JPWO2019058912A1 - Allophane membrane composite, sheet using the same, and method for producing allophane membrane composite - Google Patents

Abstract

An object is to provide an allophane film composite in which an allophane plain film is formed on a base material such as an aluminum base material and a non-woven fabric, and to increase the adhesion strength and peel strength thereof. Also provided is a method for producing an allophane membrane complex. Further, the present invention provides a sheet using an allophane film composite in which a film of allophane is formed on a substrate such as an aluminum substrate or a non-woven fabric. An allophane film composite according to an embodiment of the present invention includes a substrate and an allophane film having an average diameter of 3.5 nm or more and 10 nm or less deposited on the substrate, the substrate and the allophane. The adhesive force with the film is 4 N/10 mm or more, and the number of times the allophane film is peeled off from the substrate by repeating the bending test at 90 degrees is 1 or more.

Description

The present invention relates to an allophane film composite in which a clay mineral allophane film formed by an aerosol deposition method has adhesion to a substrate.

Allophane is a low-crystalline aluminum silicate and amorphous aluminum silicate that are mainly present in soil derived from volcanic products such as pumice and ash. Allophane is composed of silicon (Si), aluminum (Al), oxygen (O) and hydrogen (H) (hydroxyl group (OH)). Its form is a hollow sphere with a diameter of 3.5 nm to 5 nm, a specific surface area (~900 m ² /g), a single layer of gibbsite octahedral sheet as a spherical wall, and a structure in which SiO ₄ tetrahedra are bonded to the inside. And there are many through holes of 0.3 nm to 0.5 nm in the spherical wall. Due to such a characteristic structure, allophane has a large surface area and has a hydroxyl group on the surface, so that it can adsorb water, organic substances, various gas components and the like. Due to these characteristics, allophane is applied in various fields such as a fuel storage medium such as natural gas and a humidity adjusting material that autonomously controls the humidity of the living environment.

However, since allophane is nanoparticles, it is molded into various shapes and used in order to facilitate handling in industrial use. The main shapes of allophane products are powder, granules, tablets and films. Of these, powder, granule, and tablet allophane products must be packaged in small portions or filled in a dedicated case before use. Therefore, an extra volume is required for each used space, and the usable area is limited.

On the other hand, the membranous allophane that does not have such a limitation can be used in a wider area and can be expected to have an application which has not been available until now. For example, by coating allophane on the packaging material, it is possible to add drying characteristics to the packaging material itself, eliminating the need to enclose a separate desiccant. it can.

As a method for molding allophane in a film form, paints and coating materials using the following binders have been proposed. For example, Patent Document 1 describes a method in which room temperature curable glass is applied to the surface of a solid-phase coating body to which allophane is attached to form a composite body in which voids of allophane are bonded with glass to coat the composite material. .. Patent Document 2 describes a coating liquid containing a white pigment, a silane compound and a solvent.

Patent Documents 3 and 4 describe a method for producing a weather-resistant and stain-resistant emulsion paint containing allophane-coated titanium oxide composite particles and a resin component. Further, Patent Document 5 describes a coating agent composed of an allophane and a resin for forming a porous continuous film having humidity control and gas adsorption properties. Further, Patent Document 6 describes a coating film of a transparent coating material in which allophane particles are mixed in an aqueous emulsion in which a synthetic resin is mixed. Further, in Patent Document 7, the inorganic humidity control material is 5 to 95% by weight, the resin binder (solid content) is 1 to 25% by weight, and the moisture permeability imparting agent (solid content) is 0.1 to 15% by weight. The coated wall material including is described. In Patent Document 8, a moisture absorbing/releasing material granular powder is added to the surface of a moisture absorbing/releasing base material containing a hydraulic substance such as allophane, slag, and cement, and either one or both of an organic reinforcing fiber and an inorganic fiber. A moisture absorptive and desorptive fireproof building material formed by forming a coating film layer with a paint is described. Further, Patent Document 9 describes an allophane film formed by mixing allophane with an aqueous binding medium such as latex or a paint having film-forming property and uniformly formed on a thin piece or a treated substrate.

