JP2003277509A - Manufacturing method of organic/inorganic composite and organic/inorganic composite - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic/inorganic composite excellent in optical transparency and its laminate. <P>SOLUTION: In this method of manufacturing an organic/inorganic composite, wherein it is formed from an organic polymer and a metal alkoxide, the metal alkoxide is hydrolyzed and polycondensed until the metal alkoxide becomes not more than 3 vol.%, then an organic polymer is mixed to form an organic/ inorganic composite, and increasing or decreasing concentration gradient of the metal element of the metal alkoxide from one end to the other end of the laminate is given by laminating the organic/inorganic composite. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an organic-inorganic composite formed from an organic polymer and a metal alkoxide, an organic-inorganic composite obtained by this method, and a laminate thereof.

[0002]

2. Description of the Related Art Inorganic materials such as metals and ceramics are
It has excellent heat resistance, mechanical strength, electrical characteristics, optical characteristics, chemical stability, etc. and is widely used industrially by taking advantage of these functions. However, they are generally brittle and have high hardness, and in order to be processed into a desired shape, formation at high temperature, mechanical processing, and the like are required, and the use thereof may be limited.

On the other hand, the organic polymer is excellent in formability and has flexibility, so that it can be easily processed into a desired shape. However, on the other hand, it is often inferior in heat resistance and chemical stability to inorganic materials.

Therefore, in recent years, attention has been paid to organic-inorganic composite materials which have the characteristics of both by adding an inorganic material to an organic polymer material. As a composite of an organic polymer and an inorganic material, a so-called composite material in which fibers or powders of an inorganic material are dispersed in an organic polymer material has been used in a wide variety of fields from the past. In recent years, development of so-called organic-inorganic nanocomposite materials (sometimes referred to as organic-inorganic hybrid materials) in which organic and inorganic regions in organic-inorganic composite materials are compounded at the nanometer level or the molecular level is particularly active. is there.

The organic-inorganic nanocomposite material can be dispersed in the organic region and the inorganic region at the nanometer level or the molecular level, and is therefore applied as a material for electronic parts or a material for mechanical parts. Further, since the organic region and the inorganic region in the material can be designed smaller than the wavelength of light, light absorption and scattering are small. Therefore, it has been studied to use the organic-inorganic nanocomposite material in materials such as optical waveguides and optical fibers by imparting optical transparency.

A method for producing an organic-inorganic composite is disclosed in, for example, Non-Patent Documents 1 and 2 below.

[0007]

[Non-Patent Document 1] Motoyuki Toki, et.al., “Structure
of poly (vinylpyrrolidone) -silica hybrid ”, Polymer
Bulletin 29, 653-660 (1992)

[Non-Patent Document 2] Jen Ming Yang, et.al., “Organic-in
organic hybrid sol-gel materials, 1 ”, Die Angewan
dte Makromolekulare Chemi 251 (1997) 49-60 (Nr.4356)

[0008]

However, according to the production methods described in these documents, there is a problem that an organic-inorganic composite having sufficient optical transparency cannot be obtained.

An object of the present invention is to provide a production method capable of producing an organic-inorganic composite excellent in optical transparency and an organic-inorganic composite obtainable by this method.

[0010]

The production method of the present invention is a method for producing an organic-inorganic composite formed from an organic polymer and a metal alkoxide, and the amount of unreacted metal alkoxide becomes 3% by volume or less. The method is characterized by comprising a step of hydrolyzing a metal alkoxide for polycondensation, and a step of mixing the polycondensed metal alkoxide and an organic polymer to form an organic-inorganic composite.

In the present invention, the metal alkoxide is hydrolyzed and polycondensed until the unreacted metal alkoxide becomes 3% by volume or less, and then an organic polymer is mixed therewith to form an organic-inorganic composite. ing. Thereby, an organic-inorganic composite having excellent optical transparency can be manufactured.
Therefore, according to the manufacturing method of the present invention, it is possible to manufacture an organic-inorganic composite suitable as a material for optical components such as an optical waveguide and an optical fiber.

