JP4375982B2 - Organic-inorganic hybrid glassy material and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a new glassy substance starting from a gel produced by a sol-gel method and a substance produced by an acid-base reaction method, and a method for producing the same.
[0002]
[Prior art]
As materials that soften at 600 ° C. or lower, polymer materials and low-melting glass are well known, and have been used in many places such as sealing and sealing materials, passivation glasses, glazes, and the like. Polymer materials and low-melting glass have different physical properties, so they have been used properly according to the environment in which they can be used. In general, glass is used when heat resistance and hermetic performance are prioritized, and organic materials represented by polymer materials are used in fields where properties other than heat resistance and hermetic performance are prioritized. However, along with recent technological progress, attention has been paid to properties that have not been required so far, and development of materials having such properties is expected.
[0003]
For this reason, the development of polymer materials with increased heat resistance and airtight performance and so-called low-melting glass, which is a glass with a softened region lowered in temperature, has been actively carried out. Especially in the electronic materials market where heat resistance and airtightness are required, low melting point glass such as PbO-SiO ₂ -B ₂ O ₃ or PbO-P ₂ O ₅ -SnF ₂ It is an indispensable material in fields such as sealing and coating. In addition, the low melting point glass can reduce the energy required for the molding process and the cost compared to the high temperature molten glass, and therefore, it meets the recent social demand for energy saving. Furthermore, if it can be melted at a temperature that does not destroy the organic substance having optical functional performance, it can be expected to be applied to an optical information communication device such as an optical switch as a host of the optical functional organic substance-containing (nonlinear) optical material. As described above, materials having heat resistance and airtightness, which are the characteristics of general molten glass, and easily obtaining various properties such as polymer materials are demanded in many fields. Expectations are gathered. Furthermore, organic-inorganic hybrid glass is also attracting attention as one of low-melting glass.
[0004]
As the low melting point glass, for example, Tick glass represented by Sn-Pb-PFO glass (for example, see Non-Patent Document 1) is famous, and has a glass transition point around 100 ° C., and is excellent. It has been used in some markets due to its water resistance. However, since this low melting point glass contains lead as a main component, it is necessary to replace it with an alternative material from the recent trend of environmental protection. Furthermore, the required characteristics for Tick glass have changed greatly, and at the same time the demands have diversified.
[0005]
As a general glass production method, a melting method and a low-temperature synthesis method are known. The melting method is a method in which a glass raw material is directly heated to be melted and vitrified. Many glasses are produced by this method, and low-melting glass is also produced by this method. However, in the case of a low-melting glass, there are many restrictions on the glass composition that can be constructed, such as the need to contain lead, alkali, bismuth, etc. in order to lower the melting point.
[0006]
On the other hand, as a low-temperature synthesis method of amorphous bulk, a sol-gel method, a liquid phase reaction method, and an acid anhydride base reaction method are considered. In the sol-gel method, a bulk body can be obtained by hydrolysis-polycondensation of metal alkoxide and the like, and heat treatment at a temperature exceeding 500 ° C. (for example, see Non-Patent Document 2), usually 700 to 1600 ° C. However, when the bulk material produced by the sol-gel method is viewed as a practical material, it is porous due to the decomposition and combustion of organic substances such as alcohol introduced during the preparation of the raw material solution, or evaporative emission during the heating process of the decomposition gas or water of organic substances. In many cases, there were problems in heat resistance and airtightness. As described above, many problems still remain in bulk production by the sol-gel method, and in particular, low-melting glass has not been produced by the sol-gel method.
[0007]
In addition, the liquid phase reaction method has a low yield, resulting in low productivity, the use of hydrofluoric acid in the reaction system and the limited synthesis of thin films. It is almost impossible to synthesize.
[0008]
The anhydride-base reaction method is a technique developed in recent years, and it is possible to produce an organic-inorganic hybrid glass that is one of low-melting glasses (for example, see Non-Patent Document 3), but it is still under development. Not all low-melting glasses can be made.
[0009]
Therefore, many low-melting-point glasses have been manufactured not by a low-temperature synthesis method but by a melting method. For this reason, the glass composition is limited for the convenience of melting the glass raw material, and the kind of the low melting glass that can be produced is extremely limited.