The following methods have also been proposed for processing a fabric on which fibers are kneaded with allophane. For example, Patent Documents 10 and 11 describe that allophane is kneaded into a synthetic fiber and used as a fiber structure in the form of a film. Further, Patent Document 12 describes that a coating agent containing allophane is applied to the surface of a structure made of synthetic fibers.

Further, Patent Document 13 proposes a method of allowing allophane to penetrate into paper.

JP, 2014-226632, A JP, 2014-141626, A JP, 2010-150434, A JP, 2010-058994, A JP, 2008-138167, A JP, 2007-063779, A JP 2006-002407 A JP, 2003-155786, A JP 2001-047493 A JP, 2006-218403, A JP, 2005-105447, A JP, 2005-105448, A JP, 2003-073997, A

In the prior arts that provide these film-like allophane, the allophane is buried inside the binder, the fiber, and the paper, and the pores of the allophane are blocked to some extent. The present invention has been made in view of the conventional drawbacks, and an object thereof is to provide an allophane film composite in which an allophane simple film is formed on a substrate such as an aluminum substrate and a non-woven fabric, and to increase the adhesion strength thereof. And Also provided is a method for producing an allophane membrane complex. Furthermore, a sheet using an allophane film composite in which an allophane plain film is formed on a substrate such as an aluminum substrate or a non-woven fabric is provided.

An allophane film composite according to an embodiment of the present invention includes a substrate, and an allophane film having an average diameter of 3.5 nm or more and 10 nm or less and on which the allophane is deposited on the substrate. The adhesion with the allophane film is 4 N/10 mm or more, and the number of times the allophane film is peeled from the base material by repeating the 90-degree bending test is once or more.

The allophane film has a thickness of 5 μm or more and 70 μm or less, a moisture absorption rate of 10% or more and 30% or less, and a surface hardness of H or more.

The substrate is one selected from the group of glass, aluminum, alumina, non-woven fabric, non-woven fabric or alumina sheet coated with polyethylene film, alumina sheet coated with silica-containing polyethylene film, and PET sheet.

The nonwoven fabric is 24 hours of moisture permeability 9500 g / m ² or more 1100 g / m ² or less, air permeability 10 ml / cm ² or more 25 cc / cm ² or less, a density of 65 g / m ² or more 80 g / m ² or less, the thickness Is 0.14 mm or more and 0.25 mm or less.

The method for producing an allophane membrane composite according to one embodiment of the present invention is the method for producing an allophane membrane composite according to any one of the above items, wherein the allophane raw material fine particles are mixed with a carrier gas to form an aerosol, which is then aerosolized. The raw material fine particles are accelerated together with the carrier gas through a nozzle and jetted toward the surface of the base material to form an allophane film on the base material in the decompression chamber.

In one embodiment of the present invention, the water absorbent sheet includes an allophane membrane composite in which the base material is a nonwoven fabric.

In one embodiment of the present invention, the adsorption sheet includes an allophane membrane composite in which the base material is a nonwoven fabric.

In one embodiment of the present invention, the humidity control sheet includes an allophane film composite in which the base material is a non-woven fabric.

The allophane film of the present invention is characterized in that it is made of allophane alone containing no binder. Since the allophane pores are not blocked by the binder, the adsorptivity does not decrease. Compared with the allophane powder, there is no decrease in the adsorption ability of the allophane film. In addition, since it is in the form of a film, it has an advantage that the adsorption rate is faster than that of a bulk material containing only allophane.

