JP4516766B2 - Organic-inorganic hybrid glassy material and method for producing the same - Google Patents

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 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.

  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.

  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.

  That is, there has been no material that has a softening point lower than that of the current low-melting glass, does not contain lead, has chemical durability, and is transparent.

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 known. In addition, a P ₂ O ₅ —TeO ₂ —ZnF ₂ -based low-melting glass by a melting method is known (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, No., Journal of Ceramic Association, pp.614-618, 84 (1976). Masahide Takahashi, Haruki Niida, Toshinobu Yokoo, New Glass, pp.8-13, 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, no low melting point glass or low melting point material other than glass corresponding to severe heat resistance, hermetic performance and low melting point 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-point glass manufacturing methods have not been able to produce glass that simultaneously satisfies severe heat resistance, hermetic performance, low-melting-point characteristics, and transparency. In addition, no material other than glass satisfies such characteristics. Furthermore, the glass produced first has a glass whose softening temperature is 350 ° C. or lower, particularly 100 ° C. or lower, and it has not been easy to manufacture.

In the case of producing an organic-inorganic hybrid glassy material having meltability, the present invention uses at least two kinds of metal alkoxides as a raw material, and the ratio of D unit to (D unit + T ³ unit + T ² unit + T ¹ unit) is It is a manufacturing method of the organic-inorganic hybrid glassy substance which adds D unit so that it may become 0.05-0.50.

  Further, the D unit to be added is a method for producing the above organic-inorganic hybrid glassy substance, which is a crystal or liquid selected from diethoxydiphenylsilane, diethoxydimethylsilane, diethoxydiethylsilane and diethoxymethylphenylsilane. It is.

  The metal alkoxide used as a raw material for the organic-inorganic hybrid glassy material is the above-described method for producing an organic-inorganic hybrid glassy material selected from phenyltriethoxysilane, methyltriethoxysilane, and ethyltriethoxysilane.

  Further, in the method for producing an organic-inorganic hybrid glassy substance having a heating reaction step between the starting material mixing step and the melting step, and further having an aging step after the melting step, D in the heating reaction step and / or the melting step. It is a manufacturing method of said organic inorganic hybrid glassy substance which adds a unit.

  Further, in the method for producing an organic-inorganic hybrid glassy material having at least three steps of a gel body manufacturing process by a sol-gel method, a melting process by heating, and an aging process, the above-mentioned organic in which D unit is added in the melting process by heating It is a manufacturing method of an inorganic hybrid glassy substance.

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

Furthermore, a D unit and (D unit + ^{T 3} unit + ^{T 2} units + ^{T 1} unit) above organic-inorganic hybrid glassy material ratio containing D unit to be 0.05 to 0.50 of.

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

  Furthermore, it is said organic-inorganic hybrid glassy substance whose softening temperature is 50 to 350 degreeC.

  According to the present invention, it is possible to produce a transparent organic-inorganic hybrid glassy material having heat resistance and hermetic performance, which has been considered extremely difficult to produce so far, and having a high chemical durability and a very low melting point. It was.

In the case of producing an organic-inorganic hybrid glassy material having meltability, the present invention uses at least two kinds of metal alkoxides as a raw material, and the ratio of D unit to (D unit + T ³ unit + T ² unit + T ¹ unit) is It is a manufacturing method of the organic-inorganic hybrid glassy substance which adds D unit so that it may become 0.05-0.50.

