JP2004277207A - Organic-inorganic hybrid glassy material and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the following problems: up to now, a glassy material which satisfies severe requirements for heat resistance, airtightness, and low-melting point characteristics and easily handles various requirements for physical properties is not yielded; and its production method is not yet established. <P>SOLUTION: The organic-inorganic hybrid glassy material is produced by mixing a gel body prepared by a sol-gel method and a material prepared by an anhydrous acid-base reaction method and thermally melting and aging the resultant mixture. The gel body obtained by a sol-gel method contains RSiO<SB>3/2</SB>or R<SB>2</SB>SiO (R: an organic functional group), and the material prepared by an anhydrous acid-base reaction method contains R<SB>2</SB>SiO, P<SB>2</SB>O<SB>5</SB>, and SnO. The thermal melting step is conducted at 30-400°C; and the aging step, at 30-400°C for 5 min or longer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel glassy substance starting from a gel produced by a sol-gel method and a substance produced by an acid-base reaction method, and a method for producing the same.
[0002]
[Prior art]
As materials softening at 600 ° C. or lower, polymer materials and low-melting glass are well known, and have been used in many places such as sealing / sealing materials, passivation glass, and glaze since ancient times. Since various properties are different between the polymer material and the low melting point glass, they have been used properly according to the environment in which they can be used. Generally, glass is used when heat resistance and airtight performance are prioritized, and organic materials represented by polymer materials are used in fields where properties other than heat resistance and airtight performance are prioritized. However, with the recent technological progress, attention has been paid to characteristics that have not been required so far, and development of materials having such characteristics is expected.
[0003]
For this reason, the development of a polymer material having enhanced heat resistance and airtightness, and a glass having a softened region at a low temperature, a so-called low-melting glass, have been actively developed. In particular, in the electronic materials market heat resistance and airtight property is required, a low-melting glass represented by a _PbO-SiO 2 _-B 2 _{O 3} system or _{PbO-P 2} O 5 -SnF 2 based glass, electronic components It has become an indispensable material in fields such as sealing and coating. In addition, low-melting glass can reduce the energy required for its forming process and the cost as compared with the high-melting glass, and is therefore in line with recent social demands for energy saving. Furthermore, if it is possible to melt the organic material having optical functional performance at a temperature that does not destroy it, it is expected to be applied to optical information communication devices such as optical switches as hosts for optical functional organic material-containing (non-linear) optical materials. As described above, materials having heat resistance and airtightness, which are characteristics of general molten glass, and easily obtaining various characteristics such as a polymer material are demanded in many fields. Expectations are gathering. Further, an organic-inorganic hybrid glass is also attracting attention as one of the low-melting glass.
[0004]
Among low-melting glasses, for example, Tick glass represented by Sn-Pb-PFO-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 because of its excellent water resistance. However, since the low-melting glass contains lead as a main component, it has become necessary to replace the low-melting glass with an alternative material from the recent trend of environmental protection. Furthermore, the required characteristics for the Tick glass have changed significantly, and the demands have been diversified.
[0005]
As a general method for producing glass, 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 manufactured by this method, and low-melting glass is also manufactured by this method. However, in the case of low-melting glass, there are many restrictions on the glass composition that can be configured, such as the need to contain lead, alkali, bismuth, etc. in order to lower the melting point.
[0006]
On the other hand, as a low-temperature synthesis method of an amorphous bulk, a sol-gel method, a liquid phase reaction method, and an acid-base reaction method are considered. In the sol-gel method, a bulk body can be obtained by subjecting a metal alkoxide or the like to hydrolysis-polycondensation and heat treatment at a temperature exceeding 500 ° C. (for example, see Non-Patent Document 2), usually 700 to 1600 ° C. However, when a bulk material produced by the sol-gel method is considered 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 the evaporation and release of organic substance decomposition gas or water during the heating process. In many cases, there was a problem in heat resistance and airtightness. As described above, many problems still remain in the bulk production by the sol-gel method, and particularly, low-melting glass has not been produced by the sol-gel method.
