ + SnO ₂₎ + WO ₃ ) may be 0%, but if this total amount exceeds 0%, the expansion coefficient can be reduced. Therefore, when one or more of TiO ₂ component, ZrO ₂ component, SnO ₂ component and WO ₃ are contained, this total amount is preferably more than 0%, more preferably 1%, still more preferably 3 % Is the lower limit.
On the other hand, when this total amount exceeds 60%, the devitrification resistance of the glass is lowered and vitrification becomes difficult. Therefore, when one or more of TiO ₂ component, ZrO ₂ component, SnO ₂ component and WO ₃ are contained, the total amount (TiO ₂ + ZrO ₂ + SnO ₂ + WO ₃ ) is preferably 60%, more preferably The upper limit is 57%, more preferably 55%.
On the other hand,

The Rn ₂ O component (wherein Rn is one or more selected from the group consisting of Li, Na, K, Rb, and Cs) is a component that improves the meltability and stability of the glass and can be optionally contained. It is an ingredient. When the Rn ₂ O component is contained, the total amount for expressing the effect is preferably 0.1%, more preferably 0.5%, and still more preferably 1%.
On the other hand, when the total amount of the Rn ₂ O component exceeds 30%, it becomes difficult to obtain a desired average linear expansion coefficient. Therefore, when the Rn ₂ O component is contained, the total amount of the Rn ₂ O component is preferably 30%, more preferably 20%, and even more preferably 15%.

Li 2 _O component is a component that improves the meltability and stability of glass and is a component which can contain arbitrarily.
On the other hand, if the content of the Li ₂ O component exceeds 30%, it becomes difficult to obtain a desired average linear expansion coefficient. Therefore, when it contains a Li ₂ O component, the content of the Li ₂ O component is preferably 30%, more preferably 20%, and even more preferably 15%. As the Li ₂ O component, for example, Li ₂ CO ₃ , LiPO ₃ , LiNO ₃ , LiF, or the like can be used as a raw material.

Na 2 _O component is a component that improves the meltability and stability of glass and is a component which can contain arbitrarily. However, when the content of the Na ₂ O component exceeds 30%, it becomes difficult to obtain a desired average linear expansion coefficient. Therefore, if containing Na ₂ O component, the Na ₂ O content component, preferably 30%, more preferably 20%, more preferably to a maximum of 15%. As the Na ₂ O component, for example, Na ₂ O, Na ₂ CO ₃ , NaH ₂ PO ₄ , NaNO ₃ , NaF, Na ₂ S, Na ₂ SiF ₆ or the like can be used as a raw material.

K 2 _O component is a component that improves the meltability and stability of glass and is a component which can contain arbitrarily. However, when the content of the K ₂ O component exceeds 30%, it becomes difficult to obtain a desired average linear expansion coefficient. Therefore, when it contains a K ₂ O component, the content of the K ₂ O component is preferably 30%, more preferably 20%, and even more preferably 15%. As the K ₂ O component, for example, K ₂ CO ₃ , NaH ₂ PO ₄ , KNO ₃ , KF, KHF ₂ , K ₂ SiF _{6 and the} like can be used as a raw material.

The Rb ₂ O component is a component that improves the meltability and stability of the glass, and can be optionally contained. Further, it is a component that lowers the glass transition temperature and lowers the heat treatment temperature. However, when the content of the Rb ₂ O component exceeds 20%, the stability of the glass deteriorates. Therefore, when it contains an Rb ₂ O component, the content of the Rb ₂ O component is preferably 30%, more preferably 20%, and even more preferably 15%. For the Rb ₂ O component, for example, Rb ₂ CO ₃ , RbNO ₃ or the like can be used as a raw material.

Cs 2 _O component is a component that improves the meltability and stability of glass and is a component which can contain arbitrarily. However, when the content of the Cs ₂ O component exceeds 20%, the stability of the glass is deteriorated. Therefore, when it contains a Cs ₂ O component, the content of the Cs ₂ O component is preferably 30%, more preferably 20%, and even more preferably 15%. For the Cs ₂ O component, for example, Cs ₂ CO ₃ , CsNO ₃ or the like can be used as a raw material.

