JP2014189635A - Organic-inorganic composite, structure, and method for manufacturing organic-inorganic composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance functionalities of an organic-inorganic composite.SOLUTION: The organic-inorganic composite of the present invention comprises: an inorganic compound including amino groups; an organic compound including carbonyl groups; and a silver component. It is also permissible for this organic-inorganic composite to include: an inorganic compound possessing not only a metal matrix structure including a metal M and oxygen but also an amino group coupled with the side chain Rof the matrix structure; and an organic compound including carbonyl groups in a state where a certain interaction is being invoked between the amino group and carbonyl group. The carbonyl group is assumed to be coupled with the side chain Rof the organic compound and to possess a terminal group R.

Description

  The present invention relates to an organic-inorganic composite, a structure, and a method for producing the organic-inorganic composite.

Conventionally, as a composite, a nanocomposite in which silver nanoparticles are uniformly dispersed in an organic polymer having a carbonyl group such as poly (2-ethyl-2oxazoline) has been proposed (for example, see Patent Document 1). ). This composite has high permeability to olefin, stable separation performance even under dry operating conditions, and no decrease in separation performance due to silver ion reduction or the like. Moreover, as an organic-inorganic composite, an organic polymer having a carbonyl group such as polyoxazoline and a transition metal uniformly dispersed in an inorganic oxide matrix such as silica gel has been proposed (for example, , See Patent Document 2). The organic-inorganic composite is useful as a color filter, and the porous silica obtained by firing the composite is extremely useful as a highly efficient transition metal-supported inorganic catalyst. In addition, as an organic-inorganic composite, a hybrid film composed of an organic polymer having a carbonyl group such as poly (N-vinylpyrrolidone) (PVP) and a SiO ₂ skeleton with AgBF ₄ added has been proposed ( For example, refer nonpatent literature 1). The organic-inorganic composite, for example, and has a resolution of C ₂ H ₄ and C ₂ H _6.

JP 2007-021473 A JP-A-5-310994

Journal of Materials Science Letters, 21 (2002) 525-527

However, since the composite described in Patent Document 1 is an organic membrane, it may swell into, for example, a high-pressure olefin, resulting in a decrease in separation performance. In the organic-inorganic composite described in Patent Document 2, the separation performance of a fluid such as a gas has not been studied. For this reason, the addition of silver has not been studied, and the bond between the inorganic oxide matrix and the organic polymer has sometimes been insufficient for use in fluid separation. Further, the organic-inorganic composite described in Non-Patent Document 1 requires heating at a high temperature of 150 ° C. in order to sufficiently bond the organic polymer and the SiO ₂ skeleton, and the silver component aggregates by such heating. In some cases, the separation performance deteriorates.

  The present invention has been made to solve such problems, and has as its main object to provide an organic-inorganic composite, a structure, and a method for producing the organic-inorganic composite that can further enhance functionality. .

  As a result of diligent research to achieve the main object described above, the present inventors have found that when an inorganic compound having an amino group, an organic compound having a carbonyl group, and a silver component are included, the functionality is further improved. It has been found that it can be enhanced, and the present invention has been completed.

That is, the organic-inorganic composite of the present invention is
An inorganic compound having an amino group;
An organic compound having a carbonyl group;
With silver component.

  The structure of the present invention comprises a base material and the organic-inorganic composite described above formed on the base material.

The method for producing the organic-inorganic composite of the present invention comprises:
A method for producing an organic-inorganic composite comprising an inorganic compound, an organic compound, and a silver component,
Using the substance having an amino group as the raw material for the inorganic compound and using the substance having a carbonyl group as the raw material for the organic compound, the inorganic compound and the organic compound are combined to form an organic-inorganic composite. To obtain a composite process.

  The method for producing an organic-inorganic composite, structure and organic-inorganic composite of the present invention can further enhance functionality. The reason is presumed as follows. For example, since an inorganic compound has an amino group and an organic compound has a carbonyl group, even if synthesized at a relatively low temperature such as 100 ° C. or lower or normal temperature, It is thought that moderate binding force works between them. Then, it is considered that the inorganic compound and the organic compound are uniformly mixed to stabilize the structure. By the way, the silver component sometimes aggregates when heated at a temperature higher than 100 ° C. However, in this invention, even if it synthesize | combines at comparatively low temperature, since the structure of an inorganic type compound and an organic type compound can be stabilized and heating at high temperature is unnecessary, aggregation of the silver component by heating can be suppressed. And since a silver component disperse | distributes uniformly, without aggregating, the function which a silver component, such as a separation function, can express more highly. Thereby, it is thought that functionality can be improved more.