[0007]
In addition, the liquid phase reaction method has a problem of low productivity due to low yield, and in addition, the use of hydrofluoric acid or the like in the reaction system and the limitation of thin film synthesis limit the realization of bulk materials. It is almost impossible to combine them.
[0008]
The anhydride-base reaction method is a technique developed in recent years, and it is possible to produce an organic-inorganic hybrid glass which is one of low-melting glasses (for example, see Non-Patent Document 3), but it is still under development, Not all low melting glasses can be made.
[0009]
Therefore, the production of many low-melting glasses has been performed by a melting method, not by a low-temperature synthesis method. For this reason, the composition of the glass is limited due to the melting of the glass raw material, and the type of low-melting glass that can be produced is extremely limited.
[0010]
At present, low-melting glass is a promising material because of heat resistance and airtightness, and required physical properties are often obtained in a form typified by low-melting glass. However, the material is not limited to low melting point glass, and if the required physical properties are met, there is no major problem with low melting point or low softening point substances other than glass.
[0011]
In view of the known art, a method for producing quartz glass fibers by a sol-gel method (for example, see Patent Document 1), a method for producing titanium oxide fibers by a sol-gel method (for example, see Patent Document 2), and a semiconductor by a sol-gel method A method for producing a dope matrix (for example, see Patent Document 3) is disclosed. Further, a P ₂ O ₅ —TeO ₂ —ZnF ₂ -based low-melting glass based on a melting method is disclosed (for example, see Patent Document 4).
[0012]
[Patent Document 1]
JP 62-297236 A [Patent Document 2]
JP 62-223323 A [Patent Document 3]
JP-A-1-183438 [Patent Document 4]
Japanese Patent Application Laid-Open No. 7-126035 [Non-Patent Document 1]
P. A. Tick, Physics and Chemistry of Glasses, 14, 1140 (1989).
[Non-patent document 2]
Kanichi Kamiya, Saio Sakuhana, Noriko Tashiro, Journal of the Ceramic Industry Association, 618-618, 84 (1976).
[Non-Patent Document 3]
Masahide Takahashi, Haruki Niida, Toshinobu Yokoo, New Glass, 8-14, 17 (2002).
[0013]
[Problems to be solved by the invention]
The production of many low softening point materials, especially low melting glass, has been performed by the melting method. For this reason, there are many restrictions on the glass composition, and the low melting point glass that can be produced has been extremely limited due to the melting of the glass raw material.
[0014]
On the other hand, when manufactured by the sol-gel method of a low-temperature synthesis method, a processing temperature of 500 ° C. or more is required for densification. However, processing at that temperature does not result in a low-melting glass, and as a result, heat resistance and airtight performance Could not 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. Further, a low-melting-point material other than glass satisfying heat resistance and airtightness has not been found yet.
[0015]
The methods disclosed in JP-A-62-297236, JP-A-62-223323 and JP-A-1-183438 allow material production that could only be performed by high-temperature melting to be performed at low temperatures. Despite his achievements, he cannot make low melting glass. After the sol-gel treatment, treatment at 500 ° C. or higher is also required. On the other hand, the method disclosed in Japanese Patent Application Laid-Open No. H7-126035 discloses that glass having a transition point of three hundred and several tens of degrees Celsius can be produced. However, there has been no example in which glass having a transition point lower than that is manufactured without a material having a low melting point such as lead or bismuth.
[0016]
That is, the conventional method for producing a low-melting glass has not been able to produce a glass that simultaneously satisfies severe heat resistance, hermetic performance, and low-melting characteristics. Also, no material other than glass satisfies such characteristics. In addition, its manufacturing method has not been established.
[0017]
[Means for Solving the Problems]
The present invention provides a method for producing an organic-inorganic hybrid glassy substance, in which a gel obtained by a sol-gel method and a substance obtained by an acid-base reaction method are mixed, heated, melted, and further aged. And a method for producing an organic-inorganic hybrid glassy material.
