JP2005145795A - Film-like organic and inorganic hybrid glassy material and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problems that it is very difficult to form a film having thickness of ≥3 μm by one time of processing, and the processing in multiple stages is needed for forming a film having thickness of ≥3μm, thereby resulting in the rough surface. <P>SOLUTION: The method for manufacturing a film-like organic and inorganic hybrid glassy material through a gelatinizing process, a ripening process, a dissolving process into an organic solvent, a film sticking process, and a film stabilizing process after a mixing process by a metal alkoxide used as a raw material, water, an acid catalyst and alcohol is provided, wherein the metal alkoxide used as the raw material is composed of an alkoxy silane substituted with an organic substituent, the amount of water used in the mixing process is 0.1 to 5 times the alcohol by a molar ratio, the acid catalyst is an acetic acid or hydrochloric acid, the temperature is 15 to 100°C in the gelatinizing process, and the concentration in the dissolving process is 50 to 2,000 g/L. <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 an organic-inorganic hybrid glassy material formed into a film 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 organic materials with optical functional performance, it can be used as a host of optical functional organic material-containing (non-linear) optical materials for optical information communication devices such as optical switches and optical couplers. Application is expected. In this case, what is extremely important is the light transmission property, particularly in the infrared region, in addition to the low melting point property. For example, light transmission loss at a wavelength of 1553 nm is extremely important. For example, although organic materials such as UV epoxy resin and deuterated PMMA are used in optical waveguide devices, it cannot be said that satisfactory materials have been developed in the communication field. Furthermore, a material having the above-described characteristics and formed into a film has not been developed.

  Therefore, materials having heat resistance and hermetic performance, which are the characteristics of general molten glass, and being easy to obtain various properties such as polymer materials are demanded in many fields, particularly light transmittance in the infrared region. The expectation is on the low-melting-point glass. Among them, organic-inorganic hybrid glass has been attracting attention as one of materials that have low melting point characteristics and chemical stability and can be formed into a film.

  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.

  Furthermore, as a low temperature synthesis method of an amorphous material, 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 a 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 in the process of heating organic decomposition gas or water. 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 desired organic-inorganic hybrid glasses can be produced.

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. further,
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.

As for known techniques, 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. Further, 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 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). Matsuda Akinori, Ceramics, 893-895, 38 (2003).

  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 sol-gel method of the low temperature synthesis 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, the conventional low melting point glass manufacturing methods have not been able to produce glass that satisfies severe heat resistance, airtightness, and low melting point properties, and further transmits ultraviolet and infrared rays. In addition, no material other than glass satisfies such characteristics.

  The production of filmy glass has heretofore been performed by the sol-gel method. A film was obtained by dip-coating or spin-coating a sol on a glass substrate and heat-treating it, but the film was colored yellow due to the presence of catalyst acid and unreacted components in the film. The problem of poor chemical stability occurred.

  Furthermore, the film thickness that can be formed on a glass substrate by one dip coating or spin coating is about 2 μm to 3 μm. When a film having a thickness of 3 μm or more is formed, the dip coating or spin coating is performed several times. And laminated. For this reason, the film having a thickness of 3 μm or more had a rough surface and high internal non-uniformity.

  In the case of producing an organic-inorganic hybrid glassy material, the present invention provides a gelation step and an aging step for forming a precursor after a mixing step using a metal alkoxide, water, an acid catalyst and an alcohol as raw materials, and a precursor. Production of a film-like organic-inorganic hybrid glassy material characterized by undergoing a dissolution process in an organic solvent to form a solution, a film adhesion process by dip coating on a precursor solution of a substrate, and a film stabilization process Is the method.

  Moreover, the metal alkoxide used as a raw material is the above-described method for producing a film-like organic-inorganic hybrid glassy material composed of alkoxysilane substituted with an organic substituent.

  The water used in the mixing step is a method for producing the above film-like organic-inorganic hybrid glassy substance having a molar ratio of 0.1 to 5 times that of alcohol.

  The acid catalyst is a method for producing the above film-like organic-inorganic hybrid glassy substance, which is acetic acid or hydrochloric acid.

