JP2005035876A - Organic-inorganic hybrid glassy material and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problem that an organic-inorganic hybrid glassy material fulfilling heat resistance, airtightness, and a low melting point is few and its production needs much time even if it exists. <P>SOLUTION: The method for manufacturing the organic-inorganic hybrid glassy material comprises a heating reaction process between a mixing process and a melting process of starting materials and a maturing process after the melting process. At least one kind of a sol-gel material containing a phenyl group is used and the heating reaction process is implemented at 40-100°C. The melting process is implemented at 40-500°C and the maturing process at 30-400°C for ≥5 minutes. When a melt formed after the melting process is separated into 2 layers, the supernatant liquid is discarded and the lower melt is extracted and matured. The organic-inorganic hybrid glassy material manufactured by the method is also provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an organic-inorganic hybrid glassy material starting from a raw material used in the sol-gel method and a method for producing the same.

  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.

For this reason, the development of polymer materials with enhanced 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.

  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 of low melting point glass represented by Tick glass are changing greatly, and the demands are diversified.

  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.

  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.

  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.

  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.

  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.

  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.

Looking at the known technology, 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).

JP-A-62-297236 JP-A-62-223323 Japanese Unexamined Patent Publication No. 1-183438 Japanese Patent Laid-Open No. 7-126035 P.A.Tick, Physics and Chemistry of Glasses, Vol. 25 No. 6, pp. 149-154 (1984). Kamiya, K., Sakuhana, K., Tashiro, K., Ceramic Society, 618-618, 84 (1976). Masahide Takahashi, Haruki Niida, Toshinobu Yokoo, New Glass, 8-14, 17 (2002).

  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.

  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.

  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.

  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.

  Furthermore, the present inventors have developed an organic-inorganic hybrid glassy material that solves the above-mentioned problems and filed a patent application (Japanese Patent Application No. 2003-69327). However, it is the same to produce an organic-inorganic hybrid glassy material using a material used in the sol-gel method as a starting material, but a process of passing through a gel body after the mixing process of the starting material is indispensable. There was a problem of requiring about 3 days. In the conventional sol-gel method, after mixing the raw materials, the product gelled over 1 to 3 days is used as it is as the sintering step, so a low melting point material cannot be obtained. Moreover, although the low melting point material can be obtained by the change of the manufacturing process, the gelation process is still necessary in this case.

  In the case of producing an organic-inorganic hybrid glassy material using a raw material used in the sol-gel method as a starting material, the present invention has a heating reaction step between the starting material mixing step and the melting step, and further ripening after the melting step. It is the manufacturing method of the organic inorganic hybrid glassy substance which has a process.

  Moreover, it is a manufacturing method of said organic inorganic hybrid glassy substance using at least 1 sort (s) of the sol-gel raw material containing a phenyl group.

  The heating reaction step is a method for producing the organic-inorganic hybrid glassy material performed at a temperature of 40 ° C. or higher and 100 ° C. or lower.

  Further, the melting step is a method for producing the organic-inorganic hybrid glassy material that is processed at a temperature of 40 ° C. or higher and 500 ° C. or lower.

  The aging step is a method for producing the organic-inorganic hybrid glassy material, wherein the treatment is performed at a temperature of 30 ° C. to 400 ° C. and for a time of 5 minutes or more.

  In addition, when the melt after the melting step is separated into two layers, the supernatant is discarded, and the lower melt is extracted and aged to produce the organic-inorganic hybrid glassy material.

  Furthermore, it is an organic-inorganic hybrid glassy material produced by the method described above.

  Furthermore, the organic-inorganic hybrid glassy material described above having an irregular network structure in part or all of the glassy material.

  Furthermore, the organic-inorganic hybrid glassy material having a softening temperature in the range of 60 to 500 ° C.

  Furthermore, it is said organic-inorganic hybrid glassy substance containing a phenyl group.