Explanatory drawing showing an example of the organic inorganic composite of this invention. Explanatory drawing showing the specific example of an organic inorganic composite. FIG. 3 is an explanatory diagram illustrating an example of a schematic configuration of a structure body.

  An embodiment of the structure of the present invention will be described with reference to the drawings. Drawing 1 is an explanatory view showing an example of an organic inorganic composite which is one embodiment of the present invention. FIG. 2 is an explanatory diagram illustrating a specific example of an organic-inorganic composite. FIG. 3 is an explanatory diagram illustrating an example of a schematic configuration of the structure 10. The organic-inorganic composite of the present invention includes an inorganic compound having an amino group, an organic compound having a carbonyl group, and a silver component.

  The inorganic compound may have, for example, a metal matrix structure and an amino group bonded to the metal matrix structure. The metal matrix structure may be, for example, a chain structure of metal and oxygen or a three-dimensional structure. The amino group may be bonded to a metal in the metal matrix structure. This amino group may be bonded to the main chain of the metal matrix structure, or may be an amino group bonded to the side chain. Examples of the side chain include a hydrocarbon group having about 1 to 10 carbon atoms, which may have a substituent. The side chain may include one or more of N, O, S, and P. The inorganic compound may be a compound containing one or more selected from Si, Ti, Al, and Zr and O. A compound containing these metals tends to have a structure with high mechanical strength due to bonding with oxygen. In addition, a chain structure or a three-dimensional structure is preferable.

  The inorganic compound may be a hydrolyzed compound of a metal alkoxide. Metal alkoxide is preferable because it is easily hydrolyzed and polymerized. This metal alkoxide may have, for example, the above amino group. As the metal alkoxide, for example, when the metal is Si, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropyldiethoxymethylsilane, N- 2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3aminopropylmethyldimethoxysilane, 3- Ureidopropyltriethoxysilane and the like are mentioned. When the metal is Ti, 2- (dimethylaminomethyl) -4,6-dimethylphenoxytriisopropoxytitanium and the like are mentioned.

  The organic compound may have a carbon structure in which carbon atoms are bonded and a carbonyl group bonded to the carbon structure. This carbon structure may be a chain structure or a three-dimensional structure. The carbon structure may include one or more of N, O, S, and P in the main chain and side chain. The carbonyl group may be bonded to the main chain of the carbon structure, or may be a carbonyl group bonded to the side chain. Such can include polymers. Examples of the polymer include polyesters (polyethylene terephthalate, polyarylate, etc.), polycarbonates, polyamides, polyurethanes, etc., as those containing a carbonyl group in the main chain. Examples of the polymer include those containing a carbonyl group in the side chain, such as polyvinylpyrrolidone (PVP), poly (2-ethyl-2-oxazoline) (POZ), polyvinyl acetate (PVAc), polymethyl methacrylate ( PMMA).

The silver component may be metallic silver or silver ions. Since a silver component can express the function which a silver component has in a small amount, it is more preferable that it is a silver ion. When the silver component is metallic silver, the particle size D50 is preferably 1 nm or more and 10 nm or less. If the silver component is silver ion, for example, PF ₆ ^- or ^{_{BF 4 -, ClO 4 -,}} NO 3 - that constitute the anion with a salt, such as, i.e., such _{AgPF 6, AgBF 4, AgClO 4} , AgNO 3 May be included. This silver component is preferably contained in an amount of 20 mol% or more based on the metal constituting the metal matrix structure described above. This is because the silver component is contained so that the function of the silver component can be expressed more highly. In the organic-inorganic composite of the present invention, since the organic compound and the inorganic compound are uniformly mixed, the silver component is easily dispersed and contains a large amount of the silver component (for example, constituting a metal matrix structure). In the case of 20 mol% or more with respect to the metal, the silver component hardly aggregates.