  The gelation step is a method for producing the above film-like organic-inorganic hybrid glassy substance that is performed at a temperature of 15 ° C. or higher and 100 ° C. or lower.

  The aging step is a method for producing the above film-like organic-inorganic hybrid glassy material, which is performed at a temperature of 30 ° C. or higher and lower than 350 ° C. for a time of 5 minutes or longer.

  Moreover, the melt | dissolution process to an organic solvent is a manufacturing method of said film-like organic-inorganic hybrid glassy substance whose density | concentration is 50-2000 g / l.

  Further, the film adhering step is performed at a film adhering viscosity in the range of 0.1 to 10 cP and at a pulling rate of 0.1 to 65 cm / min. It is a manufacturing method.

  Moreover, a film | membrane stabilization process process is a manufacturing method of said film-form organic-inorganic hybrid glassy substance performed in 15-400 degreeC.

  Furthermore, it is a film-like organic-inorganic hybrid glassy material produced by the above method.

  Furthermore, it is said film-like organic-inorganic hybrid glassy substance whose film thickness obtained by a film | membrane adhesion process process is 3 micrometers or more.

  Furthermore, the film-like organic-inorganic hybrid glassy material having a light transmission loss at a wavelength of 1553 nm of 3 dB / cm or less and high transparency.

  Furthermore, the film-like organic-inorganic hybrid glassy material having a refractive index of 1.40 to 1.80 at a wavelength of 1553 nm.

  Furthermore, it is said film-form organic-inorganic hybrid glassy substance whose softening point is -20-400 degreeC.

  Furthermore, the film-like organic-inorganic hybrid glassy substance described above has an irregular network structure in part or all of the glassy substance.

  The present invention produces a film-like organic-inorganic hybrid glassy material that has been considered extremely difficult to produce so far, such as heat resistance, air tightness performance, low melting point characteristics, high permeability in the infrared region, and extremely uniform surface. I was able to.

  In the case of producing an organic-inorganic hybrid glassy material, the present invention provides a gelling step and an aging step for forming a precursor after a mixing step using a metal alkoxide, water, an acid catalyst and an alcohol as raw materials, and a precursor. Production of a film-like organic-inorganic hybrid glassy material characterized by undergoing a dissolution process in an organic solvent to form a solution, a film adhesion process by dip coating on a precursor solution of a substrate, and a film stabilization process Is the method. By taking the above raw materials and steps, a desired film-like organic-inorganic hybrid glassy substance can be obtained.

  The metal alkoxide used as a raw material is an alkoxysilane substituted with an organic substituent. The organic substituent is a phenyl group, a methyl group, an ethyl group, a propyl group (n-, i-), a butyl group (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, vinyl It is preferably selected from metal alkoxides consisting of methoxy, ethoxy, propoxy (n-, i-), etc. as alkoxyl groups from the 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.

  The water used in the mixing step is preferably 0.1 to 5 times the alcohol in terms of molar ratio. In the conventional sol-gel method, although it depends on the type of alcohol, water is the minimum necessary for hydrolysis. This arises from the basic problem of suppressing rapid hydrolysis and the formation of unstable sols. In the case of forming a thin sol-gel film, a large amount of water is sometimes used, but in the case of a bulk form, the amount is as small as possible, for example, about 0.3 times that of alcohol is a conventional method. In the present invention, if the water used in the mixing step is less than 0.1 times that of alcohol, there is a problem that a long time is required for the gelation step. In the present invention characterized by having an aging step, when the amount of water is 5 times or more that of alcohol, there is a problem that a long time is required for the aging step. More preferably, it is 0.1 times or more and 3 times or less of alcohol. In the mixing step, water, alcohol, and an acid catalyst are added to the raw material metal alkoxide and mixed with stirring, but this order is not particular.

  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.