The inclusion of the D unit enables a low melting point and its thermal stability. Here, the D unit is a D ² unit in which all of the four bonds of the silicon atom, excluding the bond to the organic substituent, are bonded to the silicon atom via an oxygen atom, or one is an oxygen atom. It is composed of D ¹ unit bonded to a silicon atom through and the remaining one bonded to an ethoxy group or a hydroxyl group. The T ³ unit is a state in which all three bonds of the silicon atom, excluding the bond to the organic substituent, are bonded to the silicon atom via an oxygen atom, and the T ² unit is a silicon atom. Among the four bonds, two of the three bonds excluding the bond to the organic substituent are bonded to silicon atoms via oxygen atoms, and the T ¹ unit is the four bonds of silicon atoms. Among them, one of the three bonds excluding the bond with the organic substituent means a state in which it is bonded to the silicon atom via an oxygen atom. Further, of the T ² units, ^two of the four bonds of the silicon atom, excluding the bond with the organic substituent, are bonded to the silicon atom through the oxygen atom and the remaining one is ethoxy. the state is a group and ^T 2 (-OEt). Of the T ² units, ^two of the three bonds of the silicon atom, excluding the bond to the organic substituent, are bonded to the silicon atom through the oxygen atom and the remaining one is bonded to the silicon atom. A state of being a hydroxyl group is defined as T ² (—OH). The presence and content of these can be confirmed, for example, by ²⁹ Si NMR spectroscopy.

If the ratio of D unit and (D unit + T ³ unit + T ² unit + T ¹ unit) is less than 0.05, the problem that low temperature meltability is not exhibited, and if it exceeds 0.50, the mechanical strength is inferior. Since it generate | occur | produces, 0.05-0.50 is preferable. More preferably, it is 0.08-0.40, More preferably, it is 0.10-0.30.

  The D unit to be added is preferably a crystal or liquid selected from diethoxydiphenylsilane, diethoxydimethylsilane, diethoxydiethylsilane and diethoxymethylphenylsilane. The D unit made from these raw materials contributes to lowering the softening temperature, and can be made into a more stable organic-inorganic hybrid glassy substance. It is preferable that the D unit to be added is a crystal or a liquid. Particularly, when the crystal is a crystal, the yield is high and a more preferable organic-inorganic hybrid glassy material can be obtained.

  The metal alkoxide used as the raw material for the organic-inorganic hybrid glassy substance is preferably selected from phenyltriethoxysilane, methyltriethoxysilane, and ethyltriethoxysilane. Originally, the metal alkoxide used as a raw material is an alkoxysilane substituted with an organic substituent, and the organic substituent is phenyl, methyl, ethyl, propyl (n-, i-), butyl (n-, i). -, T-), pentyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, mercaptomethyl group, mercaptopropyl group, 3,3,3-trifluoropropyl group, 3-trifluoroacetoxypropyl group It is preferably selected from metal alkoxides consisting of methoxy, ethoxy, propoxy (n-, i-), etc. as alkoxyl groups from vinyl group, benzyl group, styryl group and the like. These are extremely useful raw materials for producing an organic-inorganic hybrid glassy material, particularly a transparent material having a low softness at room temperature or lower. Metal alkoxides other than those described above may be used. Further, metal acetylacetonate, metal carboxylate, metal nitrate, metal hydroxide, metal halide and the like used in the sol-gel method can be produced. However, it is preferably selected from the above-mentioned phenyltriethoxysilane, methyltriethoxysilane and ethyltriethoxysilane.

  Further, in the method for producing an organic-inorganic hybrid glassy substance having a heating reaction step between the starting material mixing step and the melting step, and further having an aging step after the melting step, D in the heating reaction step and / or the melting step. It is preferable to add units. This manufacturing method is greatly different from the conventional sol-gel method, and is characterized by having a heating reaction step, a melting step, and an aging step, but it is most preferable to add D unit in the heating reaction step and / or the melting step. Useful. The addition in the previous mixing step decreases the yield, and the addition in the subsequent aging step may cause a problem in stabilizing the organic-inorganic hybrid glassy material.