[0018]
Further, the present invention is the above-mentioned method for producing an organic-inorganic hybrid glassy substance, wherein the gel body produced by the sol-gel method contains RSiO _3/2 or R ₂ SiO (R: organic functional group).
[0019]
Further, the present invention is the above-mentioned method for producing an organic-inorganic hybrid glassy substance, wherein the glassy substance obtained by the acid-base reaction method contains R ₂ SiO, P ₂ O ₅ and SnO.
[0020]
Further, the present invention is the above-described method for producing an organic-inorganic hybrid glassy material, wherein the melting step by heating is performed at a temperature of 30 ° C to 400 ° C.
[0021]
Further, the present invention is the above-mentioned method for producing an organic-inorganic hybrid glassy material, wherein the aging step is performed at a temperature of 30 ° C. or more and 400 ° C. or less for 5 minutes or more.
[0022]
Further, the present invention is an organic-inorganic hybrid glassy material produced by the above method.
[0023]
Further, the present invention is an organic-inorganic hybrid glassy material having an irregular network structure in part or all of the organic-inorganic hybrid glassy material.
[0024]
This organic-inorganic hybrid glassy substance can be used as a low-melting glass material, an optical waveguide, an optical functional material such as a phosphor or a photocatalyst, or a sealing material for a wet solar cell or an electronic material substrate. It can also be used for functional fibers such as optical fibers and functional thin films. Furthermore, many applications are possible, such as building materials and vehicle materials, by combining with other materials or by itself.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a method for producing an organic-inorganic hybrid glassy substance, in which a gel obtained by a sol-gel method and a substance obtained by an acid-base reaction method are mixed, heated, melted, and further aged. And a method for producing an organic-inorganic hybrid glassy material. First, a step of mixing the gel substance produced by the above two different methods and the obtained substance is necessary. Without this mixing step, it is not possible to produce an organic-inorganic hybrid glassy material that takes advantage of both.
[0026]
This is a method for producing the above-mentioned organic-inorganic hybrid glassy material in which the gel body produced by the sol-gel method contains RSiO _3/2 or R ₂ SiO (R: organic functional group). Thus, it is extremely important to have a metal unit having an organic functional group in the gel structure produced by the sol-gel method. When there is no metal unit having an organic functional group in the produced gel structure, sintering is performed but not melting.
[0027]
The organic functional group R is typically an alkyl group or an aryl group. The alkyl group may be linear, branched or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group (n-, i-), a butyl group (n-, i-, t-), a pentyl group, and a hexyl group (carbon number: 1 to 20). Particularly preferred are a methyl group and an ethyl group. Further, 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. Naturally, the organic functional group is not limited to the above-mentioned alkyl group and aryl group.
[0028]
It is extremely important that the substance obtained by the acid-anhydride reaction method contains R ₂ SiO, P ₂ O ₅ and SnO in producing an organic-inorganic hybrid glassy substance. It is extremely difficult to produce an organic-inorganic hybrid glassy material having heat resistance, airtightness, and low melting properties without containing R ₂ SiO, P ₂ O ₅ and SnO.
[0029]
The next important step is to heat the mixture of the gel body and the substance to a molten state. For example, in the conventional sol-gel method, there is almost no concept of melting a gel body, and the sintering process has been started as it is. In such a case, if the gel body is sintered as it is, for example, a transparent material having a high melting point can be obtained, but a material having a low melting point cannot be obtained.
[0030]
This is a method for producing an organic-inorganic hybrid glassy substance in which a melting step by heating is performed at a temperature of 30 ° C or more and 400 ° C or less. At a temperature lower than 30 ° C., substantially no melting is possible. On the other hand, when the temperature exceeds 400 ° C., not only a desired glassy substance cannot be obtained due to the burning of the organic group bonded to the metal element forming the network, but also the powder becomes opaque due to crushing or bubbles. Desirably, the temperature is 100 ° C. or more and 300 ° C. or less.
[0031]
It is a feature of the present production method to enter the aging step after the melting step. This aging step is also very important. For example, in the conventional sol-gel method, since there is no such a melting step, there is naturally no subsequent aging step. However, even if it has a melting step, a desired organic-inorganic hybrid glassy substance cannot be obtained without a subsequent aging step.