  The organic-inorganic composite of the present invention may have a function of selectively transmitting a specific component contained in a fluid composed of a plurality of components. Examples of the fluid include liquid and gas. For example, the organic-inorganic composite may have an olefin / paraffin separation function. At this time, the silver component may exhibit a separation function. Moreover, the organic-inorganic composite of the present invention may have a function of separating the first component contained in the fluid and the second component contained in the fluid.

  In the organic-inorganic composite of the present invention, the selectivity maintenance ratio representing the durability of the olefin / paraffin separation function is preferably 0.50 or more, more preferably 0.60 or more, and 0.70. It is still more preferable that it is above. This selectivity maintenance rate is obtained as follows. Using an olefin simple substance gas or a paraffin simple substance gas, this gas is adsorbed to the organic-inorganic composite under measurement conditions of 23 ° C. and 0 MPa to 1 MPa. This adsorption is repeated 10 times. Using this adsorption result, (ethylene adsorption amount at 1 MPa) / (ethane adsorption amount) is defined as selectivity. Further, (selectivity at the 10th measurement) / (selectivity at the first measurement) is defined as the selectivity maintenance rate. The higher the selectivity maintenance rate, the higher the durability of the gas separation function. Examples of the olefin used include olefin and ethylene. Examples of paraffin include methane, ethane, and propane.

As shown in FIG. 1, for example, the organic-inorganic composite of the present invention includes an inorganic compound having a metal matrix structure containing a metal M and oxygen and an amino group bonded to a side chain R ¹ of the matrix structure, And an organic compound having a group, and some interaction may act between the amino group and the carbonyl group. In FIG. 1, the carbonyl group is bonded to the side chain R ² of the organic compound and has a terminal group R ³ . More specifically, for example, as shown in FIG. 2, the organic-inorganic composite includes an inorganic compound having an Si matrix structure to which an aminopropyl group is bonded and an organic compound that is a polymer having a pyrrolidone structure. It is also possible to have some interaction between the amino group and the carbonyl group.

  The domain size of the organic-inorganic composite is preferably 20 nm or less, and more preferably 10 nm or less. Here, “domain size” refers to the size of the structural unit of the organic-inorganic composite. If the inorganic substance and the organic substance are hybridized in a state where the domain size is small, it is considered that the mechanical strength is excellent. Moreover, it is thought that a silver component can be disperse | distributed uniformly. The domain size shall be measured as follows. First, the surface or cross section of the organic-inorganic composite was randomly photographed with a scanning electron microscope (SEM) or a transmission microscope (TEM), and 10 fields of view were randomly picked up. , It is separated into an area close to white and an area close to black. In SEM, the cross section of the organic-inorganic composite is taken at a magnification of 2000 to 5000 times. The maximum length (major axis) of the white or black circular region included in the image is defined as the domain size, and this domain size is measured. In TEM, the surface or cross section of an organic-inorganic composite is photographed at a magnification of 200,000 times, and separated into regions of different colors, specifically, regions close to white and regions close to black. Then, the domain is measured in the same manner as the SEM. The size of all domains in 10 fields of view is measured by the above method, and the average value is set as the domain size of the organic-inorganic composite.

  Next, a method for producing this organic-inorganic composite will be described. This manufacturing method uses an inorganic compound as a raw material for an inorganic compound, and a compound having a carbonyl group as a raw material for an organic compound to combine the inorganic compound and the organic compound, thereby producing an organic-inorganic composite. A compounding step to obtain a body.

  In the compounding step, for example, a metal alkoxide having an amino group is used as a raw material for an inorganic compound, a polymer having a carbonyl group is used as a raw material for an organic compound, and the metal alkoxide is hydrolyzed with a solution containing the metal alkoxide and the polymer. By doing so, an inorganic compound may be generated and an inorganic compound and an organic compound may be combined.

  The complexing step may include, for example, a precursor generation step in which a metal alkoxide is added to a solution in which an organic compound that is a polymer having a carbonyl group is dissolved, and hydrolysis and polymerization are performed to prepare a precursor sol. . In the precursor generation step, as the polymer solution, for example, the polymer may be dissolved in a mixed solution of an organic solvent such as N-methyl-2-pyrrolidone (NMP), an alcohol, and water. The metal alkoxide preferably has, for example, one or more metals selected from Si, Ti, Al and Zr and an amino group. In this case, the compounding step may include a drying step of drying the precursor sol. The drying of the sol is preferably performed at 100 ° C. or less, and more preferably at 80 ° C. or less.