  The acid catalyst is preferably acetic acid or hydrochloric acid. Conventionally, hydrochloric acid and nitric acid are often used as catalysts in the sol-gel method. This was because the gel time was longer with other catalysts. However, acetic acid or hydrochloric acid is used in the mixing step of the present invention, and acetic acid is more preferable. By mixing acetic acid or hydrochloric acid and a large amount of water at the same time, the absorptance in the visible light region can be extremely reduced, that is, a highly transparent glassy substance can be obtained. This effect is obtained for the first time by mixing acetic acid or hydrochloric acid with water.

It is preferable to have a gelation step performed at a temperature of 15 ° C. or higher and 100 ° C. or lower between the starting material mixing step and the aging step by heating. 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 silicon unit (Ph _n SiO _{(4-n) / 2} ), a methyl group silicon unit (Me _n SiO _{(4-n) / 2} ), an ethyl group silicon unit (Et _n SiO _{(4-n) / 2} ), butyl group silicon units (Bt _n SiO _{(4-n) / 2} ) (n = 1 to 3) and the like cannot be appropriately contained, so that glass-melting 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-, t-), a pentyl group, a hexyl group (carbon number: 1 to 20). Particularly preferred are methyl and ethyl groups. Furthermore, examples of the aryl group include a phenyl group, a pyridyl group, a tolyl group, and a xylyl group, and a phenyl group is particularly preferable. Of course, the organic functional group is not limited to the above-described alkyl group or aryl group.

  The upper limit temperature of the gelation 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.

  This gelation often takes 1-3 days. In addition, after this gelation process, you may enter into an aging process immediately, and depending on the case, after cooling once, you may enter into an aging process.

  In the aging step, the treatment is preferably performed at a temperature of 30 ° C. or higher and 350 ° C. or lower. At a temperature lower than 30 ° C., it cannot be aged substantially. When it exceeds 350 ° 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. 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. Although vacuum heating is also very effective, the desirable pressure is 0.1 Torr or less. When the pressure is high, the effect of aging is small. On the other hand, if the pressure is too low, the effect does not change so much, and considering productivity, equipment, etc., about 0.01 Torr is good. By aging, a good precursor can be obtained.

  The precursor is dissolved in an organic solvent. The concentration of the precursor is important, and the concentration is preferably 50 to 2000 g / l. If the dissolution concentration in the organic solvent is less than 50 g / l, there is a problem that the amount of the precursor to be deposited is small and a film having a thickness of 3 μm or more cannot be obtained by one dip coating treatment. On the other hand, if it exceeds 2000 g / l, there arises a problem that the film becomes non-uniform. More preferably, it is 100-1500 g / l. The organic solvent includes polar solvents such as acetone, methanol, ethanol, and chloroform, but acetone is more preferable.

  The film attaching step by dip coating on the precursor solution of the substrate is preferably performed in a range where the viscosity of the precursor solution at the time of film attachment is 0.1 to 10 cP. If the viscosity of the film formation is less than 0.1 cP, a uniform film cannot be obtained and problems such as exposure of the substrate occur. On the other hand, when it exceeds 10 cP, a film having an optical surface cannot be obtained, and the problem of surface irregularities occurs. More preferably, it is 1-4 cP. Further, it is preferably performed at a substrate pulling rate of 0.1 to 65 cm / min. When the substrate pulling rate is less than 0.1 cm / min, it takes a long time to form a film, and there arises a problem that problems such as solution denaturation occur. On the other hand, when it exceeds 65 cm / min, there arises a problem that the flatness of the surface is greatly impaired. More preferably, it is 0.5-10 cm / min.

  The membrane stabilization treatment step is preferably performed in a temperature range of 15 to 400 ° C. If the treatment temperature is less than 15 ° C., a problem that a sufficient aging effect cannot be obtained occurs. On the other hand, when the temperature exceeds 400 ° C., there arises a problem that the organic substituent undergoes thermal decomposition. More preferably, it is 25-300 degreeC.

  Furthermore, it is a film-like organic-inorganic hybrid glassy material produced by the above method. As a material for forming this film-like organic-inorganic hybrid glassy substance, glass such as silica glass and soda-lime glass is typical, but there is no problem as long as it can be a substrate such as metal or ceramics.