[0032]
An aging step is a method for producing an organic-inorganic hybrid glassy material in which the treatment is performed at a temperature of 30 ° C or more and 400 ° C or less. At a temperature lower than 30 ° C., ripening cannot be performed substantially. If it exceeds 400 ° C., it may be thermally decomposed, making it difficult to obtain a stable organic-inorganic hybrid glassy substance. Desirably, the temperature is 100 ° C. or more and 300 ° C. or less. Further, this aging temperature has no effect at a temperature lower than the lower limit of melting temperature. Generally, the lower limit of the melting point to about (the lower limit of the melting point + 150 ° C) is desirable. Further, the time required for ripening is 5 minutes or more. The aging time depends on the amount of treatment, the treatment temperature and the allowable residual amount of reactive hydroxyl groups (-OH), but it is generally very difficult to reach a satisfactory level in less than 5 minutes. In addition, the productivity is lowered in a long time, so that it is desirably 10 minutes or more and 1 week or less.
[0033]
Starting materials in the sol-gel method are metal alkoxide, metal acetylacetonate, metal carboxylate, nitrate, metal hydroxide, or metal halide. First, a gel body is produced by the sol-gel method. There are no problems with this starting material as long as it is used in the sol-gel method other than the above. As a starting material in the acid-base reaction method which is not limited to the above-mentioned starting materials, for example, trialkylchlorosilane (R ₃ SiCl), dimethyldichlorosilane (Me ₂ SiCl ₂ ), and phosphoric acid (eg, H ₃ PO ₄ , H ₃ PO ₃ ) are often used, but are not limited to the above-described materials.
[0034]
By combining the above two methods, it is possible to meet the required characteristics of a low-melting glass that simultaneously satisfies severe heat resistance, airtightness, and low-melting characteristics that could not be achieved until now. Further, it is possible to easily cope with the required physical properties.
[0035]
In the melting step by heating or the aging step, the time tends to be shortened by performing it in an inert atmosphere or under reduced pressure. Microwave heating is also effective.
[0036]
In addition, the organic-inorganic hybrid glassy material produced by the above-described method is, of course, all objects, but is an organic-inorganic hybrid glassy material having an irregular network structure in part or all thereof.
[0037]
【Example】
Hereinafter, description will be given based on examples.
(Example 1)
Metal alkoxide phenyltriethoxysilane (PhSi (OEt) ₃ ) and ethanol were used as starting materials in the sol-gel method. Water, ethanol and hydrochloric acid as a catalyst were added to phenyltriethoxysilane in a container, and the mixture was stirred at room temperature for 2 hours to gel. Then, it dried at about 100 degreeC.
[0038]
Orthophosphoric acid (H ₃ PO ₄ ), dimethyldichlorosilane (Me ₂ SiCl ₂ ), diethyldichlorosilane (Et ₂ SiCl ₂ ), and tin chloride (SnCl ₂ ) were used as starting materials in the anhydrous base reaction method. Orthophosphoric acid was heated to 40 ° C. in a reactor in a nitrogen atmosphere to make a liquid, and then dialkyldichlorosilane was added, followed by heating and stirring for 3 hours. In this process, the temperature was gradually increased and heated to 100 ° C. At this stage, tin chloride was added. This was further heated at 250 ° C. for 1 hour in a nitrogen atmosphere to obtain a transparent substance.
[0039]
The gel and the transparent substance were mixed, melted at 150 ° C. for 1 hour, and subsequently aged at 200 ° C. for 5 hours to obtain a new transparent substance.
[0040]
The softening behavior starting point was determined from the change in shrinkage in TMA measurement at a temperature rise of 10 ° C./min, and the starting temperature was taken as the softening temperature. The softening temperature of this substance was 60 ° C. In addition, it was confirmed that a silicon unit was present in an infrared absorption spectrometer type AVATOR360 manufactured by Nicolet and a magnetic resonance measurement apparatus CMX-400 manufactured by JEOL. Taking into account that it has an irregular network structure, the transparent substance obtained this time is a substance having an organic-inorganic hybrid glass structure, that is, an organic-inorganic hybrid glassy substance.