[0010]
At present, low-melting glass is a promising material due to heat resistance and airtightness, and required physical properties are often obtained in a form typified by low-melting glass. However, the material is not particular about the low melting point glass, and if the required physical properties match, there is no major problem with a low melting point or low softening point substance other than glass.
[0011]
From a known technique, a method for producing quartz glass fibers by the sol-gel method (for example, see Patent Document 1), a method for producing titanium oxide fibers by the sol-gel method (for example, see Patent Document 2), and further a semiconductor by the sol-gel method. A method for manufacturing a dope matrix (see, for example, Patent Document 3) is disclosed. Further, P ₂ O ₅ —TeO ₂ —ZnF ₂ -based low-melting glass by a melting method is disclosed (for example, see Patent Document 4).
[0012]
[Patent Document 1]
JP 62-297236 A [Patent Document 2]
JP 62-223323 [Patent Document 3]
Japanese Patent Laid-Open No. 1-183438 [Patent Document 4]
Japanese Patent Laid-Open No. 7-126035 [Non-Patent Document 1]
PATick, Physics and Chemistry of Glasses, vol.25 No.6, pp.149-154 (1984).
[Non-Patent Document 2]
Kamiya, K., Sakuhana, K., Tashiro, No., Journal of Ceramic Association, pp.614-618, 84 (1976).
[Non-Patent Document 3]
Masahide Takahashi, Haruki Niida, Toshinobu Yokoo, New Glass, pp.8-13, 17 (2002).
[0013]
[Problems to be solved by the invention]
Many low softening point materials, particularly low melting glass, have been manufactured by melting methods. For this reason, the glass composition has many restrictions, and the low melting glass which can be produced was very limited on account of melting a glass raw material.
[0014]
On the other hand, when manufactured by the low temperature synthesis sol-gel method, a processing temperature of 500 ° C. or higher is required for densification, but if it is processed at that temperature, it does not become a low melting point glass, resulting in heat resistance and airtight performance. No good low melting point glass could be obtained. In particular, in the field of electronic materials, there has been no low-melting glass corresponding to severe heat resistance, airtight performance and low melting point. Furthermore, no low-melting-point material other than glass that satisfies heat resistance and hermetic performance has been found so far.
[0015]
The methods disclosed in JP-A-62-297236, JP-A-62-223323, and JP-A-1-183438 made it possible to produce materials at low temperatures that could only be handled by high-temperature melting. Although there is an achievement, low melting glass cannot be manufactured. Further, after sol-gel treatment, treatment at 500 ° C. or higher is also necessary. On the other hand, the method disclosed in Japanese Patent Application Laid-Open No. 7-126035 discloses that a glass having a transition point of 3 and several tens of degrees Celsius can be produced. However, there has been no example of manufacturing a glass having a transition point lower than that without a low melting point material such as lead or bismuth.
[0016]
In other words, conventional low-melting glass manufacturing methods have not been able to produce a glass that satisfies severe heat resistance, airtightness and low-melting characteristics at the same time. In addition, no material other than glass satisfies such characteristics. Moreover, the manufacturing method is not established.
[0017]
[Means for Solving the Problems]
In the case of producing an organic-inorganic hybrid glassy material, the present invention mixes a gel body prepared by a sol-gel method and a material obtained by an acid-anhydride reaction method, melts by heating, and is further aged. This is a method for producing an organic-inorganic hybrid glassy material.
[0018]
Further, the present invention is produced gel body RSiO _3/2 or R ₂ SiO in a sol-gel method: a method of manufacturing the organic-inorganic hybrid glassy material containing (R organic functional group).
[0019]
Further, the present invention is a method of manufacturing the organic-inorganic hybrid glassy material glassy substance obtained by anhydrous acid-base reaction method comprises R ₂ SiO, P ₂ O ₅ and SnO.
[0020]
Moreover, this invention is a manufacturing method of said organic inorganic hybrid glassy substance by which the melting process by heating is processed at the temperature of 30 degreeC or more and 400 degrees C or less.
