JP2005047779A - Organic-inorganic hybrid vitreous material, and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic-inorganic hybrid vitreous material capable of solving the problem that it is difficult to produce a vitreous material satisfying heat resistance, air tight performance and a low melting point characteristic simultaneously and being made transparent and colorless in a conventional manufacturing method, and to provide a method of manufacturing the organic-inorganic hybrid vitreous material. <P>SOLUTION: The organic-inorganic hybrid vitreous material is manufactured through a heating and reaction process, a melting process and an aging process after raw materials, water, alcohol and hydrochloric acid are mixed together. A metal alkoxide is used as a starting raw material and in a mixing process, water 10 times of the quantity of the raw material by molar ratio, hydrochloric acid and alcohol are used. The organic-inorganic hybrid vitreous material is manufactured in this way, has an irregular network structure in the whole or a part of the vitreous material and is transparent and colorless. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an organic-inorganic hybrid glassy material and a method for producing the same, and more particularly to a bulky material having properties of a low-melting glass 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—P—F—O-based glass (for example, see Non-Patent Document 1) is famous, 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 the Tick glass are changing greatly, and at the same time, 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.

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 Patent Laid-Open No. 1-183438 Japanese Patent Laid-Open No. 7-126035 PATick, Physics and Chemistry of Glasses, 14, 1140 (1989). 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 are said to enable material production that can be handled only by high-temperature melting even at low temperatures. 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.
There was also a problem that a slight yellow coloration was observed.

  The present invention relates to an organic / inorganic hybrid glass produced by mixing a raw material, water, alcohol and hydrochloric acid together in a mixing step for producing an organic / inorganic hybrid glassy material, followed by a heating reaction step, a melting step and an aging step. It is a manufacturing method of a gaseous substance.

  The starting material is a method for producing the organic-inorganic hybrid glassy material using a metal alkoxide.

  The mixing step is a method for producing the organic-inorganic hybrid glassy material using water, hydrochloric acid, and alcohol at a molar ratio of 10 times or more of the raw material.

  Moreover, a heating reaction process is a manufacturing method of said organic-inorganic hybrid glassy substance performed at the temperature of 40 to 100 degreeC.

  Moreover, it is a manufacturing method of said organic-inorganic hybrid glassy substance processed at the temperature of 30 degreeC or more and 400 degrees C or less and time for 5 minutes or more at a ripening process.

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

  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 is colorless and transparent.

  According to the present invention, it was possible to obtain a colorless and transparent glassy substance having low softening properties, which has been considered extremely difficult to produce, and having heat resistance and airtightness.

  The present invention relates to a method for producing an organic-inorganic hybrid glassy material produced by mixing a raw material, water, alcohol and hydrochloric acid together in a mixing step for producing an organic-inorganic hybrid glassy material, followed by a melting step and an aging step. Is the method. In the present invention, in addition to the new concept of melting the product obtained from the sol-gel process raw material, the gelation process which required 1 to 3 days can be eliminated. It also has the feature that can be manufactured. In addition, a desired organic-inorganic hybrid glassy substance can be obtained through the above-described mixing step, melting step, and aging step.

  Although it is a metal alkoxide as a starting material, it can be produced if it is a raw material used in the sol-gel method including metal acetylacetonate, metal carboxylic acid, metal nitrate, metal hydroxide, and metal halide, The above starting materials are desirable from the standpoint of quality and productivity.

  The mixing step is a method for producing an organic-inorganic hybrid glassy material using water, hydrochloric acid, and alcohol at a molar ratio of 10 times or more of the raw material. In the conventional sol-gel method, water is the minimum necessary for hydrolysis, and at most it is about 3 to 4 times the raw material in molar ratio. This is to address the basic problem of suppressing rapid hydrolysis and the formation of unstable sols, and the control of hydrolysis in the sol-gel process was extremely important. That is, if a portion having a high water concentration is generated in the sol, precipitation of particles may occur, resulting in a heterogeneous gel. For this reason, a large amount of water is sometimes used when forming a part of a thin sol-gel film, but a large amount of water has not been used so far when manufacturing a general material, particularly a bulk material. . There was also a production reason for shortening the drying process of the gel.

  However, the amount of this water is extremely important for making colorless and transparent, and it is necessary to use water at a molar ratio of 10 times or more of the raw material. Preferably it is 30 times or more of raw materials by molar ratio, More preferably, it is 50 times or more. In addition, containing a lot of moisture is important for making colorless and transparent, and there is no upper limit from this point. However, since it takes time at the time of production if there is much moisture, 500 times or less is desirable from the viewpoint of productivity, but it is not limited to this.

In the mixing step, hydrochloric acid 10 ⁻⁴ to 1 times that of the raw material and 1 to 10 ³ times alcohol are often used in a molar ratio. Hydrochloric acid is important as a catalyst and alcohol is important as a solvent. In ^{general, 10} -4 to 1 times of hydrochloric acid and 1 to 10 ³ times the alcohol. Examples of the alcohol 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.