In the glass or crystallized glass of the present invention, any of the Sb ₂ O ₃ component, the F component and the S component can be optionally contained. However, when a highly homogeneous bulk form without bubbles is obtained, Sb _{2 is} used as a defoaming agent. It is preferable to contain one or more components among the O ₃ component, the F component, and the S component. When one or more of Sb ₂ O ₃ component, F component and S component are contained, the total amount of these components (Sb ₂ O ₃ + F + S) is preferably 0.001 in order to obtain a desired effect. %, More preferably 0.005%, and still more preferably 0.01%.
On the other hand, when the total amount exceeds 5%, the stability of the glass tends to be lowered. Accordingly, when one or more of Sb ₂ O ₃ component, F component and S component are contained, the total amount (Sb ₂ O ₃ + F + S) is preferably 5%, more preferably 3%, and even more preferably The upper limit is 2%.
As the Sb ₂ O ₃ component, Sb ₂ O ₃ , Sb ₂ O ₅ , Na ₂ H ₂ Sb ₂ O ₇ .5H ₂ O, or the like can be used as a raw material.
As the F component, ZrF ₄ , AlF ₃ , NaF, CaF ₂ , K ₂ SiF ₆ , Na ₂ SiF ₆ , LaF ₃ or the like can be used as a raw material.
The S component is preferably a sulfate as a raw material. For example, Li ₂ SO ₄ .H ₂ O, Na ₂ SO ₄ , K ₂ SO ₄ , MgSO ₄ , CaSO ₄ .1 / 2H ₂ O, BaSO _4, SrSO ₄ , ZnSO ₄ .7H ₂ O, La ₂ (SO ₄ ) ₃ .9H ₂ O, or the like can be used.

Incidentally, components which clarified degassed glass, Sb ₂ O ₃ component, F component, is not limited to the S component. For example, in the glass or crystallized glass of the present invention, a refining agent, a defoaming agent or a combination thereof known in the production of glass or crystallized glass is arbitrarily used as a component for refining and defoaming the glass or crystallized glass. It can also be contained.

In addition, in the glass or crystallized glass of the present invention, other than the above, as long as the effect that the average linear expansion coefficient is small is not impaired for the purpose of adjusting the chemical durability, the average linear expansion coefficient, etc. or improving the meltability of the glass. These components (for example, the following components) may be appropriately contained. For example, GeO ₂ component, Ga ₂ O ₃ component, In ₂ O ₃ component, Ta ₂ O ₅ component, Bi ₂ O ₃ component, TeO ₂ component, Ln ₂ O ₃ component (wherein Ln is Sc, Y, La And at least one selected from the group consisting of Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), M _x O _y component (formula Where M is at least one selected from the group consisting of V, Cr, Mn, Fe, Co, and Ni, and x and y are minimum natural numbers satisfying x: y = 2: M valence, respectively. Here, the valence of V is 5, the valence of Cr is 3, the valence of Mn is 2, the valence of Fe is 3, the valence of Co is 2, and the valence of Ni is 2. As ₂ O ₃ component, CeO ₂ component, TeO ₂ component, non-metallic element component (including Cl component, Br component, N component, and C component) Or at least one selected from the group consisting of Cu, Ag, Au, Pd, Re, and Pt).

  However, lead compounds such as PbO, and components of Th, Cd, Tl, Os, Se, and Hg have tended to refrain from being used as harmful chemical substances in recent years. Environmental measures are required until the process and disposal after commercialization. Therefore, when importance is placed on the environmental impact, it is preferable not to substantially contain them except for inevitable mixing. As a result, the glass is substantially free from substances that pollute the environment. Therefore, this glass or crystallized glass can be manufactured, processed, and discarded without taking any special environmental measures.