Examples of the metal alkoxide used in the present invention include alkoxides of Si, Ti, Zr, Al, Sn, Zn and the like. In particular, Si, Ti, or Zr alkoxide is preferably used. Therefore, alkoxysilane, titanium alkoxide, and zirconium alkoxide are preferably used, and alkoxysilane is particularly preferably used. Examples of alkoxysilane include tetraethoxysilane, tetramethoxysilane, and tetra-n.
-Propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, etc. Can be mentioned.

The organic polymer in the present invention is not particularly limited as long as it forms an organic-inorganic composite with a metal alkoxide. Examples of the organic polymer include polyvinylpyrrolidone, polycarbonate, polymethylmethacrylate, polyamide, polyimide, polystyrene, polyethylene, polypropylene, epoxy resin, phenol resin, acrylic resin, urea resin, and melamine resin. From the viewpoint of forming an organic-inorganic composite having excellent optical transparency, polyvinylpyrrolidone,
Polycarbonate, polymethylmethacrylate, polystyrene or a mixture thereof is preferably used as the organic polymer.

The hydrolysis of the metal alkoxide is preferably carried out in the presence of water for hydrolysis and an acid serving as a catalyst for hydrolysis. The ratio of water for hydrolysis to metal alkoxide (water / metal alkoxide) is 1.0 to 3.
It is preferably 0, more preferably 1.5 to
It is 2.5. As the acid used as a catalyst for hydrolysis, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and organic acids can be used, and hydrochloric acid is particularly preferably used. Ratio of hydrochloric acid to metal alkoxide (hydrochloric acid / metal alkoxide)
Is preferably 0.001 to 0.01, more preferably 0.001 to 0.5, and particularly preferably 0.002 in terms of molar ratio.

The amount of unreacted metal alkoxide, that is, the amount of metal alkoxide remaining can be measured by gas chromatography or the like. The metal alkoxide is hydrolyzed under conditions such as a predetermined temperature and concentration, and the reaction time at which the residual amount of the metal alkoxide is 3% by volume or less is measured in advance, and the reaction time is hydrolyzed to cause polycondensation. After that, an organic polymer is mixed with this to form an organic-inorganic composite. Alternatively, the measurement may be performed each time it is formed.

The organic-inorganic composite of the present invention is characterized by being manufactured by the manufacturing method of the present invention. The organic-inorganic composite of the present invention can be formed, for example, by preparing a mixed solution obtained by mixing a hydrolyzed and polycondensed metal alkoxide solution and an organic polymer, and applying the mixed solution. The organic-inorganic composite can be formed on the substrate by applying such a coating liquid on the substrate. As the substrate, a substrate made of an organic material, a metal material, or the like can be used. When the organic-inorganic composite of the present invention is used as an optical material, the organic-inorganic composite can be formed on a transparent substrate.

The organic-inorganic composite of the present invention can have a thickness of 10 μm and a transmittance of 90% with respect to light having a wavelength of 600 to 1000 nm. The content of the metal element in the organic-inorganic composite of the present invention is 0.1 to 46% by weight.
Is preferable, and more preferably 5 to 37% by weight.

The laminate of the present invention has a structure in which the organic-inorganic composite produced by the production method of the present invention is laminated. For example, by sequentially applying a plurality of mixed liquids having different metal alkoxide contents and stacking them, it is possible to form a laminate in which the content of the metal element of the metal alkoxide is different in each layer.

In the first aspect of the laminated body of the present invention, there is a concentration gradient in which the metal element of the metal alkoxide increases or decreases from one surface to the other surface of the laminated body. Generally, the refractive index of the organic-inorganic composite can be changed by changing the concentration of the metal element in the organic-inorganic composite. Therefore, in the laminate according to the first aspect,
Due to the concentration gradient of the metal element, it is possible to provide a graded structure in which the refractive index decreases or increases from one surface to the other surface of the stack. The laminated body having such an inclined structure can be used as an optical component material such as an optical waveguide or an optical fiber.

In the second aspect of the laminated body of the present invention, the concentration gradient is such that the metal element of the metal alkoxide once increases and then decreases from one surface to the other surface of the laminated body.
Therefore, the laminated body of the second aspect can be provided with an inclined structure in which the refractive index generally decreases from one surface to the other surface of the laminated body and then increases.