[0021]
Moreover, this invention is a manufacturing method of said organic-inorganic hybrid glassy substance by which a ripening process is processed at the temperature of 30 to 400 degreeC for 5 minutes or more.
[0022]
Moreover, this invention is the organic-inorganic hybrid glassy substance manufactured by said method.
[0023]
The present invention is also an organic-inorganic hybrid glassy material having an irregular network structure in part or all of the organic-inorganic hybrid glassy material.
[0024]
This organic-inorganic hybrid glassy substance can be used for low melting glass materials, optical waveguides, optical functional materials such as phosphors and photocatalysts, sealing materials such as wet solar cells and electronic material substrates, and the like. It can also be used for functional fibers such as optical fibers and functional thin films. Furthermore, many applications such as building materials and vehicle materials are possible by combining with other materials or alone.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
In the case of producing an organic-inorganic hybrid glassy material, the present invention mixes a gel body prepared by a sol-gel method and a material obtained by an acid-anhydride reaction method, melts by heating, and is further aged. This is a method for producing an organic-inorganic hybrid glassy material. A step of mixing the gel body prepared by the two different methods and the obtained substance is first required. Without this mixing step, an organic-inorganic hybrid glassy material that takes advantage of both advantages cannot be produced.
[0026]
This is a method for producing the above organic-inorganic hybrid glassy material in which the gel body produced by the sol-gel method contains RSiO _3/2 or R ₂ SiO (R: organic functional group). Thus, having a metal unit having an organic functional group in a gel body structure produced by a sol-gel method is extremely important. When the prepared gel body structure does not have a metal unit having an organic functional group, it is sintered but not melted.
[0027]
The organic functional group R is typically an alkyl group or an aryl group. The alkyl group may be linear, branched or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group (n-, i-), a butyl group (n-, i-, t-), a pentyl group, a hexyl group (carbon number: 1 to 20). Particularly preferred are methyl and ethyl groups. Furthermore, examples of the aryl group include a phenyl group, a pyridyl group, a tolyl group, and a xylyl group, and a phenyl group is particularly preferable. Of course, the organic functional group is not limited to the above-described alkyl group or aryl group.
[0028]
The fact that the material obtained by the acid-base reaction method contains R ₂ SiO, P ₂ O ₅ and SnO is extremely important in producing an organic-inorganic hybrid glassy material. It is extremely difficult to produce an organic-inorganic hybrid glassy material that does not contain R ₂ SiO, P ₂ O _5, and SnO and has heat resistance, airtightness, and low meltability.
[0029]
The next important step is to heat the gel body and substance mixture to a molten state. For example, in the conventional sol-gel method, there is almost no concept of melting the gel body, and it has entered the sintering process as it is. In such a case, even if the gel body is sintered as it is, for example, a transparent material having a high melting point can be obtained, but a low melting point material cannot be obtained.
[0030]
This is a method for producing an organic-inorganic hybrid glassy material in which a melting step by heating is performed at a temperature of 30 ° C. or higher and 400 ° C. or lower. At temperatures lower than 30 ° C., it cannot be melted substantially. Further, when the temperature exceeds 400 ° C., the organic group bonded to the metal element forming the network burns, so that a desired glassy substance cannot be obtained, and it is crushed or becomes bubbled and opaque. Desirably, it is 100 degreeC or more and 300 degrees C or less.
[0031]
It is a feature of this production method that the aging step is entered after the melting step. This aging process is also extremely important. For example, in the conventional sol-gel method, since there is no melting step, there is naturally no subsequent aging step. However, even if it has a melting step, a desired organic-inorganic hybrid glassy material cannot be obtained unless a subsequent aging step is performed.
[0032]
This is a method for producing an organic-inorganic hybrid glassy material in which an aging step is performed at a temperature of 30 ° C. or higher and 400 ° C. or lower. At a temperature lower than 30 ° C., it cannot be aged substantially. If it exceeds 400 ° C., it may be thermally decomposed, making it difficult to obtain a stable organic-inorganic hybrid glassy substance. Desirably, it is 100 degreeC or more and 300 degrees C or less. Furthermore, this aging temperature has no effect at a temperature lower than the melting lower limit temperature. Generally, the lower limit of melting temperature to the lower limit of melting temperature (+ 150 ° C.) is desirable. Furthermore, the time required for aging is 5 minutes or more. The aging time varies depending on the processing amount, processing temperature, and allowable residual amount of reactive hydroxyl group (—OH), but generally it is extremely difficult to reach a satisfactory level in less than 5 minutes. Moreover, since productivity falls in a long time, it is 10 minutes or more and less than 1 week desirably.