  According to the present invention, an organic-inorganic hybrid glassy material that simultaneously satisfies heat resistance, hermetic performance, and low melting point characteristics, which has been considered extremely difficult to manufacture, can be manufactured in an extremely short period of time. .

  In the case of producing an organic-inorganic hybrid glassy material using a raw material used in the sol-gel method as a starting material, the present invention has a heating reaction step between the starting material mixing step and the melting step, and further ripening after the melting step. It is the manufacturing method of the organic inorganic hybrid glassy substance which has a process.

  The method for producing the organic-inorganic hybrid glassy material of the present invention is basically different from a conventional method called a sol-gel method and a new method including melting and aging proposed by the present applicant. In the conventional sol-gel method, several types of sol-gel raw materials are mixed, stirred for several hours at room temperature, and then allowed to stand at room temperature for 2 days to 1 week to obtain a wet gel. After that, it is dried at room temperature to about 100 ° C. for several hours to 3 days to obtain a dry gel, and if necessary, pulverized, washed and filtered, and then sintered at least at 400 ° C. and usually at 800 ° C. or higher to obtain a bulk body. Or fibrous. In the case of a film, it is formed into a thin film in a wet gel state, dried and sintered to obtain a thin film.

  Further, in the new method proposed by the present inventors, after mixing several kinds of sol-gel raw materials, the mixture is stirred for 1 to 3 days at room temperature to be gelled, and after the gel is dried, the melting step and the aging step are performed. Then, a predetermined glassy substance is obtained. In this case, since a step of sintering is not required, a high temperature treatment of 400 ° C. or higher, usually 800 ° C. or higher, is not required at least. This method can obtain a new material that could not be obtained by the conventional sol-gel method by paying attention to the new property that has never been seen so far, such as melting property of dry gel and glass change due to aging (glass stabilization). it can. That is, the conventional sol-gel method can obtain a sintered glass or a thin glass, but it is difficult to obtain a thick film or a bulk glass.

  On the other hand, in the present invention, a raw material that can be directly melted without requiring a gelation step can be obtained by adding a heating reaction step after mixing the sol-gel raw materials. That is, it is directly melted from the mixing step, and the sol is directly melted by concentrating the sol. This point of not gelling and directly melting the melt is greatly different from conventional sol-gel methods and new methods involving melting and aging of dried gels. Moreover, since the time required for this heat treatment is about 30 minutes to 5 hours, the manufacturing time is greatly different from the conventional sol-gel method and the above-mentioned new method, which required 1 to 3 days for gelation. Furthermore, there is a characteristic due to a large difference in product that an organic-inorganic hybrid glassy material having a lower softening temperature can be obtained even by using almost the same sol-gel raw material. In the method of the present invention, the melting step may be started immediately after the heating reaction step, or the melting step may be started after cooling once.

  Furthermore, it is also a feature of the present invention to have an aging step after the melting step. However, the aging referred to in the present invention is completely different from the aging referred to in the conventional sol-gel method. In other words, aging does not refer to standing for obtaining a wet gel over 2 days to 1 week, but refers to an operation of stabilizing the glassy substance by changing the structure of the organic-inorganic hybrid glass after melting. In the conventional sol-gel method, there is no melting step, and since the dried gel is sintered as it is, there is no subsequent aging step. This aging step is extremely important, and even a glassy material having meltability cannot obtain a desired organic-inorganic hybrid glassy material unless the subsequent aging step is performed. Reactively active hydroxyl group (-OH) remains in the system simply by melting, and even if it is cooled and hardened, the residual hydroxyl group (-OH) causes hydrolysis-dehydration condensation, resulting in Thus, cracks are generated or broken, and a good organic-inorganic hybrid glassy substance cannot be obtained. For this reason, it is an extremely important step to stabilize this reactive hydroxyl group (—OH) within the glassy material by aging. This is a significant difference between the present invention and the conventional sol-gel method.