  The compounding step may include, for example, a silver component addition step of adding a silver component. This silver component addition process may be performed before hydrolysis or may be performed after hydrolysis, for example. When performed after hydrolysis, for example, a silver component may be added to the precursor sol obtained in the precursor generation step described above. In addition, when the thing containing a silver component is used as the raw material of an inorganic compound or the raw material of an organic compound, the silver component addition process does not need to be. To add the silver component, metallic silver or a salt containing silver ions may be added. As the metal silver or the salt containing silver ions, those described above can be used.

  In this method for producing an organic-inorganic composite, the steps after the compounding step including the drying step described above are preferably performed at a temperature of 100 ° C. or lower, and more preferably performed at a temperature of 80 ° C. or lower. By so doing, the silver component is less likely to aggregate, and a decrease in functionality can be suppressed.

  Next, the structure of the present invention will be described. The structure of the present invention comprises a base material and any one of the organic-inorganic composites described above formed on the base material. Although a base material is not specifically limited, For example, organic materials, such as resin, an inorganic material, a metal material, etc. can be used. Examples of the inorganic material include one or more selected from cordierite, Si-bonded SiC, recrystallized SiC, aluminum titanate, mullite, silicon nitride, sialon, zirconium phosphate, zirconia, titania, alumina, and silica. it can. The organic-inorganic composite may be formed on the substrate as a film, for example. At this time, the thickness of the organic-inorganic composite can be, for example, about 0.01 μm to several tens of μm.

  A specific example of this structure will be described. As shown in FIG. 3, the structure 10 of the present invention includes a porous partition wall portion 14 as a base material for forming a plurality of cells 12 serving as a flow path for a mixed fluid, and the partition wall formed of the organic-inorganic composite described above. And a functional layer 16 provided on the inner surface 15 of the portion 14. In addition, a seal portion 18 is formed on the end surface 17 of the partition wall portion 14. The seal portion 18 is formed of a dense material such as glass, ceramics, or resin, and prevents inflow or outflow of fluid from the end surface 17 of the partition wall portion 14. In the structure 10, the functional layer 16 functions as a separation membrane that separates the mixed fluid. Specifically, among the mixed fluid entering the cell 12 from the inlet side, the fluid having a high affinity with the silver component of the functional layer 16 passes through the porous partition wall 14 in which the functional layer 16 is formed and is concentrated. And discharged from the side surface of the structure 10 as a concentrated fluid. On the other hand, a fluid that has a low affinity with the silver component and cannot pass through the functional layer 16 flows along the flow path of the cell 12 and is discharged from the outlet side of the cell 12 as a separation fluid. The partition wall portion 14 may have a multilayer structure of two or more layers in which a fine particle portion 14b having a small pore diameter is formed on the surface of a coarse particle portion 14a having a large pore diameter. The pore diameter of the coarse particle portion 14a can be set to, for example, about 0.1 μm to several hundred μm. The pore diameter of the fine-grained portion 14b only needs to be smaller than the pore diameter of the coarse-grained portion 14a. For example, the pore diameter can be about 0.001 to 1 μm. If it carries out like this, the permeation | transmission resistance of the partition part 14 can be reduced. Thus, the structure 10 can be formed and an organic-inorganic composite can be utilized.

  According to the organic-inorganic composite described above, since the inorganic compound has an amino group and the organic compound has a carbonyl group, the inorganic compound and the organic compound can be synthesized even at a relatively low temperature. Can be uniformly mixed to stabilize the structure, and heating at a high temperature is unnecessary. For this reason, aggregation of the silver component by heating can be suppressed. And since the dispersibility is high, without a silver component aggregating, the function which silver, such as a separation function, can express more highly. Thereby, functionality can be improved more.

  It should be noted that the present invention is not limited to the above-described embodiment, and it goes without saying that the present invention can be implemented in various modes as long as it belongs to the technical scope of the present invention.