It is a schematic diagram which shows the allophane membrane composite 10 which concerns on one Embodiment of this invention, (a) shows the perspective view of the allophane membrane composite 10, (b) shows the cross section of the allophane membrane composite 10. FIG. The allophane raw material fine particle 17 which concerns on one Embodiment of this invention is shown, (a) is a schematic diagram of the allophane raw material fine particle 17, (b) is a SEM image of the allophane raw material fine particle 17. FIG. It is a schematic diagram which shows an example of the manufacturing apparatus 1 by AD method used for the manufacturing method of the allophane film composite which concerns on one Embodiment of this invention. 1 shows an allophane film composite 10 according to an embodiment of the present invention, (a) shows a field emission electron microscope image of a cross section of the allophane film composite 10, and (b) shows an allophane film composite 20 using FIB. The cross-sectional image of is shown. 3 is a transmission electron microscope image of the allophane film 13 of the allophane film composite 10 according to one example of the present invention. 4 is a correlation curve between relative humidity and moisture absorption rate of the allophane film according to one example of the present invention. It is the figure which plotted the moisture absorption amount with respect to the weight of the allophane film which concerns on one Example of this invention. The result of the fatty acid adsorption test of the allophane membrane complex which concerns on one Example of this invention is shown. The result of the oil adsorption test of the allophane membrane composite concerning one example of the present invention is shown. 5 shows the results of a phosphate ion adsorption test of an allophane membrane composite according to an example of the present invention. The result of the humidity control test of the allophane membrane composite concerning one example of the present invention is shown. It is the figure which plotted the moisture absorption rate with respect to the moisture absorption time of the allophane membrane composite which concerns on one Example of this invention.

Hereinafter, an allophane membrane composite according to the present invention, a sheet using the same, and a method for producing the allophane membrane composite will be described with reference to the drawings. The allophane membrane composite of the present invention, the sheet using the same, and the method for producing the allophane membrane composite are not construed as being limited to the description of the embodiments and examples below. In the drawings referred to in the present embodiment and examples described later, the same portions or portions having similar functions are denoted by the same reference numerals, and repeated description thereof will be omitted.

FIG. 1 is a schematic diagram showing an allophane film composite 10 according to one embodiment of the present invention. FIG. 1A shows a perspective view of the allophane membrane composite 10, and FIG. 1B shows a sectional view of the allophane membrane composite 10. The allophane film composite 10 includes a base material 11 and an allophane film 13 in which the allophane fine particles 15 are deposited on the base material 11. The allophane film composite 10 includes an allophane film 13 which is made of allophane alone (only the allophane fine particles 15) containing no binder. Therefore, it has an unprecedented adsorption capacity comparable to that of a bulk material containing allophane alone. In addition, the allophane film 13 has a higher adsorption rate than the bulk body containing only allophane.

As allophane (also referred to as clay mineral allophane), one naturally produced in Japan and overseas can be adopted. Allophane can also be synthesized by a neutralization reaction of a coexisting solution of silicic acid and aluminum ions with an alkali such as sodium hydroxide. This synthetic allophane may be adopted in the allophane membrane composite according to the present invention. Although it is possible to use natural allophane as it is, preferably, the purity of the allophene film formed by using a raw material whose allophane purity is increased by a method of separating impurities such as quartz and volcanic glass contained therein by a method such as hydrangea separation. Can be increased.

FIG. 2 shows the allophane raw material fine particles 17. FIG. 2A is a schematic view of the allophane raw material fine particles 17, and FIG. 2B is a scanning electron microscope (SEM) image of the allophane raw material fine particles 17. The allophane raw material fine particles 17 have a structure in which a plurality of allophane fine particles 15 are aggregated. The allophane raw material fine particles 17 are amorphous particles having a particle diameter of several μm to several tens of μm.

The allophane film 13 has pores, and the allophane fine particles 15 have a dense to sparse deposition state from the side of the base material 11 toward the surface of the allophane film 13, and in the dense state of the base material 11 and the allophane film 13. is there. The allophane film 13 has a thickness of 5 μm or more and 70 μm or less, a moisture absorption rate of 10% or more and 30% or less, and a surface hardness of H or more. In one embodiment, in the allophane film 13, the allophane fine particles 15 having voids of several tens of nm on the base material 11 side are in a dense state, and the allophane fine particles 15 having relatively large voids of 1 μm or less exist near the surface. It is in a sparse state.

The allophane film 13 comprises allophane which is a hollow aluminum silicate (SiO ₂ /Al ₂ O ₃ ). Allophane has an average diameter of 3.5 nm or more and 10 nm or less. The allophane film 13 has hygroscopicity, and as the weight of the allophane film 13 increases, the amount of moisture absorption also increases. The allophane film 13 can retain its shape even in water.