  The starting material is a metal alkoxide, a metal acetylacetonate, a metal carboxylic acid, a metal hydroxide, or a metal halide, and it is preferable to first prepare a sol by a sol-gel method. Other than the above, this starting material is not limited to the above starting materials as long as it is used in the sol-gel method. However, the preparation of this sol is an important first step.

The starting material preferably has a metal unit having an organic functional group. Without a metal unit, it will sinter but not melt. This metal unit is characterized by having an organic functional group R, and a silicon unit represented by (R _n SiO _{(4-n) / 2} ) (n = 1 to 3) is exemplified. Here, n is a natural number and is selected from 1, 2, and 3. More specifically, it is more preferable to have a phenyl group metal unit (Ph _n SiO _{(4-n) / 2} ). Further, a methyl group metal unit (Me _n SiO _{(4-n) / 2} ), an ethyl group metal unit (Et _n SiO _{(4-n) / 2} ), a butyl group metal unit (Bt _n SiO _{(4 -n)} A combination with _{n) / 2} ) (n = 1 to 3) or the like is also effective.

  The organic functional group R is typically an aryl group or an alkyl group. 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. 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. Of course, the organic functional group is not limited to the above-described alkyl group or aryl group. The alkyl group may be linear, branched or cyclic. From the above points, it is preferable to use at least one sol-gel raw material containing a phenyl group.

  It is preferable to have a heating reaction step before entering the melting step, that is, between the starting material mixing step and the melting step by heating. This heating reaction step is performed at a temperature of 40 ° C. or higher and 100 ° C. or lower. Outside this temperature range, the above-described metal unit having the organic functional group R cannot be appropriately contained in the structure, and thus it is extremely difficult to obtain an organic-inorganic hybrid glassy material capable of melting glass.

  The upper limit temperature of the heating reaction step is 100 ° C. or lower when an alcohol having a boiling point exceeding 100 ° C., for example, 1-butanol having a boiling point of 118 ° C. is used. . For example, when ethanol is used, the boiling point tends to be better at 80 ° C. or lower. This is presumably because when the boiling point is exceeded, the alcohol rapidly evaporates, so that it is difficult to achieve a uniform reaction from the amount of alcohol and changes in state.

  The melting step by heating is preferably performed at a temperature of 40 ° C. or higher and 500 ° C. or lower. At temperatures lower than 40 ° C., it cannot be melted substantially. Further, when the temperature exceeds 500 ° C., the organic group bonded to the metal element forming the network burns, so that a desired organic-inorganic hybrid glassy material cannot be obtained, and it becomes opaque due to crushing or generation of bubbles. Or Desirably, it is 100 degreeC or more and 300 degrees C or less.

  A stabilized organic-inorganic hybrid glassy material can be obtained through the heating reaction step, the melting step, and the aging step. In the conventional sol-gel method, since there is no melting step, there is naturally no subsequent aging step. Further, the organic-inorganic hybrid glassy substance can be obtained by the heating reaction step and the melting step even when the gel body is not passed. However, since a more stable organic-inorganic hybrid glassy material can be obtained through a subsequent aging step, it is preferable to include an aging step.

  The melting step by heating is preferably performed at a temperature of 40 ° C. or higher and 500 ° C. or lower. At temperatures lower than 40 ° C., it cannot be melted substantially. Further, when the temperature exceeds 500 ° C., the organic group bonded to the metal element forming the network burns, so that a desired organic-inorganic hybrid glassy material cannot be obtained, and it becomes opaque due to crushing or generation of bubbles. Or Desirably, it is 100 degreeC or more and 300 degrees C or less.

  The aging step is preferably 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. When it exceeds 400 ° C., it may be thermally decomposed, and it becomes difficult to obtain a stable glassy substance. Desirably, it is 100 degreeC or more and 300 degrees C or less. Further, the effect of the aging temperature becomes extremely small at a temperature lower than the lower limit melting 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.