  For example, in the above-described embodiment, the structure 10 includes a plurality of cells 12 and fluid flows. However, if the structure 10 includes a base material and an organic-inorganic composite formed on the base material, It is not limited to this shape. For example, it may be a tubular shape with one cell. Alternatively, the organic-inorganic composite of the present invention may be used in a powder state. The organic-inorganic composite powder can be used, for example, as an adsorbent or a catalyst.

  In the above-described embodiment, the functional layer 16 made of an organic-inorganic composite functions as a separation membrane that separates a mixed fluid as a fluid. However, the functional layer 16 is not limited to this, and sterilization that sterilizes and purifies liquids and gases. -It may function as a purification membrane. The structure 10 provided with the functional layer 16 as such a sterilization / purification film can be used as a sterilization / purification filter.

  Hereinafter, an example in which an organic-inorganic composite is specifically produced will be described as an experimental example. Experimental examples 1 to 4 and 7 correspond to examples of the present invention, and experimental examples 5 to 6 correspond to comparative examples.

[Experimental Example 1]
First, a precursor sol was synthesized. A polymer solution was prepared by mixing 2 g of polyvinylpyrrolidone as a polymer and 80 g of a mixed solvent of ethanol and water (9: 1 in molar ratio) as a solvent. Next, 1 g of nitric acid as a catalyst was added to the polymer solution. 10 g of 3-aminopropyltriethoxysilane as a raw material for the inorganic compound was added to the polymer solution and stirred. Then, hydrolysis and polymerization of 3-aminopropyltriethoxysilane proceeded. Furthermore, ₄ g of AgBF ₄ was added to this solution and stirred to obtain a precursor sol. This precursor sol was put in a petri dish and dried to prepare a gel. The obtained gel was dried at 70 ° C. overnight, and the obtained organic-inorganic composite was used as Experimental Example 1.

[Experimental Example 2-4]
Except for using poly (2-ethyl-2-oxazoline) in place of polyvinylpyrrolidone, the same steps as in Experimental Example 1 were performed, and the obtained organic-inorganic composite was set as Experimental Example 2. Further, the same process as in Experimental Example 1 was performed except that polyvinyl acetate was used instead of polyvinyl pyrrolidone, and the obtained organic-inorganic composite was taken as Experimental Example 3. Moreover, it is the same as that of Experimental Example 1 except that N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was used instead of 3-aminopropyltriethoxysilane in the hydrolysis and polymerization steps of the metal alkoxide. The organic-inorganic composite obtained by performing the above process was used as Experimental Example 4.

[Experimental Example 5]
The addition of the catalyst and the addition of the metal alkoxide in Experimental Example 1 were omitted, and Experimental Example 5 was the one containing no inorganic compound.

[Experimental Example 6]
In the step of hydrolysis and polymerization of metal alkoxide, the same steps as in Experimental Example 1 were carried out except that tetraethoxysilane was used instead of 3-aminopropyltriethoxysilane, and the resulting organic-inorganic composite was tested as an experimental example. It was set to 6.

[Experimental Example 7]
The precursor sol produced in Experimental Example 1 was applied onto a porous alumina substrate having a diameter of 10 mm, a length of 10 cm, and a surface pore diameter of 0.1 μm, and dried at 70 ° C. overnight to produce a structure. One end of this structure was sealed, a glass tube was connected to the other end, and the resulting structure was referred to as Experimental Example 7.

(Durability evaluation of adsorption performance)
The measurement regarding the gas separation function of Experimental Examples 1 to 6 was performed using a high-pressure gas adsorption amount measuring apparatus (MSB-AD-H manufactured by Nippon Bell Co., Ltd.) having a magnetic floating balance. Here, the separation function of olefin / paraffin was considered, and as a model, ethylene and ethane adsorption measurements were repeated 10 times. If either ethylene or ethane is more adsorbed, it can be determined that the olefin / paraffin separation function is higher. The adsorption measurement was carried out using ethylene simple gas or ethane simple gas under measurement conditions of 23 ° C. and 0 MPa to 1 MPa. Using the results of adsorption measurement, (ethylene adsorption amount at 1 MPa) / (ethane adsorption amount) was defined as selectivity. Further, (selectivity at the 10th measurement) / (selectivity at the first measurement) was defined as the selectivity maintenance rate. It can be determined that the higher the selectivity maintenance rate, the higher the durability of the gas separation function.