In the third aspect of the laminated body of the present invention, the concentration gradient is such that the metal element of the metal alkoxide once decreases and then increases from one surface to the other surface of the laminated body.
Therefore, in the laminated body according to the third aspect, generally, a graded structure in which the refractive index once increases from one surface to the other surface of the laminated body and then decreases can be provided.

In the laminated body according to the second aspect and the third aspect, the laminate having the above-mentioned graded refractive index structure is the first
Like the laminate of the above aspect, it can be used as a material for optical parts such as an optical waveguide and an optical fiber.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

[Preparation of Metal Alkoxide Solution] Tetraethoxysilane (TEOS) was used as the metal alkoxide. Tetraethoxysilane was mixed with isopropyl alcohol (IPA) as a solvent and 0.05N hydrochloric acid in the proportions shown in Table 1 to prepare a metal alkoxide solution (solution A). In solution A, the molar ratio of water to metal alkoxide (water / TEOS) is 2.0.
Is.

[0025]

[Table 1]

The solution A was kept at 26 ° C. in a beaker, and TEOS in the solution A was hydrolyzed with stirring to cause polycondensation. The solution A was sampled at a predetermined time, and the amount of unreacted TEOS in the solution A, that is, TEO
The residual amount of S was analyzed by gas chromatography.

FIG. 1 is a diagram showing the relationship between the reaction time of hydrolysis and the remaining amount of TEOS. As shown in FIG. 1, it can be seen that the remaining amount of TEOS decreases with the reaction time. From the graph shown in FIG. 1, it can be seen that when the reaction time is 12 hours or more, the remaining amount of TEOS becomes 3% by volume or less.

[Preparation of Organic Polymer Solution] Polyvinylpyrrolidone (PVP) was used as the organic polymer. PVP
Was dissolved in IPA as a solvent at a ratio shown in Table 2 to prepare an organic polymer solution (solution B).

[0029]

[Table 2]

[Evaluation of Relationship between Remaining Amount of TEOS in Solution A and Transmittance] As shown in Table 3, reaction was performed for a predetermined time,
The remaining amount of TEOS is 1% by volume, 3% by volume, 5% by volume,
Solution A and solution B, which were adjusted to 10% by volume and 20% by volume, were mixed to prepare five types of coating solutions. In addition, solution A3
To 7.7 g, 12.3 g of solution B was mixed to give a total of 50
It was mixed so as to be g.

The thus obtained five types of coating solutions were applied on a quartz glass substrate having a thickness of 1 mm by a spin coating method, and then dried in an electric furnace at about 110 ° C. for 1 hour to give a thickness of 10
A thin film of organic-inorganic composite having a thickness of μm was formed on the substrate. For the thin film on this substrate, a wavelength of 630n was measured in the direction perpendicular to the substrate.
m light was irradiated and the transmittance was measured. The measurement results are shown in Table 3.

[0032]

[Table 3]

As is clear from the results shown in Table 3, by setting the residual amount of TEOS in the solution A to 3% by volume or less, a high transmittance is obtained and excellent optical transparency is obtained. I understand.

[Evaluation of Relationship between Remaining Amount of TEOS in Solution A and Size of Domain in Thin Film] The reaction time was changed in the same manner as described above, so that the remaining amount of TEOS was 1% by volume, 3% by volume, 5% by volume, 10% by volume, 20% by volume, and 30% by volume of each solution A were prepared, and each solution A and solution B were mixed to prepare 6 types of coating solutions. In addition, solution A37.7
Solution B (12.3 g) was mixed with g so that the total amount was 50 g.

The thus obtained six types of coating solutions were applied onto a quartz glass substrate by spin coating in the same manner as above,
A thin film of an organic-inorganic composite was formed on the substrate. For each film, the size of the domains in the film was measured. The domain is a domain formed from an organic region or an inorganic region. Regarding the thin film using the solution A in which the remaining amount of TEOS was 1% by volume and 3% by volume, the size of the domain was small. Therefore, the thin film was observed by an electron microscope to measure the size of the domain in the thin film. Solution A with remaining TEOS content of 5% by volume, 10% by volume, 20% by volume, and 30% by volume
Since the domain size of the thin film using was large, the domain size was measured using an optical microscope.
FIG. 13 is a diagram showing the relationship between the amount of TEOS remaining in the solution A and the size of domains in the thin film. Since the size of the domains in the thin film has a distribution, the width between the minimum value and the maximum value is indicated by a line in FIG.