[0033]
The starting material in the sol-gel method is a metal alkoxide, metal acetylacetonate, metal carboxylate, nitrate, metal hydroxide, or metal halide. First, a gel body is produced by the sol-gel method. Other than the above, this starting material is not a problem as long as it is used in the sol-gel method. For example, trialkylchlorosilane (R ₃₎ SiCl), dimethyldichlorosilane (Me ₂ SiCl ₂ ), and phosphoric acid (eg, H ₃ PO ₄ , H ₃ PO ₃ ) are often used, but of course, the raw materials are not limited to the above.
[0034]
By combining the two methods described above, it is possible to meet the required characteristics of low-melting-point glass that satisfies the severe heat resistance and hermetic performance and low-melting-point characteristics that have not been possible so far. In addition, the required physical properties can be easily handled.
[0035]
In the melting step or aging step by heating, the time tends to be shortened by carrying out under an inert atmosphere or under reduced pressure. Microwave heating is also effective.
[0036]
Of course, all the organic-inorganic hybrid glassy materials produced by the above-mentioned method are targets, but some or all of them are organic-inorganic hybrid glassy materials having an irregular network structure.
[0037]
【Example】
Hereinafter, description will be made based on examples.
Example 1
The starting materials in the sol-gel method were metal alkoxides phenyltriethoxysilane (PhSi (OEt) ₃ ) and ethanol. In a container, water, ethanol, and hydrochloric acid as a catalyst were added to phenyltriethoxysilane, and the mixture was stirred at room temperature for 2 hours to gel. Then, it dried at about 100 degreeC.
[0038]
Orthophosphoric acid (H ₃ PO ₄ ), dimethyldichlorosilane (Me ₂ SiCl ₂ ), diethyldichlorosilane (Et ₂ SiCl ₂ ) tin chloride (SnCl ₂ ) were used as starting materials in the anhydrous base reaction method. In a nitrogen atmosphere reactor, orthophosphoric acid was heated to 40 ° C. to form a liquid, and then dialkyldichlorosilane was added thereto, followed by heating and stirring for 3 hours. During this process, the temperature was gradually raised and heated to 100 ° C. At this stage tin chloride was added. This was further heated at 250 ° C. for 1 hour under a nitrogen atmosphere to obtain a transparent substance.
[0039]
The gel body and the transparent material were mixed, melted at 150 ° C. for 1 hour, and then aged at 200 ° C. for 5 hours to obtain a new transparent material.
[0040]
The starting point of softening behavior was determined from the change in shrinkage in the TMA measurement with the temperature raised at 10 ° C / min, and the starting temperature was taken as the softening temperature. The softening temperature of this substance was 60 ° C. It was also confirmed that silicon units were present in Nicolet infrared absorption spectrometer AVATOR360 type and JEOL magnetic resonance measuring device CMX-400 type. In consideration of having an irregular network structure, the transparent material obtained this time is a material having an organic-inorganic hybrid glass structure, that is, an organic-inorganic hybrid glassy material.
[0041]
In order to check the airtight performance of the organic-inorganic hybrid glassy material, the organic dye methylene blue was put into the obtained organic-inorganic hybrid glassy material, and the bleeding state after one month was observed. As a result, no oozing was observed and it was found that the airtight performance was satisfied. Further, the transition point of this organic-inorganic hybrid glassy substance placed in an atmosphere of 100 ° C. for 300 hours was measured, but no change was observed, and it was confirmed that there was no problem in heat resistance. Furthermore, although the obtained organic-inorganic hybrid glassy substance was left in the atmosphere for one month, no particular change was observed, and it was confirmed that it was excellent in chemical durability.