In the case where a heating reaction step is included before entering the melting step, that is, between the mixing step of the starting materials and the melting step by heating, the heating reaction step is preferably performed at a temperature of 40 ° C. or higher and 100 ° C. or lower. Outside this temperature range, a metal unit having an organic functional group R in its structure, for example, a silicon unit represented by (R _n SiO _{(4-n) / 2} ) (selected from n = 1, 2, 3), Further, in detail, a phenyl group metal unit (Ph _n SiO _{(4-n) / 2} ), a methyl group metal unit (Me _n SiO _{(4-n) / 2} ), an ethyl group metal unit (Et _n SiO _{(4-n) / 2} ), butyl group metal units (Bt _n SiO _{(4-n) / 2} ) (n = 1 to 3) and the like cannot be appropriately contained, so that the glass can be melted organic Obtaining an inorganic hybrid glassy material becomes extremely difficult.

  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, but it is desirable to consider the boiling point of alcohol having a boiling point of 100 ° C. or lower. 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 is preferably performed at a temperature of 30 ° C to 400 ° C. 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 organic-inorganic hybrid glassy material cannot be obtained. Or Desirably, it is 100 degreeC or more and 300 degrees C or less.

  In the aging step, the treatment is preferably performed at a temperature of 30 ° C. to 400 ° C. and a pressure of 0.1 Torr or less. 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. At this time, it is preferable to carry out at the same time under a pressure of 0.1 Torr or less. When the pressure exceeds 0.1 Torr, the problem of remaining bubbles occurs. 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.

  A stable organic-inorganic hybrid glassy substance can be obtained through the melting step and / or the aging step. In the conventional sol-gel method, neither the melting process nor the aging process is performed, and therefore the organic-inorganic hybrid glassy material of the present invention cannot be obtained.

  In addition, in the melting step or the aging step by heating, it is performed under an inert atmosphere or microwave heating is also effective.

  Typical alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 1,1-dimethyl-1-ethanol and the like. However, it is not limited to these.

  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.

  Furthermore, it is an organic-inorganic hybrid glassy material having at least D units in part or all of the glassy material.

The organic-inorganic hybrid glassy substance has a ratio of D unit to (D unit + T ³ unit + T ² unit + T ¹ unit) of 0.05 to 0.50 and at the same time T ³ unit and (D unit + T ³ unit). + T ² units + T ¹ unit) is preferably 0.30 to 0.95. That T ³ units and the ratio of (D unit + ^{T 3} unit + ^{T 2} units + ^{T 1} unit) is a problem that the mechanical strength is poor is less than 0.30 does not express low temperature melting property exceeds 0.95 A problem occurs. More preferably, it is 0.50-0.90. Further, if the ratio of D unit to (D unit + T ³ unit + T ² unit + T ¹ unit) is less than 0.05, the problem of not exhibiting low temperature meltability is said to exceed 0.50, and the mechanical strength is inferior. A problem occurs. More preferably, it is 0.10-0.40. In this range, a stable organic-inorganic hybrid glassy material having a softening temperature of 50 ° C. to 350 ° C. can be obtained. In addition, the softening temperature of the organic-inorganic hybrid glassy substance was judged from TMA measurement which was heated at 10 ° C./min. That is, the shrinkage was measured under the above conditions, and the change start temperature of the shrinkage was defined as the softening temperature.
Hereinafter, description will be made based on examples.

The metal alkoxide diethoxydiphenylsilane (Ph ₂ Si (OEt) ₂ ) was used as a raw material for introducing the D unit. At room temperature, 4 ml of diethoxydiphenylsilane and about 45 ml of water (molar ratio to diethoxydiphenylsilane is about 170), about 30 ml of ethanol (molar ratio to diethoxydiphenylsilane is about 30), and the catalyst acetic acid to about 0 .30 ml (molar ratio to diethoxydiphenylsilane of about 0.3) was added, mixed with stirring, and heated at 60 ° C. with stirring for 3 hours to obtain colorless and transparent needle-like crystals. D units are introduced into the organic-inorganic hybrid glassy material by adding the needle crystals.