As is clear from FIG. 13, T in solution A
By setting the residual amount of EOS to be 3% by volume or less, the size of the domain can be set to 0.1 μm or less. Therefore, it may be used as a wavelength for optical communication.
A small domain size that does not hinder the transmission of light in the wavelength range of 0 nm to 1600 nm can be obtained.

[Evaluation of Relationship Between TEOS Remaining Amount in Solution A and Delamination Occurrence Area of Thin Film] Similarly to the above, the reaction time was changed so that the TEOS remaining amount was 1% by volume, 3% by volume,
6% coating liquids were prepared in the same manner as above using the solution A containing 10% by volume, 20% by volume, and 30% by volume.

On a glass substrate having a length of 2.5 cm and a length of 2.5 cm, each coating solution was applied in the same manner as above to form a thin film of an organic-inorganic composite having a thickness of 10 μm. After standing for 10 days, the area of the portion where the thin film was peeled from the substrate was measured. The measurement result is shown in FIG. 14
As is clear from the above, by setting the residual amount of TEOS in the solution A to 3 vol% or less, good adhesion to the substrate can be obtained.

[Preparation of Solution C and Solution D, and their mixed coating solution] TEOS was mixed with acetone as a solvent and 0.
A 05N hydrochloric acid aqueous solution was mixed at a ratio shown in Table 4 to prepare a solution C.

[0040]

[Table 4]

Polymethyl methacrylate (PMMA) as an organic polymer was mixed with acetone as a solvent at a ratio shown in Table 5 to prepare a solution D.

[0042]

[Table 5]

Solution D was mixed with solution C having a residual TEOS content of 3% by volume to prepare a mixed coating solution. In addition,
The solution C (16.6 g) was mixed with the solution D (5.4 g). Similarly to the above, this mixed coating solution was applied onto a quartz glass substrate to form a thin film having a thickness of 10 μm, and the thin film was shaped,
When the transmittance of light having a wavelength of 630 nm was measured for the obtained thin film, the transmittance was 95 to 90%.

[Preparation of Solution E and Solution F and their mixed coating solutions] Phenyltriethoxysilane was used as the metal alkoxide. Phenyltriethoxysilane was added at a ratio shown in Table 6 to N-methyl-2- as a solvent.
Solution P was prepared by mixing pyrrolidone (NMP) with a 0.05 N hydrochloric acid aqueous solution.

[0045]

[Table 6]

PMMA was mixed with NFP as a solvent in a ratio shown in Table 7 to prepare a solution F.

[0047]

[Table 7]

The residual amount of phenyltriethoxysilane is 3
The solution F was mixed with the solution E having a volume% to prepare a mixed coating solution. In addition, solution F (4.4 g) was added to solution E (15.6 g).
Were mixed.

The mixed coating solution was coated on a quartz glass substrate in the same manner as described above to form a thin film of an organic-inorganic composite having a thickness of 10 μm, and this was irradiated with light having a wavelength of 630 nm to measure the transmittance. . The transmittance was 95 to 90%.

[Preparation of coating liquids having different Si contents and measurement of refractive index of organic-inorganic composite thin film] Solution A and solution B
Were mixed at the ratios shown in Table 8 to prepare coating liquids 1 to 5 having different Si contents. As the solution A, a solution which was hydrolyzed and polycondensed until the residual amount of TEOS became 1% by volume was used.

[0051]

[Table 8]

The coating liquids 1 to 5 were respectively coated on the glass substrate in the same manner as above to form a thin film of the organic-inorganic composite having a thickness of 2 μm. The refractive index of the formed thin film was measured. Figure 2
FIG. 4 is a diagram showing the refractive index of a thin film formed from coating liquids 1 to 5. In FIG. 2, the relationship between the Si content in the organic-inorganic composite and the refractive index is shown.