  In addition, in the melting step or the aging step by heating, it is effective because the time can be shortened by carrying out under an inert atmosphere or under reduced pressure. Microwave and ultrasonic heating are effective for shortening the time, but are often effective for improving mechanical properties such as strength and hardness and electrical properties such as dielectric constant. .

  Further, when the melt after the melting step is separated into two layers, the supernatant is preferably discarded and the lower melt is extracted and aged. Although the method of the present invention has a great feature in melting, the melt after the melting step often occurs in a state of being separated into two layers. In such a case, the so-called supernatant liquid above the two layers is discarded, and the lower melt can be extracted and aged to obtain an organic-inorganic hybrid glassy material that is stable in physical properties. . By adopting this method, an organic-inorganic hybrid glassy substance having a low softening temperature is generally obtained. Even when separated into two layers, it can be aged as it is, but in that case, the optical characteristics such as light transmittance tend to be somewhat low.

  Of course, all the organic-inorganic hybrid glassy materials produced by the above method are targeted, but organic-inorganic hybrid glassy materials having an irregular network structure in part or all thereof are preferred.

  The softening temperature is preferably 500 ° C. or lower. When the softening temperature exceeds 500 ° C., the organic group bonded to the metal element that forms the network at the time of melting burns, so that the desired organic-inorganic hybrid glassy material cannot be obtained, and it is crushed or bubbles are generated. It becomes opaque. More preferably, it is 50 degreeC or more and 350 degrees C or less, More preferably, they are 60 degreeC or more and 300 degrees C or less. In addition, it is very preferable if the softening temperature before aging is 60 to 150 ° C and the softening temperature after aging is 100 to 300 ° C.

  Further, it preferably contains a phenyl group. This is because an organic-inorganic hybrid glassy material containing a phenyl group often falls within the above temperature range and is very stable.

Hereinafter, description will be made based on examples.
(Example 1)
The starting materials used were metal alkoxides phenyltriethoxysilane (PhSi (OEt) ₃ ) and ethanol. As a mixing step, 45 ml of water, 30 ml of ethanol and hydrochloric acid as a catalyst were added to 10 ml of phenyltriethoxysilane at room temperature, and after stirring at 80 ° C. for 3 hours as a heating reaction step, the mixture was heated to 150 ° C. and melted for 1 hour. After melting, the supernatant and melt were separated into two layers. The supernatant was discarded, the lower melt was extracted and aged at 200 ° C. for 5 hours, cooled to room temperature, and transparent. A material was obtained. Thus, the organic-inorganic hybrid substance could be obtained in about 10 hours, which is about 1/10 of the case where the conventional sol-gel method was used.

  The softening temperature of this transparent material was 89 ° C., which was lower than the decomposition temperature of the phenyl group of about 400 ° C. Considering that the irregular network structure was confirmed by Nicolet's infrared absorption spectrometer AVATOR360 and JEOL's magnetic resonance analyzer CMX-400, the transparent material obtained this time has an organic-inorganic hybrid glass structure. It is an organic-inorganic hybrid glassy material.

  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.

  In addition, as shown in FIG. 1, the softening temperature of the organic-inorganic hybrid glassy substance was judged from the TMA measurement heated at 10 ° C./min. FIG. 1 shows the results of this example. That is, the softening behavior was obtained from the shrinkage change under the above conditions, and the starting temperature was defined as the softening temperature.

(Example 2)
The starting material is a mixed system of phenyltriethoxysilane (PhSi (OEt) ₃ ) and methyltriethoxysilane, which are metal alkoxides. The ratio was 9: 1. Acetic acid as a catalyst was added to 10 ml of phenyltriethoxysilane, 1 ml of methyltriethoxysilane, 40 ml of water, and 30 ml of ethanol in a container, and the mixture was stirred at 80 ° C. for 3 hours and then heated to 150 ° C. for 1 hour. Melted. Unlike Example 1, it was a colorless and transparent melt without phase separation after melting. Further, after aging at 200 ° C. for 5 hours, the mixture was cooled to room temperature to obtain a transparent substance.