It is a feature of the present invention to have a heating reaction step before entering the melting step, that is, between the mixing step of the starting materials 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, 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 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-, s-, t-), a pentyl group, and a hexyl group (carbon number: 1 to 20). Particularly preferred are a methyl group and an ethyl group. 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.

  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.

  Since the time required for this heat treatment is about 30 minutes to 5 hours, it is greatly different from the treatment time by the conventional sol-gel method, which takes 1 to 3 days for gelation. In addition, after this heating reaction process, you may enter into a melting process immediately, and may enter into a melting process after cooling once.

  The melting step by heating is performed at a temperature of 40 ° C. or more and 500 ° C. or less. 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 stable organic-inorganic hybrid glassy material can be obtained through 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. Moreover, in this invention which does not go through a gel body, an organic-inorganic hybrid glassy substance can be obtained by a melting process. However, a more stable organic-inorganic hybrid glassy material can be obtained through a subsequent aging step.

  In the aging process, the treatment is performed at a temperature of 30 ° C. to 400 ° C. 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, the time tends to be shortened by performing it under an inert atmosphere or under pressure or reduced pressure. Microwave heating is also effective.

  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, the organic-inorganic hybrid glassy material is characterized by being colorless and transparent. In general, an organic-inorganic hybrid glassy substance often has a pale yellow coloration, but a colorless and transparent organic-inorganic hybrid glassy substance can be obtained.

Hereinafter, description will be made based on examples.
The starting materials used were metal alkoxides phenyltriethoxysilane (PhSi (OEt) ₃ ) and ethanol. As a mixing step, about 45 ml of water (molar ratio to phenyltriethoxysilane is about 50), about 30 ml of ethanol, and about 0.01 ml of hydrochloric acid as a catalyst are added to about 10 ml of phenyltriethoxysilane at room temperature as a heating reaction step. After stirring at 60 ° C. for 3 hours, the mixture was heated to 150 ° C. and melted for 1 hour 30 minutes. In this state, the phases were separated into a transparent glass melt layer and an emulsion aqueous layer. Here, after cooling to room temperature to solidify the glass melt layer and removing only the aqueous layer, the glassy material was washed with purified water to obtain a colorless and transparent glassy material. Furthermore, 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 120 ° C., which was lower than the decomposition temperature of the phenyl group of about 400 ° C. 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. Since this substance was not colored yellow after 100 hours in an atmosphere of 200 ° C., an ultraviolet-visible light absorption spectrum was measured. As shown in FIG. 1, it can be seen that the absorption curve in each wavelength region of the organic-inorganic hybrid glassy material has no significant coloration, particularly absorption in the blue region which has been conventionally observed. In addition, Hitachi U-3500 type self-recording spectrophotometer was used as a measuring apparatus.

  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)
The starting materials used were metal alkoxides phenyltriethoxysilane (PhSi (OEt) ₃ ) and 2-methyl-1-propanol. As a mixing step, about 3 ml of water (molar ratio to phenyltriethoxysilane is about 3), about 30 ml of ethanol and about 0.01 ml of hydrochloric acid as a catalyst are added to about 10 ml of phenyltriethoxysilane at room temperature, and the heating reaction step is performed. After stirring at 105 ° C. for 3 hours, the temperature was raised to 150 ° C. and melted for 1 hour 30 minutes to obtain a pale yellow glassy substance. Furthermore, after aging at 160 ° C. for 5 hours and cooling to room temperature, the glassy substance remained pale yellow.

  The ultraviolet-visible light absorption spectrum of this substance was measured and indicated by a broken line. As shown in FIG. 1, it can be seen that large absorption is observed in the blue region of the absorption curve in each wavelength region of the organic-inorganic hybrid glassy substance, and there is yellow coloring.

The absorptivity measurement result shown in Example 1 and Comparative Example of the present invention.

Claims (8)

An organic-inorganic hybrid characterized in that, in a mixing step for manufacturing an organic-inorganic hybrid glassy material, the raw material, water, alcohol and hydrochloric acid are mixed together and then manufactured through a heating reaction step, a melting step and an aging step. A method for producing a glassy substance. The method for producing an organic-inorganic hybrid glassy material according to claim 1, wherein a metal alkoxide is used as a raw material. The method for producing an organic-inorganic hybrid glassy material according to claim 1 or 2, wherein the mixing step uses water at a molar ratio of 10 times or more of the raw material. The method for producing an organic-inorganic hybrid glassy material according to any one of claims 1 to 3, 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 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. An organic-inorganic hybrid glassy material produced by the method according to claim 1. The organic-inorganic hybrid glassy material according to claim 6, wherein a part or all of the glassy material has an irregular network structure. The organic-inorganic hybrid glassy material according to claim 6 or 7, which is colorless and transparent.

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