As shown in FIG. 2, it can be seen that the refractive index decreases as the Si content increases. Hereinafter, examples according to the first aspect of the laminate of the present invention will be described.

FIG. 3 is a schematic sectional view showing an embodiment according to the first aspect of the laminated body of the present invention. Referring to FIG. 3, on the substrate 1, thin films 2a, 2 of organic-inorganic composite are provided.
b, 2c, and 2d are stacked. Thin film 2a-2d
The laminated body 2 is constituted by the above. Thin films 2a, 2b,
2c and 2d are thin films in which the metal elements in the thin film increase or decrease in this order. For example, when alkoxysilane is used as the metal alkoxide, the thin films 2a-2
The thin films 2a to 2d are formed so that the Si content in d gradually increases or decreases. Therefore, the laminated body 2 has a concentration gradient such that the Si element concentration increases or decreases from the substrate 1 toward the surface of the laminated body 2.

As described with reference to FIG. 2, the refractive index of the thin film decreases as the Si content increases. Therefore, when the laminated body 2 has a concentration gradient such that the Si content increases from the substrate 1 toward the surface of the laminated body 2, the gradient in which the refractive index decreases from the substrate 1 toward the surface of the laminated body 2. The structure is formed. On the contrary, when the laminated body 2 has a concentration gradient such that the Si content decreases from the substrate 1 toward the surface of the laminated body 2, the refractive index increases from the substrate 1 toward the surface of the laminated body 2. An inclined structure is formed.

(Example 1) The above coating solution 5, coating solution 4, coating solution 3, coating solution 2 and coating solution 1 were applied in this order on a quartz glass substrate to form a thin film of an organic-inorganic composite. 5 layers were laminated to form a laminate. The coating liquid was applied by spin coating. The thickness of each layer was set to be 2 μm after drying. The film thickness was controlled by the rotation speed of the substrate in the spin coating method. Also,
After applying each coating solution, it was dried in an electric furnace at about 110 ° C. for 1 hour. Since the thin films are laminated in five layers, they were dried in the electric furnace five times in total.

FIG. 4 is a diagram showing the concentration distribution of the Si element in the laminated body formed as described above. The concentration of Si element was measured by secondary ion mass spectrometry (SIMS). In FIG. 4, the horizontal axis represents the distance from the substrate surface. As is clear from FIG. 4, in the laminated body of Example 1, the concentration of Si element increases from the substrate toward the surface of the laminated body.

No cracks were observed on the surface of the laminate of Example 1. For comparison, a thin film was formed on a quartz glass substrate using only the coating liquid 3 so that the thickness after drying was 10 μm. In this comparative thin film, cracks were found to occur on the surface.
In the laminated body of Example 1, since there is a concentration gradient such that the concentration of Si element increases toward the surface, the stress at the time of forming the laminated body is relaxed by the concentration gradient, and therefore the surface is It seems that no cracks occurred. Therefore, it is considered that the adhesion to the substrate is improved by imparting such a concentration gradient to the laminated body.

(Example 2) As in Example 1, coating liquid 5, coating liquid 4, coating liquid 3, coating liquid 2, and coating liquid 1 were formed on a quartz glass substrate (refractive index: 1.46). Was applied in this order to form a laminate. However, in Example 2, the thickness of each layer after drying was 20 μm and 10 μm, respectively.
m, 5 μm, 3 μm, and 22 μm.

FIG. 5 is a diagram showing the distribution of the refractive index in the thickness direction of the layered product of Example 2. As shown in FIG. 5, this laminated body is provided with an inclined structure in which the refractive index gradually decreases from the substrate toward the surface of the laminated body.

As shown in FIG. 6, this laminate was used as a graded index type planar optical waveguide. Figure 6
Referring to, a laminated body 4 is provided on the quartz glass substrate 3. This laminated body 4 is the laminated body of the second embodiment. The laser beam 5 was introduced to the end surface of the layer of the laminate 4 having a low refractive index close to the substrate 3. Laminated body 4 on the side opposite to the side where laser light 5 is introduced
An optical system 6 was arranged near the end face of the screen, and a screen 7 was arranged at a position separated from the optical system 6 by a predetermined distance. The laser light 5 introduced to the one end surface of the laminated body 4 passes through the optical system 6,
It was projected on the screen 7. It was confirmed that the laminated body of Example 2 projected as a sharp light spot on the screen 7 and functions as a planar optical waveguide.