The substrate 11 is one selected from the group consisting of glass, aluminum, alumina, a non-woven fabric, a non-woven fabric or an alumina sheet coated with a polyethylene film, an alumina sheet coated with a silica-containing polyethylene film, and a PET sheet.

When a non-woven fabric is selected as the base material 11, the non-woven fabric has a moisture permeability of 9500 g/m in 24 hours. ²1100g/m or more²Below, air permeability is 10ml/cm²25 ml/cm or more²Below, mass is 65g/m²80g/m or more²Hereinafter, the thickness is not less than 0.14 mm and not more than 0.25 mm.

[Production method]
It is preferable to use the aerosol deposition method (AD method) to form the allophane film composite 10 according to the embodiment of the present invention. FIG. 3 is a schematic diagram showing an example of the manufacturing apparatus 1 by the AD method used in the method for manufacturing an allophane film composite according to one embodiment of the present invention. Regarding the AD method, for example, Japanese Patent No. 3265481 can be referred to. In the manufacturing apparatus 1, for example, the base material 11 and the nozzle 4 are arranged in the decompression chamber 2. The base material 11 supports the formed allophane film 13.

The nozzle 4 supplies the allophane raw material fine particles 17 onto the base material 11 to form the allophane fine particle green compact 12. The allophane fine particles 12 are sprayed with the allophane fine particles 15 from the nozzle 4 onto the base material 11, and the mechanical impact force acts on the allophane fine particles 15 by the spraying so that the joined state occurs between the allophane fine particles 15. is there. The substrate 11 is attached to the substrate driving device 6 and is displaceable in the chamber 2 by being driven by the substrate driving device 6. The nozzle 4 may also be displaceable in the chamber.

The allophane raw material fine particles 17 are mixed with a carrier gas to form an aerosol, and together with the carrier gas, the allophane fine particles 15 are accelerated through the nozzle 4 and jetted toward the surface of the deposition target substrate 11, whereby the decompression chamber 2 is evacuated. The allophane film 13 is formed on the base material 11. At this time, the flow rate of the carrier gas is preferably about 2 L/min to 7 L/min, and the speed of the substrate driving device 6 is preferably 4 mm/sec to 10 mm/sec. Further, the pressure inside the chamber 2 is preferably 100 Pa to 90 Pa. As the carrier gas, for example, an inert gas such as nitrogen or argon, dry air, or the like can be used.

Further, in one embodiment, the breaking strength such as mechanical strength (brittle breaking strength) of the allophane fine particle material to be used is easily crushed by the above-mentioned shocking force in accordance with the shocking force caused by spraying from the nozzle 4. Alternatively, it may be subjected to a crushing machine such as a ball mill or a jet mill for a long time to form cracks in advance.

By using such an allophane particle material, it is possible to crush the allophane raw material fine particles 17 to at least 100 nm or less, form a clean new surface, cause low temperature bonding, and realize bonding of the particles to each other at room temperature. .. At this time, when the particle size of the original allophane raw material fine particles 17 to be used is 50 nm or less, it is considered that the above impact pulverization is unlikely to occur. Further, in the case of the method of spraying onto the substrate, if the particle size is too large, it becomes difficult to apply the impact force necessary for crushing. Therefore, it is considered that an appropriate particle size range (approximately 50 nm to 5 μm) exists for each of the above-mentioned molding methods.

Zeolite, kaolinite, talc, etc. are known as clay minerals, but the structure of allophane differs greatly from these clay minerals. Common clay minerals such as zeolite, kaolinite and talc have a long-range ordered crystal structure of atomic arrangement. On the other hand, allophane has the above-mentioned hollow spherical structure and has a short-range order in the atomic arrangement within the spherical particles, but does not have a long-range order in the atomic arrangement like a general crystal. The above-mentioned AD method is a film forming method using raw material fine particles having high crystallinity, and it is considered that plastic deformation of crystals contributes to the film forming mechanism. It was never applied to low (amorphous) materials.