  This transparent material has a softening temperature of 86 ° C. Considering that the irregular network structure was confirmed by Nicolet's infrared absorption spectrometer AVATOR360 and JEOL's magnetic resonance analyzer CMX-400. The obtained transparent material is a material having an organic-inorganic hybrid glass structure, that is, an organic-inorganic hybrid glassy material. As shown in FIG. 2, the transmittance curve in the wavelength range of 300 to 2500 nm of the organic-inorganic hybrid glassy substance was measured with a Hitachi U-3500 self-recording spectrophotometer. The solid line data written as Example 2 corresponds to this. As is clear from this result, it can be seen that there is no coloration observed in the visible region, particularly absorption in the blue region observed conventionally. The average transmittance at a wavelength of 300 to 800 nm was 89.7%.

  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.

(Example 3)
As a starting material, a mixed system of metal alkoxides phenyltriethoxysilane and diethoxydiphenylsilane was used, and the ratio was 7: 3. Acetic acid as a catalyst was added to 9 ml of phenyltriethoxysilane, 4 ml of diethoxydiphenylsilane, 40 ml of water and 30 ml of ethanol in a container, and the mixture was stirred at 80 ° C. for 3 hours and then heated to 150 ° C. for 1 hour. Melted. Unlike Example 1, it was a colorless and transparent melt without phase separation after melting. Further, after aging at 200 ° C. for 5 hours, the mixture was cooled to room temperature to obtain a transparent substance.

  The softening temperature of this transparent material was 83 ° C., and an irregular network structure could be confirmed by Nicolet infrared absorption spectrometer AVATOR360 type and JEOL magnetic resonance measuring device CMX-400 type as shown in FIG. Considering this, the transparent material obtained this time is a material having an organic-inorganic hybrid glass structure, that is, an organic-inorganic hybrid glassy material. 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.

(Example 4)
As a starting material, a mixed system of metal alkoxides phenyltriethoxysilane and diethoxydimethylsilane was used, and the ratio was 8: 2. Acetic acid as a catalyst was added to 10 ml of phenyltriethoxysilane, 2 ml of diethoxydimethylsilane, 40 ml of water, and 30 ml of ethanol in a container, and the mixture was stirred at 80 ° C. for 3 hours as a heating reaction step, then raised to 150 ° C. for 1 hour. Melted. Unlike Example 1, it was a colorless and transparent melt without phase separation after melting. Further, after aging at 200 ° C. for 5 hours, the mixture was cooled to room temperature to obtain a transparent substance.

  The softening temperature of this transparent material is 85 ° C. Considering that the irregular network structure was confirmed by Nicolet's infrared absorption spectrometer AVATOR360 and JEOL's magnetic resonance analyzer CMX-400. Considering that it has a regular 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. 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.

(Example 5)
As a starting material, a mixed system of metal alkoxides phenyltriethoxysilane and diethoxydiethylsilane was used, and the ratio was 9: 1. Acetic acid as a catalyst was added to 10 ml of phenyltriethoxysilane, 1 ml of diethoxydiethylsilane, 40 ml of water and 30 ml of ethanol in a container, and the mixture was stirred at 80 ° C. for 3 hours as a heating reaction step, then raised to 150 ° C. for 1 hour. Melted. Unlike Example 1, it was a colorless and transparent melt without phase separation after melting. Further, after aging at 200 ° C. for 5 hours, the mixture was cooled to room temperature to obtain a transparent substance.

  Considering that the softening temperature of this transparent material is 82 ° C. and has an irregular network structure, the transparent material obtained this time is a material having an organic-inorganic hybrid glass structure, ie, an organic-inorganic hybrid glassy material. It is. 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.