Next, examples according to the second and third aspects of the laminate of the present invention will be described. FIG. 7 is a schematic cross-sectional view showing an example according to the second aspect of the laminate of the present invention. With reference to FIG. 7, a laminated body 9 is formed by laminating thin films 9a, 9b, 9c, 9d, 9e, 9f, and 9g of an organic-inorganic composite on a substrate 8. In the thin films 9a to 9g, the metal element content of the thin film 9d is the highest. The content of the metal element of the metal alkoxide becomes higher as the thin films 9a, 9b, 9c, and 9d become higher, and the content of the metal element becomes lower as the thin films 9d, 9e, 9f, and 9g become lower. Therefore, in the stack 9, a concentration gradient is formed in which the metal element of the metal alkoxide once increases and then decreases.
As described above, since the refractive index decreases as the Si content increases, the laminated body 9 has a graded structure in the thickness direction in which the refractive index once decreases and then increases.

FIG. 8 is a schematic sectional view showing an embodiment according to the third aspect of the laminated body of the present invention. Referring to FIG.
On the substrate 10, the organic-inorganic composite thin films 11a and 11 are formed.
b, 11c, 11d, 11e, 11f and 11g are laminated in this order. The laminated body 11 is composed of the thin films 11a to 11g. In the laminated body 11, the thin film 11d is formed so that the concentration of the metal element is the lowest. Thin films 11a, 11b, 11c, and 11
The concentration of the metal element decreases as the thickness becomes d, and the thin film 11
The metal element concentration increases as d, 11e, 11f, and 11g. Therefore, in the laminated body 11, a concentration gradient is formed in the thickness direction in which the metal element of the metal alkoxide once decreases and then increases. As described above, the refractive index decreases as the Si content increases. Therefore, in the laminated body 11, an inclined structure in which the refractive index once increases and then decreases is formed in the thickness direction.

(Example 3) Coating liquid 5, coating liquid 4, coating liquid 3, coating liquid 2, coating liquid 1, coating liquid 2, coating liquid 3, coating liquid 4, and coating liquid 5 on a quartz glass substrate. Was applied in this order, and thin films were laminated. The coating method and the drying method of the coating liquid were the same as in Example 1. The thickness of each layer was set to be 2 μm after drying. A laminated body was produced by laminating a total of 9 thin films.

FIG. 9 is a diagram showing the concentration distribution of the Si element in the thickness direction of the laminate measured by SIMS. As shown in FIG. 9, the Si element concentration is highest in the center of the laminated body, and the Si element concentration once increases and then decreases in the thickness direction of the laminated body. Therefore, the refractive index once decreases in the thickness direction and then increases.

As shown in FIG. 9, in the laminated body, the distance from the substrate surface is about 1, 3, 5, 7, 9, 11, 1.
Regions having a thickness of about 1 μm in which the Si element concentration is substantially constant are formed at the locations of 3, 15, and 17 μm.
Further, between these regions, there is a region in which the Si element continuously changes. Such areas are
It is considered to be formed by the diffusion of the Si element near the interface between the layers.

(Example 4) A laminated body was prepared in the same manner as in Example 3 except that each coating solution was formed so that each thin film had a thickness after drying of 0.5 µm. Formed. Since nine layers having a thickness after drying of 0.5 μm are laminated, the thickness of the laminated body is 4.5 μm.

FIG. 10 is a diagram showing the concentration distribution of the Si element in the laminate measured by SIMS. As shown in FIG. 10, since the thickness of each layer is thin in this laminated body, S
The i element concentration is continuously changing. Similar to the laminated body of Example 3, the Si element concentration is highest in the center, and the laminated body has a concentration gradient in which the Si element once increases and then decreases. Therefore, in the thickness direction of the laminated body, an inclined structure in which the refractive index once decreases and then increases is formed.