  It is preferable that the film obtained by one dip coating treatment has a film thickness of 3 μm or more. This is because the film formation by this method is a so-called pulling method, and an unstable film is often obtained when the film thickness is less than 3 μm.

  A film-like organic-inorganic hybrid glassy material having a light transmission loss at a wavelength of 1553 nm of 3 dB / cm or less and high transparency is preferable.

  This is because if the light transmission loss in the infrared region, particularly in the wavelength of 1553 nm, exceeds 3 dB / cm, it becomes difficult to use as a light transmission member. Moreover, it is preferable that transparency in the visible light region is high. This is because, in addition to the light transmission characteristics in the infrared region, the transparency in the visible light region widens its application. Here, the wavelength 1553 nm is based on the optical communication wavelength band, but light transmission in the infrared region is also used in many wavelength regions, so it is a single barometer.

  Moreover, it is preferable that the refractive index in wavelength 1553nm is 1.40-1.80. The reason why the refractive index at the wavelength of 1553 nm is 1.40 to 1.80 is that when the refractive index at the wavelength of 1553 nm is smaller than 1.40 or larger than 1.80, loss due to refractive index mismatch with the silica fiber is caused. This is because it increases.

  The softening point is preferably -20 to 400 ° C. When the softening point is less than -20 ° C, it cannot be used substantially. On the other hand, when the softening point exceeds 400 ° C, the organic-inorganic hybrid glassy material becomes unstable.

  Furthermore, the film-like organic-inorganic hybrid glassy substance described above has an irregular network structure in part or all of the glassy substance.

  Hereinafter, description will be made based on examples.

Hereinafter, description will be made based on examples.

A metal alkoxide phenyltriethoxysilane (PhSi (OEt) ₃ ) was used as a starting material. As a mixing step, about 3 ml of water (molar ratio to phenyltriethoxysilane is about 3), about 30 ml of ethanol (molar ratio to phenyltriethoxysilane is about 10) and 10 ml of hydrochloric acid as a catalyst at room temperature About 0.02 ml (molar ratio to phenyltriethoxysilane is about 0.01) and mixed with stirring. After stirring at room temperature for 3 hours, about 3 ml of diphenyldiethoxysilane (Ph ₂ Si) was added to the mixed solution. (OEt) ₂ ) (molar ratio to phenyltriethoxysilane was about 0.2) and about 3 ml of ethanol (molar ratio to phenyltriethoxysilane was about 2) were dropped and stirred at room temperature for 2 days to gel. . This wet gel was aged by heating in vacuum at 120 ° C. for 2 hours to obtain a precursor.

This precursor was dissolved in acetone to prepare a solution having a concentration of 900 g / l. The viscosity of this solution was 3.5 cP by the Ostwald method. The film forming operation was performed by so-called dip coating. That is, a 35 mm × 20 mm silica glass plate treated with alkali in this solution was immersed vertically at a speed of 4 cm · min ⁻¹ , and then the substrate was pulled up vertically at a speed of 6 cm · min ⁻¹ . Then, it dried at about 35 degreeC.

A colorless and transparent thick film was obtained after drying, and the film thickness was about 8.54 μm. The relationship between the substrate pulling speed and the film thickness is shown in FIG. When the refractive index and optical transmission loss of this thick film were measured with a planar waveguide evaluation apparatus MPLCA-01 manufactured by Sakai Corporation, the refractive index was 1.5961 at 473.0 nm, 1.5776 at 1312.8 nm, and 1319.0 nm. 1.5583 at 1.553 and 1.5574 at 1553 nm. The light transmission loss of this thick film was 1.15 dB · cm ⁻¹ at a wavelength of 1553 nm.

Further, when this sample was vacuum heated at 200 ° C. for 2 hours, a colorless and transparent thick film having a thickness of 8.35 μm without cracks was obtained, and its refractive index was 1.5976 at 473.0 nm, and 1.5787 at 632.8 nm. 1319.0 nm increased to 1.5596 and 1553 nm increased to 1.5587, and light transmission loss decreased to 0.98 dB · cm ⁻¹ .