(Evaluation of gas permeability of structure)
The measurement regarding the gas separation function of Experimental Example 7 was performed. The gas permeability was evaluated using an ethylene / ethane mixed gas (1: 1) under measurement conditions of 23 ° C. and 1 MPa.

(Results and discussion)
It shows in Table 1 collectively about the structure and selectivity maintenance factor of the organic inorganic composite of Experimental Examples 1-6. As shown in Table 1, in Examples 5 and 6, the gas selectivity maintenance rate was extremely low. In Experimental Example 6, although the selectivity maintenance rate was higher than that in Experimental Example 5 as an effect of the addition of the inorganic compound, the value thereof was lower than in Experimental Examples 1 to 4. This is because the inorganic compound does not have an amino group, so the affinity between the inorganic compound and the organic compound is low, and peeling occurs between the inorganic compound and the organic compound, resulting in deterioration. Inferred. On the other hand, in Experimental Examples 1-4, it turned out that the selectivity maintenance rate of gas shows a high value with 0.50 or more. Considering this, it is presumed that the inorganic compound has a metal matrix structure having a metal-oxygen bond, and an amino group is bonded to the metal matrix structure. On the other hand, the organic compound has a carbonyl group. For this reason, it was considered that an ionic bond interaction was acting between the molecules of the amino group of the inorganic compound and the carbonyl group of the organic compound. It was speculated that this interaction strengthens the inorganic compound and the organic compound. Moreover, as a result of evaluating gas permeability in Experimental Example 7, it was confirmed that ethylene permeates selectively as compared with ethane.

  The present invention can be used in the field of functional materials such as filters and honeycomb structures.

  DESCRIPTION OF SYMBOLS 10 Structure, 11 End surface, 12 Cell, 14 Partition part, 14a Coarse grain part, 14b Fine grain part, 15 Inner surface, 16 Functional layer, 17 End surface, 18 Seal part.

Claims (13)

An inorganic compound having an amino group;
An organic compound having a carbonyl group;
Silver component,
An organic-inorganic composite comprising   The organic-inorganic composite according to claim 1, wherein the inorganic compound has a metal matrix structure and an amino group bonded to the metal matrix structure.   The organic-inorganic composite according to claim 1, wherein the inorganic compound is a compound containing one or more selected from Si, Ti, Al, and Zr and O.   The organic-inorganic composite according to any one of claims 1 to 3, wherein the inorganic compound is a hydrolyzed compound of a metal alkoxide.   The organic-inorganic composite according to any one of claims 1 to 4, wherein the organic compound has a carbon structure in which carbon atoms are bonded and a carbonyl group bonded to the carbon structure.   The organic-inorganic composite according to any one of claims 1 to 5, wherein the organic compound is a polymer having the carbonyl group.   The organic-inorganic composite according to any one of claims 1 to 6, which has a function of selectively transmitting a specific component contained in a fluid composed of a plurality of components. The inorganic compound has a metal matrix structure and an amino group bonded to the metal matrix structure.
The organic-inorganic composite according to any one of claims 1 to 7, wherein the silver component is contained in an amount of 20 mol% or more based on the metal constituting the metal matrix structure. A substrate;
The organic-inorganic composite according to any one of claims 1 to 8, formed on the substrate,
A structure with A method for producing an organic-inorganic composite comprising an inorganic compound, an organic compound, and a silver component,
Using the substance having an amino group as the raw material for the inorganic compound and using the substance having a carbonyl group as the raw material for the organic compound, the inorganic compound and the organic compound are combined to form an organic-inorganic composite. A compounding step to obtain,
A method for producing an organic-inorganic composite.   In the complexing step, a metal alkoxide having an amino group is used as a raw material of the inorganic compound, a polymer having a carbonyl group is used as the organic compound, and the metal alkoxide is added in a solution containing the metal alkoxide and the polymer. The method for producing an organic-inorganic composite according to claim 10, wherein the inorganic compound and the organic compound are compounded by hydrolysis.   The method for producing an organic-inorganic composite according to claim 11, wherein in the complexing step, the silver component is added after the hydrolysis.   The manufacturing method of the organic inorganic composite of any one of Claims 10-12 which performs the process after the said composite process at the temperature of 100 degrees C or less.

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