As a comparison, the thickness after drying is 4.5.
The coating liquid 3 alone was applied so as to have a thickness of μm to form a thin film of the organic-inorganic composite. When the surface of the thin film was observed after the thin film was formed, many cracks were observed. In contrast,
In the laminates of Examples 3 and 4, no cracks were found on the surface. In Example 3 and Example 4, since there is a concentration gradient of Si element in the laminated body, it is considered that the stress at the time of thin film formation was relaxed by this concentration gradient and no crack was generated on the surface. .

Example 5 Quartz glass substrate (refractive index:
1.46), and then apply coating liquid 1, coating liquid 2, coating liquid 3, coating liquid 4, coating liquid 5, coating liquid 4, coating liquid 3, coating liquid 2, and coating liquid 1 in this order. A laminated body was formed by laminating thin films of the organic-inorganic composite. The thickness of each coating solution after drying was 22 μm, 3 μm, 5 μm, and 10 μm, respectively.
m, 20 μm, 10 μm, 5 μm, 3 μm, and 22 μ
It was set to be m. The application of the coating solution and the drying were carried out in the same manner as in Example 1.

FIG. 11 is a diagram showing the distribution of the refractive index in the thickness direction of the obtained laminated body. As shown in FIG. 11, the refractive index is high in the center of the laminated body, and a graded structure is formed in which the refractive index once increases and then decreases in the thickness direction of the laminated body.

For the laminate of Example 5, the function as an optical waveguide was confirmed in the same manner as in Example 2. Figure 12
It is a schematic diagram which shows this state. As shown in FIG. 12, the laminated body 13 is formed on the substrate 12. Laminate 13
As shown in FIG. 11, a layer having a high refractive index is formed in the center thereof. Laser light 5 was introduced to the end face of the layer having a high refractive index, as in Example 2. As a result, a sharp light spot was observed on the screen 7. Therefore, it was confirmed that the laminated body of this example also functions as a planar optical waveguide.

In the above-mentioned embodiment, the concentration distribution of the Si element in the laminated body was measured by the secondary ion mass spectrometry (SIM).
S), but X-ray photoelectron spectroscopy (XP
The concentration gradient can also be measured by S), observing a cross section with an electron beam microanalyzer (EPMA), observing a cross section with a transmission electron microscope (TEM), and the like.

The organic-inorganic composite and the laminate thereof of the present invention are used not only for optical parts but also for various electronic parts,
It can also be used as a material for machine parts, various coating materials, insulating film materials and the like.

[0075]

According to the manufacturing method of the present invention, an organic-inorganic composite having excellent optical transparency can be manufactured. Further, the organic-inorganic composite and the laminate thereof of the present invention have excellent optical transparency and are useful as materials for optical parts such as optical waveguides and optical fibers. In addition, various electronic parts materials, machine parts materials, various coating materials,
It can also be used as an insulating film material or the like.

[Brief description of drawings]

FIG. 1 is a diagram showing a relationship between a reaction time of hydrolysis of a metal alkoxide and a residual amount of the metal alkoxide.

FIG. 2 is a diagram showing the relationship between the Si content and the refractive index in the organic-inorganic composite of the present invention.

FIG. 3 is a schematic cross-sectional view showing an example according to the first aspect of the laminate of the present invention.

FIG. 4 is a diagram showing a concentration distribution of Si element in an example according to the first aspect of the laminated body of the present invention.

FIG. 5 is a diagram showing a refractive index distribution in an example according to the first aspect of the laminated body of the present invention.

FIG. 6 is a schematic view showing an apparatus for an optical waveguide confirmation test in an example according to the first aspect of the laminate of the present invention.

FIG. 7 is a schematic cross-sectional view showing an example according to the second aspect of the laminate of the present invention.

FIG. 8 is a schematic cross-sectional view showing an example of the third aspect of the laminate of the present invention.

FIG. 9 is a diagram showing a concentration distribution of Si element in an example according to the second aspect of the laminated body of the present invention.

FIG. 10 is a diagram showing a concentration distribution of Si element in an example according to the second aspect of the laminated body of the present invention.

FIG. 11 is a diagram showing a refractive index distribution in an example according to the third aspect of the laminated body of the present invention.

FIG. 12 is a schematic diagram showing an apparatus for an optical waveguide confirmation test in an example according to the third aspect of the laminate of the present invention.