When the refractive index distribution of this thick film was measured by a planar waveguide evaluation apparatus MPLCA-01 manufactured by Sakai Corporation, it was a very small value of 10 ⁻⁴ or less in the film thickness direction.

As shown in FIG. 2, the transmittance curve in each wavelength region of the organic-inorganic hybrid glassy material was measured using a Hitachi U-3500 type self-recording spectrophotometer. The solid line data written as Example 1 corresponds to this. As is apparent from this result, it can be seen that there is no large coloration, particularly absorption in the blue region which has been conventionally observed. The average visible light transmittance at a wavelength of 300 to 800 nm was 98%. When the surface roughness of the thick film was measured using an operation type near-field optical microscope JSPM-5300 manufactured by JEOL Ltd., the roughness factor for the film thickness of 8.54 μm was 1.8 × 10 ⁻³ μm.

The same precursor gel as in Example 1 was dissolved in acetone to prepare a solution having a concentration of 800 g / l. The viscosity of this solution was 1.9 cP by the Ostwald method. A 35 mm × 20 mm silica glass plate treated with alkali in this solution was immersed vertically at a speed of 4 cm · min ⁻¹ , then pulled up vertically at a speed of 51 cm · min ⁻¹ and dried at a temperature of about 150 ° C.

  After drying, a colorless and transparent thick film was obtained, and the film thickness was about 14.82 μm as shown in FIG.

The same precursor gel as in Example 1 was dissolved in acetone to prepare a solution having a concentration of 600 g / l. The viscosity of this solution was 1.0 cP by the Ostwald method. A 35 mm × 20 mm silica glass plate treated with an alkali was vertically immersed in this solution at a speed of 4 cm · min ⁻¹ , then pulled up vertically at a speed of 51 cm · min ⁻¹ and dried at a temperature of about 300 ° C.

  After drying, a colorless and transparent thick film was obtained, and the film thickness was about 9.91 μm as shown in FIG.

(Comparative Example 1)
As a starting material, metal alkoxide phenyltriethoxysilane (PhSi (OEt) ₃ ) was used as in the example. About 10 ml of phenyltriethoxysilane at room temperature to about 3 ml of water (molar ratio to phenyltriethoxysilane is about 3), about 30 ml of ethanol (molar ratio to phenyltriethoxysilane is about 10), about 0.02 ml of catalyst as catalyst Add hydrochloric acid (molar ratio to phenyltriethoxysilane is about 0.01) and about 3 ml of diphenyldiethoxysilane (Ph ₂ Si (OEt) ₂ ) (molar ratio to phenyltriethoxysilane is about 0.25) and mix. A sol was prepared. A silica glass plate (35 mm × 20 mm treated with alkali) was vertically immersed in this sol at a speed of 4 cm · min ⁻¹ , then pulled up vertically at a speed of 6 cm · min ⁻¹ , dried at room temperature, and then 200 By heating at 0 ° C. for 2 hours, a colorless and transparent film having a thickness of 0.30 μm and no cracks was obtained. This sample was again immersed in the sol, dried and vacuum heated 30 times to obtain a colorless transparent thick film having a thickness of 9.00 μm and no cracks.

When the refractive index, optical transmission loss, and refractive index distribution of this thick film were measured with a planar waveguide evaluation apparatus MPLCA-01 manufactured by Sakai Corporation, the refractive index was 1.5976 at 473.0 nm and 1.5787 at 632.8 nm. 1319.0 nm, 1.5596, 1553 nm, 1.5587, optical transmission loss is 4.2 dB · cm ⁻¹ , and the refractive index distribution is 10 ^{−2 in the} film thickness direction, which is larger than that of Example 1. It was.

Furthermore, as shown in FIG. 2, the transmittance curve in each wavelength region of the organic-inorganic hybrid glassy substance was measured using a Hitachi U-3500 type self-recording spectrophotometer. The broken line data written as Comparative Example 1 corresponds to this. The average visible light transmittance at a wavelength of 300 to 800 nm was 97%, which was lower than that of Example 1.
Furthermore, when the surface roughness of the thick film was measured using an operation type near-field optical microscope JSPM-5300 manufactured by JEOL Ltd., the roughness factor for the film thickness of 9.00 μm was 800 × 10 ⁻³ μm.