The glass or crystallized glass of the present invention cannot be directly expressed in units of mass% because the composition is expressed in units of “mol% with respect to the total amount of oxide-based composition”, but is required in the present invention. The composition in units of mass% of each component present in the composition satisfying the various properties generally takes the following values in terms of oxide composition.
P ₂ O ₅ component 10 to 50 mass%,
Nb ₂ O ₅ component 0 to 80% by mass,
TiO ₂ component 0-65 mass%,
RO component 0.5-50 mass%,
(R is at least one selected from Zn, Mg, Ca, Sr and Ba)
SiO ₂ component 0 to 20% by mass,
B ₂ O ₃ component 0 to 10% by weight,
Al ₂ O ₃ component 0-20% by mass,
ZrO ₂ component 0 to 20% by mass,
SnO ₂ component 0-20 mass%,
WO ₃ components 0-30% by mass,
Rn ₂ O component 0 to 40% by mass,
(Rn is at least one selected from the group consisting of Li, Na, K, Rb and Cs)
ZnO component 0 to 40% by mass
MgO component 0-40% by mass

[About the manufacturing method of the glass of this invention]
The glass of the present invention is produced by the following melting step and cooling step.

(About melting process)
The melting step is a step of obtaining a melt by mixing raw materials having the above-described composition. More specifically, the raw materials are prepared so that each component of the glass is within a predetermined content range, and the mixture prepared by uniformly mixing is put into a platinum crucible, quartz crucible or alumina crucible, and an electric furnace Is melted in the temperature range of 1200 ° C. to 1450 ° C. for 1 to 24 hours, and stirred and homogenized to prepare a melt. The conditions for melting the raw material are not limited to the above temperature range, and can be appropriately set according to the composition and blending amount of the raw material composition.
The melting temperature of the glass raw material is preferably 1450 ° C. or lower, more preferably 1350 ° C. or lower, and most preferably 1300 ° C. or lower in order to reduce the cost of glass production and facilitate glass refining. The melting temperature of the glass of the present invention can be as low as about 1200 ° C.

(About the cooling process)
The cooling step is a step for producing the glass of the present invention by cooling and vitrifying the melt obtained in the melting step. Specifically, a vitrified glass body is formed by allowing the melt to flow out and cooling appropriately. Here, the conditions for vitrification are not particularly limited, and may be appropriately set according to the composition and amount of the raw material. Moreover, the shape of the glass body obtained by this process is not specifically limited, A plate shape, a granular form, etc. may be sufficient.

[About the crystallized glass of the present invention]
The crystallized glass of the present invention is a material obtained by precipitating a crystal phase in a glass phase by heat-treating the above-described glass of the present invention, and is also called glass ceramic. The crystallized glass may include not only a material composed of a glass phase and a crystal phase, but also a material in which the glass phase is entirely changed to a crystal phase, that is, a material whose crystal amount (crystallinity) in the material is 100% by mass. . In general, engineering ceramics and ceramic sintered bodies to which glass powder is added may also be expressed as “glass ceramics”, but it is difficult to form a pore-free completely sintered body. Therefore, the crystallized glass of the present invention can be distinguished from such glass ceramics by the presence or absence of such pores (for example, pores). On the other hand, the crystallized glass of the present invention can control the crystal grain size, the type of crystal precipitated, and the degree of crystallinity by controlling the glass composition and the crystallization process.

[Method for producing crystallized glass of the present invention]
Next, the manufacturing method of the crystallized glass of the present invention will be described by illustrating specific steps. However, the manufacturing method of the crystallized glass of this invention is not limited to the method shown below.

  The method for producing crystallized glass of the present invention comprises the steps of obtaining the glass of the present invention, a reheating step of raising the temperature of the glass to the crystallization temperature region, and maintaining the temperature within the crystallization temperature region. A crystallization step for generating crystals, and a recooling step for reducing the temperature to outside the crystallization temperature region to obtain crystallized glass.