The present inventors performed film formation using zeolite, which is a crystalline porous material, as raw material fine particles by using a film formation method similar to the method for producing an allophane film composite according to the present invention. It is unpredictable that it is possible to form a film by using allophane having a low hollow spherical structure as a raw material fine particle, and even if a film can be formed, the hollow structure collapses and the hygroscopic property etc. Was expected to be lost. This is the first report to realize a film formation while maintaining the hygroscopic property according to the present invention.

Further, the allophane membrane composite has a significant effect in that zeolite has hygroscopicity under low humidity conditions, whereas allophane has hygroscopicity under medium humidity conditions. Furthermore, since allophane has the ability to adsorb phosphoric acid and organic acids, the allophane membrane complex can be used as a deodorant and the like.

Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples.

(Example 1)
As Example 1, the allophane raw material fine particles 17 were sprayed onto a non-woven fabric (non-woven fabric whose surface was coated with a polyethylene film) substrate to form an allophane film by the AD method. A sized allophane powder is aerosolized with nitrogen gas at a flow rate of 2.5 L/min, and is placed in a chamber with a vacuum atmosphere of 20 Pa through a nozzle having an opening width of 30 mm×0.2 mm (a nonwoven fabric whose surface is coated with a polyethylene film). ) An allophane film was formed by spraying on a substrate to prepare an allophane film-nonwoven fabric composite. The substrate was reciprocated while being displaced at a speed of 4 mm/s with respect to the nozzle, and the film formation time was 500 seconds and the film formation area was 30×100 mm ² .

The weight of the allophane film-nonwoven fabric composite was measured, and the weight of the allophane film was calculated from the difference from the weight of the non-woven fabric before film formation. As a result, the weight of the allophane film was 0.09 g.

A cross section of the allophane film-nonwoven fabric composite was prepared with a cross section polisher and observed with a field emission electron microscope. FIG. 4A shows a field emission electron microscope image of a cross section of the allophane film composite 10 according to Example 1. In FIG. 4A, it was confirmed that the allophane film 13 was formed on the non-woven fabric substrate 11. The thickness of the allophane film 13 was about 22 μm.
apparatus:
Cross section polisher: SM-09010
Field Emission Electron Microscope: JSM-7400F

The allophane film-nonwoven fabric composite was observed with a transmission electron microscope. FIG. 5 shows a transmission electron microscope image of the allophane film 13 of the allophane composite 10 according to Example 1. In FIG. 5, it was confirmed that the allophane film had spherical particles with a diameter of 5 to 10 nm that were densified, and that the hollow structure of allophane was not collapsed but formed into a film.
apparatus:
Transmission electron microscope: JEM-2010

The surface hardness of the allophane film of the allophane film-nonwoven fabric composite was evaluated by a scratch hardness test (hand scratching pencil method). As a result, the allophane film had a surface hardness of H or higher.

The allophane film-nonwoven fabric composite was folded and the adhesion of the allophane film to the nonwoven fabric substrate was evaluated. The allophane film did not peel off when bent once at 90°.

A cellophane adhesive tape having an adhesive force of 4.01 N/10 mm was attached to the allophane film-nonwoven fabric composite and peeled off, and the adhesion of the film was evaluated. As a result, it was found that the allophane film did not peel off even if the cellophane adhesive tape was peeled off, and had an adhesive force of 4.0 N/10 mm or more.

The relationship between the relative humidity and the moisture absorption rate was verified for the allophane film-nonwoven fabric composite. After drying at 130° C., the relative humidity was changed at 40° C. to obtain a correlation curve for the allophane film-nonwoven fabric composite and the allophane raw material fine particles (FIG. 6). The allophane film-nonwoven fabric composite of this example has a moisture absorption performance equivalent to that of the allophane raw material fine particles. Further, the allophane film-nonwoven fabric composite after drying at 130° C. was allowed to stand in an atmosphere having a temperature of 40° C. and a relative humidity of 80% for 48 hours to evaluate the hygroscopic property. The weight increase of the allophane film-nonwoven fabric complex was evaluated as the moisture absorption amount, and the moisture absorption amount per 1 g of allophane film-nonwoven fabric complex was evaluated as the moisture absorption rate. As a result, the moisture absorption amount was 0.023 g and the moisture absorption rate was 25.3%. there were.