The metal alkoxide phenyltriethoxysilane (PhSi (OEt) ₃ ) was used as a raw material for the organic-inorganic hybrid glassy material into which the D unit was introduced. As a mixing step, about 45 ml of water (molar ratio to phenyltriethoxysilane is about 50), about 20 ml of ethanol (molar ratio to phenyltriethoxysilane is about 10), 10% phenyltriethoxysilane at room temperature, and acetic acid as a catalyst. 0.30 ml (molar ratio with respect to phenyltriethoxysilane is about 0.1) and mixed with stirring. After heating for 3 hours with stirring at 60 ° C. as a heating reaction step, the temperature is raised to 150 ° C. to obtain acicular crystals. 1 g was added. This product was melted at 150 ° C. for 2 hours, aged at 150 ° C. for 3 hours, and then cooled to room temperature to obtain a flaky transparent material having a thickness of 3 mm. The ratio of D unit of this transparent material to (D unit + T ³ unit + T ² unit + T ¹ unit) is 0.11, and the ratio of T ³ unit to (D unit + T ³ unit + T ² unit + T ¹ unit) is 0. .38.

  The softening temperature of this transparent material was 88 ° C., which was 41 ° C. lower than 129 ° C., which was the softening temperature when no needle-like crystals were added. From this, it was confirmed that the low-temperature meltability was promoted by adding needle-like crystals. Further, considering that it has 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.

  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. 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.

The metal alkoxide phenyltriethoxysilane (PhSi (OEt) ₃ ) was used as a raw material for the organic-inorganic hybrid glassy material into which the D unit was introduced. As a mixing step, about 45 ml of water (molar ratio to phenyltriethoxysilane is about 50) to about 10 ml of phenyltriethoxysilane at room temperature, about 30 ml of ethanol (molar ratio to phenyltriethoxysilane is about 10), acetic acid as a catalyst About 0.3 ml (molar ratio to phenyltriethoxysilane is about 0.1), and after stirring at 60 ° C. for 1 hour as a heating reaction step, metal alkoxide diethoxydiphenylsilane (Ph ₂ Si) is used as a raw material for introducing D unit. (OEt) ₂ ) was added in an amount of about 4 ml (molar ratio to phenyltriethoxysilane was about 0.3), and the mixture was further stirred at 60 ° C. for 2 hours. Thereafter, the mixture was melted at 150 ° C. over 2 hours and aged at 150 ° C. for 3 hours, and then cooled to room temperature to obtain a flaky transparent material having a thickness of 3 mm. The ratio of D unit of this transparent material to (D unit + T ³ unit + T ² unit + T ¹ unit) is 0.25, and the ratio of T ³ unit to (D unit + T ³ unit + T ² unit + T ¹ unit) is 0. 37.

  The softening temperature of this transparent material was 67 ° C., which was lower than 129 ° C., which is the softening temperature when diethoxydiphenylsilane is not added. From this, it was confirmed that the low-temperature meltability was promoted by adding needle-like crystals. Further, considering that it has 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.

  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. 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 metal alkoxide phenyltriethoxysilane (PhSi (OEt) ₃ ) was used as a starting material. As a mixing step, about 45 ml of water (molar ratio to phenyltriethoxysilane is about 50) to about 10 ml of phenyltriethoxysilane at room temperature, about 30 ml of ethanol (molar ratio to phenyltriethoxysilane is about 10), acetic acid as a catalyst Was added at about 0.3 ml (molar ratio to phenyltriethoxysilane was about 0.1), stirred at 60 ° C for 3 hours as a heating reaction step, melted at 150 ° C for 2 hours, and aged at 150 ° C for 3 hours. Thereafter, the mixture was cooled to room temperature, and a flaky transparent material having a thickness of 3 mm was obtained. The ratio of D unit to (D unit + T ³ unit + T ² unit + T ¹ unit) in this product is naturally 0, and the ratio of T ³ unit to (T ³ unit + T ² unit + T ¹ unit) is 0. .43.