(About reheating process)
The reheating step is a step of raising the temperature of the glass of the present invention obtained in the cooling step to the crystallization temperature region.

(About crystallization process)
The crystallization step is a step of generating crystals by holding for a predetermined time in the crystallization temperature region. The crystallization temperature region is, for example, a temperature region exceeding the glass transition temperature. The lower limit of the preferable crystallization temperature region is 500 ° C, more preferably 550 ° C, and further preferably 580 ° C. On the other hand, when the crystallization temperature becomes too high, the tendency of the crystal phase other than the target to precipitate becomes strong. Therefore, the upper limit of the crystallization temperature region is preferably 1100 ° C, more preferably 1000 ° C, and still more preferably 900 ° C. The crystallization process may go through a one-stage heat treatment process, or may go through two or more heat treatment processes. The heat treatment process of two or more steps here is not only a process in which heat treatment is performed n times (n is 1 or more) at another temperature after heat treatment at a predetermined temperature. It also includes a process of performing heat treatment n times (n is 1 or more) at a predetermined temperature after the temperature is lowered by performing a heat treatment process in stages.

(About re-cooling process)
The recooling step is a step of obtaining crystallized glass by lowering the temperature outside the crystallization temperature region after crystallization is completed.

[Physical properties of the glass or crystallized glass of the present invention]
(About average linear expansion coefficient)
The average linear expansion coefficient of the glass or crystallized glass of the present invention is preferably 80 × 10 ⁻⁷ / ° C. or less at −30 to 70 ° C. in order to be preferably applicable to various applications, and 70 × 10 ⁻⁷ / More preferably, it is 65 degrees C < ^-7 > / degrees C or less.
The average linear expansion coefficient (10 ⁻⁷ / ° C.) of the glass or crystallized glass of the present invention is measured according to Japan Optical Glass Industry Association Standard JOGIS16-2003 “Measuring Method of Average Linear Expansion Coefficient of Optical Glass Near Room Temperature”. It is an average linear expansion coefficient in -30 degreeC-70 degreeC.

(About glass transition point (Tg) and yield point (At))
The glass transition point (Tg) and the yield point (At) are one of indices indicating the low temperature softening property of glass.
The Tg (° C.) of the glass of the present invention is preferably 700 ° C., more preferably 680 ° C., and further preferably 670 ° C. in order to be preferably applicable to various applications. In addition, although the minimum of Tg (degreeC) of the glass of this invention is not specifically limited, Tg of the glass of this invention is good also considering 300 degreeC as a minimum.
The At (° C.) of the glass of the present invention is preferably 750 ° C., more preferably 730 ° C., and even more preferably 710 ° C. in order to be preferably applicable to various applications. In addition, although the minimum of At (degreeC) of the glass of this invention is not specifically limited, As for At of the glass of this invention, it is good also considering 330 degreeC as a minimum.
In addition, Tg (degreeC) and At (degreeC) of the glass of this invention measure the relationship between temperature and the elongation of a sample according to Japan Optical Glass Industry Association standard JOGIS08-2003 "Measurement method of thermal expansion of optical glass". It is temperature (degreeC) calculated | required from the thermal expansion curve obtained by this.