[0041]
To check the airtightness of this organic-inorganic hybrid glassy substance, an organic dye methylene blue was put into the obtained organic-inorganic hybrid glassy substance, and the state of bleeding after one month was observed. As a result, no seepage was observed at all, and it was found that the airtightness was satisfied. Further, the transition point of the organic-inorganic hybrid glassy substance placed in an atmosphere at 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, the obtained organic-inorganic hybrid glassy substance was left in the air for one month, but no particular change was observed, and it was confirmed that the organic-inorganic hybrid glassy substance was excellent in chemical durability.
[0042]
(Example 2)
As starting materials in the sol-gel method, metal alkoxide ethyltriethoxysilane (EtSi (OEt) ₃ ) and ethanol were used. Water, ethanol and hydrochloric acid as a catalyst were added to ethyltriethoxysilane in a container, and the mixture was stirred at room temperature for 2 hours to gel. Phosphorous acid (H ₃ PO ₃ ), dimethyldichlorosilane (Me ₂ SiCl ₂ ), diethyldichlorosilane (Et ₂ SiCl ₂ ), and tin chloride (SnCl ₂ ) were used as starting materials in the anhydrous base reaction method. After the phosphorous acid was heated to 40 ° C. in a reactor under a nitrogen atmosphere to make it a liquid, dialkyldichlorosilane was added, and the mixture was heated and stirred for 3 hours. In this process, the temperature was gradually increased and heated to 100 ° C. At this stage, tin chloride was added. This was further heated at 250 ° C. for 1 hour in a nitrogen atmosphere to obtain a transparent substance.
[0043]
The gel and the transparent substance were mixed, melted at 150 ° C. for 1 hour, and subsequently aged at 200 ° C. for 5 hours to obtain a new transparent substance.
[0044]
When the softening behavior starting point was determined from the change in shrinkage in TMA measurement at a temperature rise of 10 ° C./min, and the starting temperature was taken as the softening temperature, the softening temperature of this substance was 120 ° C. In addition, it was confirmed that a silicon unit was present in an infrared absorption spectrometer type AVATOR360 manufactured by Nicolet and a magnetic resonance measurement apparatus CMX-400 manufactured by JEOL. Taking into account that it has an irregular network structure, the transparent substance obtained this time is a substance having an organic-inorganic hybrid glass structure, that is, an organic-inorganic hybrid glassy substance.
[0045]
In order to check the airtightness of the organic-inorganic hybrid glassy substance, an organic dye was put into the obtained organic-inorganic hybrid glassy substance, and the state of bleeding after one month was observed. As a result, no seepage was observed at all, and it was found that the airtightness was satisfied. Further, the transition point of the organic-inorganic hybrid glassy substance placed in an atmosphere at 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, the obtained organic-inorganic hybrid glassy substance was left in the air for one month, but no particular change was observed, and it was confirmed that the organic-inorganic hybrid glassy substance was excellent in chemical durability.
[0046]
(Comparative Example 1)
Using substantially the same raw materials as in Example 1, the gel obtained by each method and the glassy substance were mixed, and then fired at 600 ° C.
[0047]
As a result, the obtained substance did not soften even at 800 ° C. and could not be said to be a low melting point substance.
[0048]
(Comparative Example 2)
Using the same raw materials as in Example 2, the gel obtained by each method and the vitreous substance were mixed, and then fired at 700 ° C.
[0049]
As a result, the obtained substance did not soften even at 800 ° C. and could not be said to be a low melting point substance.
[0050]
【The invention's effect】
According to the present invention, an organic-inorganic hybrid glass-like material that simultaneously satisfies severe heat resistance, airtightness, and low melting point characteristics, which have been considered extremely difficult to produce, and can easily cope with various required physical properties, and its production Managed to get the way.

Claims (7)

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