  The softening temperature of this transparent material was 129 ° C., which was higher than the softening temperature when D unit was introduced. Further, considering that it has 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.

  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. 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.

  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.

²⁹ Si NMR spectrum diagram shown in Example 1 and Comparative Example 1 of the present invention.

Claims (10)

In the case of producing an organic-inorganic hybrid glassy material having a meltability, alkoxysilane and silicon bond four bonds that form a D unit in which two of the four bonds of silicon atoms are bonded to an organic substituent. hands one can at least two kinds of alkoxysilanes of the alkoxysilane to form a T unit combined with organic substituents as the starting material, the temperature at and the organic radical of the mixing step and 30 to 400 ° C. at room temperature of the starting material A heating reaction step performed at 40 ° C. or higher and 100 ° C. or lower and a boiling point or lower of the alcohol between the melting step performed at a temperature below the combustion temperature of 30 ° C. and lower than the thermal decomposition temperature after the melting step. In the method for producing an organic-inorganic hybrid glassy material having an aging step, D unit is added in the heating reaction step or / and the melting step, D The ratio of the unit to (D unit + T ³ unit + T ² unit + T ¹ unit) is 0.05 to 0.50 , and the ratio of T ³ unit to (D unit + T ³ unit + T ² unit + T ¹ unit) is 0.30. A method for producing an organic-inorganic hybrid glassy material, wherein D unit is added so as to be ˜0.95 .
Here, the D unit is one in which all or one of the four bonds of the silicon atom, excluding the bond to the organic substituent, is bonded to the silicon atom via an oxygen atom, and the T ³ unit is Of the four bonds of silicon atoms, all three bonds excluding bonds with organic substituents are bonded to silicon atoms via oxygen atoms. T ² unit is the four bonds of silicon atoms 2 of the 3 bonds excluding the bond with the organic substituent in the group, and T ¹ unit is ¹ out of the 3 bonds with the bond with the organic substituent in the 4 bonds of the silicon atom. The book is in a state of being bonded to a silicon atom through an oxygen atom. The D unit to be added is a crystalline or liquid material selected from diethoxydiphenylsilane, diethoxydimethylsilane, diethoxydiethylsilane, and diethoxymethylphenylsilane. A method for producing a hybrid glassy material. The organic-inorganic hybrid glassy material according to claim 1 or 2, wherein the metal alkoxide used as a raw material of the organic-inorganic hybrid glassy material is selected from phenyltriethoxysilane, methyltriethoxysilane, and ethyltriethoxysilane. A method for producing a substance. In the method for producing an organic-inorganic hybrid glassy material having a heating reaction step between the mixing step and the melting step of the starting material and further having an aging step after the melting step, the D unit is provided in the heating reaction step and / or the melting step. The method for producing an organic-inorganic hybrid glassy material according to any one of claims 1 to 3, which is added. In a method for producing an organic-inorganic hybrid glassy material having at least three steps of a gel body manufacturing process by a sol-gel method, a melting process by heating, and an aging process, a D unit is added in the melting process by heating. The manufacturing method of the organic inorganic hybrid glassy substance in any one of Claims 1 thru | or 3. An organic-inorganic hybrid glassy material produced by the method according to claim 1. 7. The organic-inorganic hybrid glassy material according to claim 6, comprising a D unit having a ratio of D unit to (D unit + T ³ unit + T ² unit + T ¹ unit) of 0.05 to 0.50. . The organic-inorganic hybrid glassy material according to claim 6 or 7, wherein the organic-inorganic hybrid glassy material contains a phenyl group. The organic-inorganic hybrid glassy material according to any one of claims 6 to 8, wherein a part or all of the glassy material has an irregular network structure. The organic-inorganic hybrid glassy material according to any one of claims 6 to 9, wherein a softening temperature is 50 ° C to 350 ° C.