(Chemical durability)
The glass or crystallized glass of the present invention preferably has chemical durability when applied to applications that require long-term reliability, for example, a composition for sealing electronic components mounted on precision equipment or the like. . For example, the glass or crystallized glass of the present invention functions as a sealing composition for a long period of time even in an environment where a temperature difference is likely to occur due to high humidity and in an environment where condensation is likely to occur or in an environment where it is exposed to acidic rain for a long time. It is preferable that it can be maintained. Here, “chemical durability” refers to durability against water erosion of glass (water resistance) or durability against acid erosion of glass (acid resistance).
The water resistance of the glass or crystallized glass of the present invention is preferably class 3 to 1, more preferably class 2 to 1, further preferably class 1 in order to be applicable to various uses. . “Water resistance is class 3 to 1” means that the water resistance measured according to JOGIS06-1999 is less than 0.25 wt% in terms of weight loss of the sample before and after measurement. In class 1, the weight loss rate of the sample before and after the measurement is less than 0.05 wt%, class 2 is 0.05 wt% or more and less than 0.10 wt%, and class 3 is 0.10 wt% or more and 0 Less than 25 wt%.
The water resistance of the glass or crystallized glass of the present invention is preferably class 4 to 1, more preferably class 3 to 1, more preferably class 2 to 1, in order to be applicable to various uses. More preferably, it is class 1. “Acid resistance is class 4 to 1” means that the acid resistance measured according to JOGIS06-1999 is a weight loss rate of the sample before and after measurement and is less than 1.20 wt%. In class 1, the weight loss rate of the sample before and after measurement is less than 0.20 wt%, class 2 is 0.20 wt% or more and less than 0.35 wt%, and class 3 is 0.35 wt% or more and 0 Less than .65 wt%, class 4 is 0.65 wt% or more and less than 1.20 wt%.

[Other]
In the method for producing glass or crystallized glass of the present invention, the glass or crystallized glass can be processed into an arbitrary shape by providing a molding step such as polishing or grinding as necessary.

  The glass or crystallized glass of the present invention includes, for example, fluorescent display tube-package sealing, insulating layer formation, plasma display-panel hermetic sealing, insulating layer and dielectric layer formation, barrier rib formation, magnetic head -It can be used as a seal between cores or between a core and a slider. Moreover, the form at the time of use does not have a restriction | limiting in particular, What is necessary is just to shape | mold and use it in various forms according to the use, such as powder form, plate shape, rod shape.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to a following example.

Examples 1-38:
Tables 1 to 6 show the compositions and physical properties of the glasses of Examples 1 to 38 of the present invention. The glasses of Examples 1 to 38 are all used for ordinary glasses such as oxides, hydroxides, carbonates, nitrates, fluorides, chlorides, and metaphosphate compounds corresponding to the raw materials of the respective components. Purity raw materials were selected and used. These raw materials are weighed so as to have the composition ratios of the respective examples shown in Tables 1 to 6 and mixed uniformly, and then charged into a quartz crucible or a platinum crucible, and depending on the melting difficulty of the glass composition. It melt | dissolved in the temperature range of 1200 to 1450 degreeC with an electric furnace for 1 to 24 hours, and homogenized by stirring, and foaming etc. were performed. Thereafter, a glass melt was cast into a mold and gradually cooled to produce amorphous glass. In each Example, it was possible to melt completely at a temperature of 1450 ° C. or less, and a glass melt could be produced.

As seen in Tables 1 to 6, the glasses of Examples 1 to 38 of the present invention have an average linear expansion coefficient of 64 × 10 ⁻⁷ / ° C. or less. In addition, about the glass of Examples 5-38 of this invention, although the glass transition point (Tg) and the yield point (At) were measured, Tg (degreeC) is 545 to 639 degreeC, and At (degreeC) is It was 590 degreeC-700 degreeC.

Examples 39-48:
Tables 7 and 8 show the compositions and physical properties of the crystallized glasses of Examples 39 to 48 of the present invention.
The crystallized glasses of Examples 39 to 48 are all used as ordinary materials such as oxides, hydroxides, carbonates, nitrates, fluorides, chlorides, and metaphosphate compounds as raw materials for the respective components. High-purity raw materials were selected and used. These raw materials were weighed so as to have the composition ratios of the respective examples shown in Tables 7 and 8 and mixed uniformly, and then put into a quartz crucible or a platinum crucible, and according to the melting difficulty of the glass composition. It melt | dissolved in the temperature range of 1200 to 1450 degreeC with an electric furnace for 1 to 24 hours, and homogenized by stirring, and foaming etc. were performed. In each Example, it was possible to melt completely at a temperature of 1450 ° C. or less, and a glass melt could be produced.
Thereafter, a glass melt was cast into a mold and slowly cooled to produce glass. The obtained glass was polished, and the glass was crystallized under the heat treatment conditions described in Examples of Tables 7 and 8. In more detail, the obtained glass was polished and heated to the temperature (° C.) described in each Example of Tables 7 and 8, and the time (hr) described in each Example of Tables 7 and 8 The glass was crystallized by maintaining at this temperature (° C.) for a long time. Then, it cooled from this temperature (degreeC) and crystallized glass was obtained.