(Comparative Example 1)
A gel body was obtained by a conventional sol-gel method using substantially the same raw material as in Example 1. That is, after stirring at about 20 ° C. for 5 hours, the mixture was allowed to stand at about 20 ° C. for 3 days to obtain a wet gel. Then, it was dried at about 100 ° C. for about 10 hours to form a dry gel, and after pulverization, washing, and filtration, it was sintered at 750 ° C. or more to obtain a bulk body or a fiber. It took a total of about 100 hours (about 4 days) to complete this entire process.

  Further, after the wet gel body was dried at about 100 ° C., it was immediately sintered at about 600 ° C. As a result, the obtained substance was blackened and did not soften even at 800 ° C. and could not be said to be a low melting point substance.

(Comparative Example 2)
A gel body was obtained by a conventional sol-gel method using substantially the same raw material as in Example 1. The gel body was melted at 135 ° C. for 1 hour, and then aging at 20 ° C. was attempted. Treated at 20 ° C. for 1 week, this material was an unstable product whose softening temperature varies with time and processing temperature, for example. That is, it was not a stable glassy substance.

(Comparative Example 3)
A gel body was obtained by a conventional sol-gel method using substantially the same raw material as in Example 2. The gel body was melted at 450 ° C. for 5 hours, and aging at 500 ° C. was attempted. As a result, the obtained substance was brown and did not soften even at 800 ° C. and could not be said to be a low melting point substance.

(Comparative Example 4)
An organic-inorganic hybrid glassy material was obtained in substantially the same manner using the same raw material as in Example 1. However, the melt separated into two layers after the melting step was aged as it was. As shown in FIG. 3, the transmittance | permeability curve in the wavelength range of 300-2500 nm of the obtained organic-inorganic hybrid glassy substance was measured similarly to Example 2. The solid line data written as Comparative Example 4 corresponds to this. As is clear from this result, the light transmittance was lower than that in Example 2. The average transmittance at a wavelength of 300 to 800 nm was 46.6%.

  Materials for sealing and covering display components such as PDP, optical information communication device materials such as optical switches and optical couplers, optical equipment materials such as LED chips, optical functional (non-linear) optical materials, It can be used in fields where low-melting glass is used, such as adhesive materials, and fields where organic materials such as epoxy are used.

Softening temperature measurement data (TMA measurement result) shown in Example 1 of the present invention Ultraviolet-visible transmission spectrum data shown in Example 2 and Comparative Example 4 of the present invention NMR measurement data shown in Example 3 of the present invention

Claims (10)

In the case of producing an organic-inorganic hybrid glassy material using a raw material used in the sol-gel method as a starting material, it has a heating reaction step between the starting material mixing step and the melting step, and further has an aging step after the melting step. A method for producing an organic-inorganic hybrid glassy material. The method for producing an organic-inorganic hybrid glassy material according to claim 1, wherein at least one kind of sol-gel raw material containing a phenyl group is used. The method for producing an organic-inorganic hybrid glassy material according to claim 1 or 2, wherein the heating reaction step is performed at a temperature of 40 ° C to 100 ° C. The method for producing an organic-inorganic hybrid glassy material according to any one of claims 1 to 3, wherein the melting step is performed at a temperature of 40 ° C or higher and 500 ° C or lower. The method for producing an organic-inorganic hybrid glassy material according to any one of claims 1 to 4, wherein in the aging step, the treatment is performed at a temperature of 30 ° C or more and 400 ° C or less and for a time of 5 minutes or more. 6. The organic material according to claim 1, wherein when the melt after the melting step is separated into two layers, the supernatant is discarded and the lower melt is extracted and aged. A method for producing an inorganic hybrid glassy material. An organic-inorganic hybrid glassy material produced by the method according to claim 1. The organic-inorganic hybrid glassy material according to claim 7, wherein a part or all of the glassy material has an irregular network structure. The organic-inorganic hybrid glassy material according to claim 7 or 8, wherein the softening temperature is in the range of 60 to 500 ° C. The organic-inorganic hybrid glassy material according to any one of claims 7 to 9, comprising a phenyl group.