(Comparative Example 2)
The same precursor gel as in Example 1 was dissolved in acetone to prepare a solution having a concentration of 800 g / l. The viscosity of this solution was 3.5 cP by the Ostwald method. A 35 mm × 20 mm silica glass plate treated with an alkali was vertically immersed in this solution at a speed of 4 cm · min ⁻¹ , then pulled up vertically at a speed of 51 cm · min ⁻¹ and dried at about 10 ° C.

  A colorless and transparent thick film was obtained after drying, but the film thickness was uneven.

  Electronic material protective film, insulating film, optical waveguide circuit, micro optical element, optical filter, grating, optical switch, nonlinear optical element, LED protective film, plastic material protective film, gas barrier film, anti-reflective film and many others The field can be used.

The relationship between the pulling rate and the film thickness shown in Example 1 and Comparative Example 1 of the present invention. The transmittance | permeability measurement result shown in Example 1 and Comparative Example 1 of this invention.

Claims (15)

In the case of producing an organic-inorganic hybrid glassy material, after a mixing step using a metal alkoxide as a raw material, water, an acid catalyst and an alcohol, a gelation step and an aging step for forming a precursor, and a precursor solution are formed. A method for producing a film-like organic-inorganic hybrid glassy material, comprising: a dissolving step in an organic solvent, a film attaching step by dip coating on a precursor solution of a substrate, and a film stabilizing step. 2. The method for producing a film-like organic-inorganic hybrid glassy material according to claim 1, wherein the metal alkoxide used as a raw material comprises an alkoxysilane substituted with an organic substituent. The method for producing a film-like organic-inorganic hybrid glassy material according to claim 1 or 2, wherein the water used in the mixing step is 0.1 to 5 times as much as the alcohol in a molar ratio. The method for producing a film-like organic-inorganic hybrid glassy material according to any one of claims 1 to 3, wherein the acid catalyst is acetic acid or hydrochloric acid. The method for producing a film-like organic-inorganic hybrid glassy material according to any one of claims 1 to 4, wherein the gelation step is performed at a temperature of 15 ° C or higher and 100 ° C or lower. 6. The method for producing a film-like organic-inorganic hybrid glassy material according to claim 1, wherein the aging step is performed at a temperature of 30 ° C. or higher and lower than 350 ° C. for a time of 5 minutes or longer. The method for producing a film-like organic-inorganic hybrid glassy material according to any one of claims 1 to 6, wherein the concentration in the dissolving step in the organic solvent is 50 to 2000 g / l. The film deposition step is performed at a substrate pulling speed of 0.1 to 65 cm / min in which the viscosity of the precursor solution during film deposition is in the range of 0.1 to 10 cP. A method for producing a film-like organic-inorganic hybrid glassy material according to claim 1. The method for producing a film-like organic-inorganic hybrid glassy material according to any one of claims 1 to 8, wherein the film stabilization treatment step is performed in a temperature range of 15 to 400 ° C. A film-like organic-inorganic hybrid glassy material produced by the method according to any one of claims 1 to 9. The film-like organic-inorganic hybrid glassy material according to claim 10, wherein the film thickness obtained by the film adhesion process is 3 µm or more. The film-like organic-inorganic hybrid glassy material according to claim 10 or 11, which has a light transmission loss of 3 dB / cm or less at a wavelength of 1553 nm and high transparency. The film-like organic-inorganic hybrid glassy material according to any one of claims 10 to 12, wherein a refractive index at a wavelength of 1553 nm is 1.40 to 1.80. The film-like organic-inorganic hybrid glassy material according to any one of claims 10 to 13, having a softening point of -20 to 400 ° C. The film-like organic-inorganic hybrid glassy material according to any one of claims 10 to 14, wherein a part or all of the glassy material has an irregular network structure.