As seen in Tables 7 and 8, the crystallized glass of Examples 39 to 48 of the present invention has an average coefficient of linear expansion of 60 × 10 ⁻⁷ / ° C. or less.

In addition, the following titles described in Tables 1 to 8 represent the following contents (mol%).
P ₂ O _5: the content of _P 2 _{O 5} component _{Nb 2 O 5: Nb 2 O} 5 ingredient content ZnO: content of ZnO component MgO: the content of MgO component CaO: CaO content component SrO: SrO the content of the component BaO: BaO content components _SiO 2: SiO ₂ content component _{B 2 O 3: B 2 O} 3 component of the content _{Al 2 O 3: Al 2 O} 3 ingredient content _TiO 2: TiO the content of the _two components _ZrO 2: content of ZrO ₂ component _SnO 2: SnO ₂ content component _WO 3: the content of WO ₃ components _Li 2 O: Li ₂ O content components _Na 2 O: _Na 2 O the content of the component _K 2 O: _{K 2} O content component _Nb + Ti: Nb 2 _{O 5} component and the total content of TiO ₂ component RO: RO component (wherein, R Zn, Mg, Ca, Sr and Ba One selected from the group The total content of the upper) component Si + B + Al: total content of SiO ₂ component and _B 2 _{O 3} component and _Al 2 _{O 3} component Ti + Zr + Sn + W: the total content of TiO ₂ component and ZrO ₂ component and SnO ₂ component and WO ₃ components Rn ₂ O: Rn ₂ O component (wherein Rn is one or more selected from the group consisting of Li, Na, K, Rb and Cs) Zn + Mg: Total content of ZnO component and MgO component The following titles listed in Tables 1 to 8 indicate the following physical properties of the glass or crystallized glass of the examples.
α (× 10 ⁻⁷ / ° C.): Average linear expansion coefficient (× 10 ⁻⁷ / ° C.) at −30 ° C. to 70 ° C.

(Chemical durability)
Regarding the glass or crystallized glass of Examples 1 to 48 of the present invention, the water resistance and acid resistance were measured according to JOGIS06-1999, a standard for measuring the chemical durability of optical glass by the Japan Optical Glass Industry Association. Was also class 1 and acid resistance was also class 1. Therefore, this measurement showed that the glass or crystallized glass of Examples 1 to 48 of the present invention has excellent water resistance and acid resistance.

(Preparation of sealing composition (molded body))
Since the glass or crystallized glass of the present invention has an expansion coefficient close to that of a metal such as tungsten or Kovar, it can be used for sealing these metals. Further, since it is possible to obtain the same expansion coefficient as that of silicon crystal, it is useful as a silicon crystal plate and anodic bonding glass.
Moreover, the adjustment of an expansion coefficient and improvement of chemical durability become remarkable by mix | blending the glass or crystallized glass of this invention with the existing low melting-point sealing glass as a filler. By adding the glass or crystallized glass of the present invention having a small expansion coefficient as a filler to the existing low melting point sealing glass having a high expansion coefficient, the expansion coefficient of the low melting point sealing glass can be reduced. is there. Below, it shows that the glass or crystallized glass of the present invention functions as a filler.