[0042]
(Example 2)
The starting materials in the sol-gel method were metal alkoxides ethyltriethoxysilane (EtSi (OEt) ₃ ) and ethanol. In a container, water, ethanol, and hydrochloric acid as a catalyst were added to ethyltriethoxysilane, and the mixture was stirred at room temperature for 2 hours to gel. Phosphorous acid (H ₃ PO ₃ ), dimethyldichlorosilane (Me ₂ SiCl ₂ ), diethyldichlorosilane (Et ₂ SiCl ₂ ) tin chloride (SnCl ₂ ) were used as starting materials in the anhydrous base reaction method. After heating phosphorous acid to 40 degreeC and making it a liquid in the reaction apparatus of nitrogen atmosphere, the dialkyl dichlorosilane was added and it heated and stirred for 3 hours. During this process, the temperature was gradually raised and heated to 100 ° C. At this stage tin chloride was added. This was further heated at 250 ° C. for 1 hour under a nitrogen atmosphere to obtain a transparent substance.
[0043]
The gel body and the transparent material were mixed, melted at 150 ° C. for 1 hour, and then aged at 200 ° C. for 5 hours to obtain a new transparent material.
[0044]
The starting point of the softening behavior was determined from the change in shrinkage in the TMA measurement with the temperature raised at 10 ° C./min. The starting temperature was taken as the softening temperature, and the softening temperature of this substance was 120 ° C. It was also confirmed that silicon units were present in Nicolet infrared absorption spectrometer AVATOR360 type and JEOL magnetic resonance measuring device CMX-400 type. In consideration of having an irregular network structure, the transparent material obtained this time is a material having an organic-inorganic hybrid glass structure, that is, an organic-inorganic hybrid glassy material.
[0045]
In order to check the airtight performance of the organic-inorganic hybrid glassy material, an organic dye was put into the obtained organic-inorganic hybrid glassy material, and the bleeding state after one month was observed. As a result, no oozing was observed and it was found that the airtight performance was satisfied. Further, the transition point of this organic-inorganic hybrid glassy substance placed in an atmosphere of 100 ° C. for 300 hours was measured, but no change was observed, and it was confirmed that there was no problem in heat resistance. Furthermore, although the obtained organic-inorganic hybrid glassy substance was left in the atmosphere for one month, no particular change was observed, and it was confirmed that it was excellent in chemical durability.
[0046]
(Comparative Example 1)
The raw materials substantially the same as in Example 1 were used, and the gel body and glassy material obtained by each method were mixed and then fired at 600 ° C.
[0047]
As a result, the obtained substance was not softened even at 800 ° C. and could not be said to be a low melting point substance.
[0048]
(Comparative Example 2)
Using substantially the same raw materials as in Example 2, the gel body and glassy material obtained by the respective methods were mixed and then fired at 700 ° C.
[0049]
As a result, the obtained substance was not softened even at 800 ° C. and could not be said to be a low melting point substance.
[0050]
【The invention's effect】
According to the present invention, an organic-inorganic hybrid glassy material that simultaneously satisfies severe heat resistance, airtightness, and low melting point characteristics, which have been considered extremely difficult to produce, and can easily meet various required physical properties, and production thereof. Could get the way.

Claims (5)

In the case of producing an organic-inorganic hybrid glassy material, a gel body containing RSIO _3/2 or R ₂ SiO (R: organic functional group) produced by a sol-gel method and an R ₂ obtained by an acid-base reaction method A method for producing an organic-inorganic hybrid glassy material, characterized in that a material containing SiO, P ₂ O ₅ and SnO is mixed, heated and melted, and further aged. The method for producing an organic-inorganic hybrid glassy material according to claim 1, wherein the melting step by heating is performed at a temperature of 30 ° C. or higher and 400 ° C. or lower. The method for producing a glassy low-melting-point substance according to claim 1, wherein the aging step is performed at a temperature of 30 ° C. or more and 400 ° C. or less and for a time of 5 minutes or more. An organic-inorganic hybrid glassy material produced by the method according to any one of claims 1 to 3 . The organic-inorganic hybrid glassy material according to claim 4, wherein a part or all of the organic-inorganic hybrid glassy material has an irregular network structure.