FIG. 13 is a graph showing the relationship between the amount of TEOS remaining in solution A and the size of thin film domains.

FIG. 14 is a diagram showing the relationship between the amount of TEOS remaining in solution A and the peeling occurrence area of a thin film.

[Explanation of symbols]

1 ... Substrate 2 ... Laminated body 2a to 2d ... Thin film of organic-inorganic composite 3 ... Substrate 4 ... Laminated body 5 ... Laser light 6 ... Optical system 7 ... Screen 8 ... Substrate 9 ... Laminated body 9a-9g ... Thin film of organic-inorganic composite 10 ... Substrate 11 ... Laminated body 11a to 11g ... Thin film of organic-inorganic composite 12 ... Substrate 13 ... Laminated body

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 39/06 C08L 39/06 4J246 69/00 69/00 83/02 83/02 83/04 83/04 101/00 101/00 G02B 6/12 C08G 77/42 6/13 G02B 6/12 N // C08G 77/42 M (72) Inventor Koji Yamano 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Yo Electric Co., Ltd. (72) Inventor Hitoshi Hirano 2-5-5 Keihan Hondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. F-term (reference) 2H047 KA02 PA02 PA28 QA02 QA05 4D075 AE03 BB16X BB92Z CA23 CB01 CB06 DA06 DB13 DB43 DC16 DC21 DC24 EA07 EB13 EB14 EB19 EB22 EB32. 00W CG00W CL00W CM04W CP02X CP03X CP16X GF00 GP02 HA03 4J031 AA12 AA13 AA20 AA25 AA44 AA45 AA47 AA52 AA55 AA59 AB01 AB04 AD01 AF10 AF12 CA21 CA21 CA21 CA21 CA21 CA140 CA40 CA40 CATBA40 AZB 409 BB ABABAXBA120 BA40X EA19 EA24 EA25 EA26 FA071 FA121 GB40 GC24 GD08 HA14

Claims (12)

[Claims] 1. A method for producing an organic-inorganic composite formed from an organic polymer and a metal alkoxide, wherein the metal alkoxide is hydrolyzed and polycondensed until the unreacted metal alkoxide becomes 3% by volume or less. A method for producing an organic-inorganic composite, comprising: a step; and a step of mixing the condensation-polymerized metal alkoxide and the organic polymer to form an organic-inorganic composite. 2. The method for producing an organic-inorganic composite according to claim 1, wherein the metal alkoxide is an alkoxysilane. 3. The method for producing an organic-inorganic composite according to claim 1, wherein the organic polymer is polyvinylpyrrolidone, polycarbonate, polymethylmethacrylate, or a mixture thereof. 4. An organic-inorganic composite produced by the method according to any one of claims 1 to 3. 5. The organic-inorganic composite according to claim 4, which is formed on a transparent substrate. 6. A laminate having a structure in which organic-inorganic composites produced by the method according to any one of claims 1 to 3 are laminated, and the laminate has one surface facing toward the other surface. A laminate having a concentration gradient in which the metal element of the metal alkoxide increases or decreases. 7. The laminated structure according to claim 6, wherein a gradient structure in which the refractive index decreases or increases from one surface to the other surface of the laminated body is provided by the concentration gradient of the metal element. body. 8. A laminate having a structure in which organic-inorganic composites produced by the method according to any one of claims 1 to 3 are laminated, the laminate from one surface to the other surface. A laminate having a concentration gradient in which the metal element of the metal alkoxide once increases and then decreases. 9. The gradient structure in which the refractive index once decreases from one surface to the other surface of the laminate and then increases due to the concentration gradient of the metal element is provided. Stack of. 10. A laminate having a structure in which organic-inorganic composites produced by the method according to any one of claims 1 to 3 are laminated, and the laminate has one surface facing toward the other surface. A laminate having a concentration gradient in which the metal element of the metal alkoxide once decreases and then increases. 11. The tilted structure according to claim 10, wherein a gradient structure is provided in which the refractive index once increases from one surface to the other surface of the laminate and then decreases due to the concentration gradient of the metal element. Stack of. 12. An optical waveguide comprising the laminated body according to claim 7, 9, or 11.