Phosphoric acid-based (P ₂ O ₅ —ZnO—BaO—CaO—Al ₂ O ₃ -based) glass powder, which is well known as a low-melting sealing glass, and glass powder having the composition of Example 4 of the present invention as a filler (Glass powder of Example 4) was used. This P ₂ O ₅ —ZnO—BaO—CaO—Al ₂ O ₃ -based glass is mol%, P ₂ O ₅ component is 44%, ZnO component is 45%, BaO component is 5%, and CaO is 5%. and _Al 2 _{O 3} component is contained 1%, Tg is 450 ° C., an average linear expansion coefficient of -30 ° C. to 70 ° C. is 92 × ^{10 -7} / ℃, glass.
A predetermined amount of the glass powder of Example 4 was blended into the P ₂ O ₅ —ZnO—BaO—CaO—Al ₂ O ₃ glass powder, mixed well, and then press-molded to form three cylindrical columns having a diameter of 10 mm. Molded bodies (Sample 1, Sample 2, Sample 3) were produced. The breakdown of Samples 1 to 3 is as follows.
Sample 1: Molded body sample 2 in which the glass powder of Example 4 is not blended Sample 2: The glass powder of Example 4 is 15 wt% with respect to the P ₂ O ₅ —ZnO—BaO—CaO—Al ₂ O ₃ glass powder. % Of the molded body sample 3: P ₂ O ₅ —ZnO—BaO—CaO—Al ₂ O ₃ -based glass powder containing 30 wt% of the glass powder of Example 4

About the obtained molded object, it baked for 10 minutes in the range of 500 to 550 degreeC in air | atmosphere. The result of having measured the average linear expansion coefficient ( ^x10 < ^-7 > / degreeC) in -30 degreeC-70 degreeC about each sample after baking is shown in FIG. The average linear expansion coefficient at −30 ° C. to 70 ° C. of sample 1 is 92 × 10 ⁻⁷ / ° C., whereas the average linear expansion coefficient at −30 ° C. to 70 ° C. of sample 2 is 79 × 10 ⁻⁷ / ° C. The average linear expansion coefficient of Sample 3 at −30 ° C. to 70 ° C. was 72 × 10 ⁻⁷ / ° C. Thereby, it became clear that the glass or crystallized glass of the present invention functions as a filler and is effective in controlling the expansion coefficient of the existing low melting point sealing glass.

  As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not restrict | limited to the said embodiment. Those skilled in the art can make many modifications without departing from the spirit and scope of the present invention, and these are also included within the scope of the present invention.

Claims (9)

The glass the total amount of substance of the oxide composition in terms of a _{molar%, P 2 O 5 50%} 16% or more of the components below, one or more components of _Nb 2 _{O 5} component and TiO ₂ component in total Glass containing 10% or more and 70% or less and RO component in a total amount of 1% or more and 55% or less (R is one or more selected from the group consisting of Zn, Mg, Ca, Sr and Ba). 1% or more of SiO ₂ component, B ₂ O ₃ component and Al ₂ O ₃ component are contained in a total amount of 0% or more and 20% or less in mol% with respect to the total amount of glass of oxide conversion composition The glass according to claim 1. Containing 0% or more and 60% or less of the total amount of one or more of TiO ₂ component, ZrO ₂ component, SnO ₂ component and WO ₃ component in mol% with respect to the total amount of glass of oxide conversion composition The glass according to claim 1 or 2. The glass according to any one of claims 1 to 3, comprising a total amount of Rn ₂ O components of 0% or more and 30% or less in terms of mol% with respect to the total amount of glass having an oxide equivalent composition. One or more selected from the group consisting of Li, Na, K, Rb and Cs).   5. The composition according to claim 1, wherein the total amount of the glass having an oxide conversion composition is at least 1% of ZnO component and MgO component in mol%, and the total amount is 3% or more and 50% or less. Glass according to item.   Crystallized glass produced by heat-treating the glass according to any one of claims 1 to 5. The glass or crystallized glass according to any one of claims 1 to 6, wherein an average linear expansion coefficient at -30 ° C to 70 ° C is 80 × 10 ^-7 / ° C or less.   The filler containing the glass or crystallized glass of any one of Claim 1 to 7.   The sealing composition containing the glass or crystallized glass of any one of Claim 1 to 7.

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