When the allophane film-nonwoven fabric composite was put into water, the allophane film retained its morphology without collapsing.

(Example 2)
An allophane film-nonwoven fabric composite was prepared in the same manner as in Example 1 except that the time for spraying the aerosol onto the substrate was set to about 100 seconds.

As a result of calculating the weight of the allophane film in the same manner as in Example 1, it was 0.16 g. As a result of measuring the thickness of the allophane film in the same manner as in Example 1, it was about 38 μm. As a result of evaluating the surface hardness of the allophane film in the same manner as in Example 1, the allophane film had a surface hardness of H or higher. As a result of evaluating the adhesiveness of the allophane film in the same manner as in Example 1, the allophane film was not peeled off when bent once at 90°. As in Example 1, the cellophane adhesive tape was used to evaluate the adhesion of the allophane film to the substrate. As a result, it was found that the adhesion was 4.0 N/10 mm or more. As a result of evaluating the hygroscopic property of the allophane film-nonwoven fabric composite in the same manner as in Example 1, the hygroscopic amount was 0.033 g and the hygroscopic rate was 20.6%. When the allophane membrane composite was put into water in the same manner as in Example 1, the allophane membrane maintained its morphology without collapsing.

(Example 3)
A film-forming sample was prepared in the same manner as in Example 1 except that the aerosol injection time on the substrate was set to about 1250 seconds.

As a result of calculating the weight of the allophane film in the same manner as in Example 1, it was 0.21 g. As a result of measuring the thickness of the allophane film in the same manner as in Example 1, it was about 50 μm. As a result of evaluating the surface hardness of the allophane film in the same manner as in Example 1, the allophane film had a surface hardness of H or higher. As a result of evaluating the adhesiveness of the allophane film in the same manner as in Example 1, the allophane film was not peeled off when bent once at 90°. As in Example 1, the cellophane adhesive tape was used to evaluate the adhesion of the allophane film to the substrate. As a result, it was found that the adhesion was 4.0 N/10 mm or more. As a result of evaluating the hygroscopic property of the allophane membrane-nonwoven fabric composite in the same manner as in Example 1, the hygroscopic amount was 0.041 g and the hygroscopic rate was 19.5%. When the allophane membrane composite was put into water in the same manner as in Example 1, the allophane membrane maintained its morphology without collapsing.

(Example 4)
A film-forming sample was prepared in the same manner as in Example 1 except that the aerosol injection time on the base material was set to about 1500 seconds.

As a result of calculating the weight of the allophane film in the same manner as in Example 1, it was 0.26 g. As a result of measuring the thickness of the allophane film in the same manner as in Example 1, it was about 62 μm. As a result of evaluating the surface hardness of the allophane film in the same manner as in Example 1, the allophane film had a surface hardness of H or higher. As a result of evaluating the adhesiveness of the allophane film in the same manner as in Example 1, the allophane film was not peeled off when bent once at 90°. As in Example 1, the cellophane adhesive tape was used to evaluate the adhesion of the allophane film to the substrate. As a result, it was found that the adhesion was 4.0 N/10 mm or more. As a result of evaluating the hygroscopic property of the allophane film-nonwoven fabric composite in the same manner as in Example 1, the hygroscopic amount was 0.053 g, and the hygroscopic rate was 20.4%. When the allophane membrane composite was put into water in the same manner as in Example 1, the allophane membrane maintained its morphology without collapsing.

The moisture absorption of the allophane membrane composites of Examples 1-5 was evaluated. FIG. 7 is a diagram in which the amount of moisture absorption is plotted against the weight of the allophane film. From FIG. 7, it was confirmed that as the weight of the allophane film increases, the moisture absorption amount also increases.

(Example 5)
A non-woven fabric which has been sized into aerosol by compressed air with a flow rate of 2.1 L/min and passed through a nozzle with an opening width of 7 mm x 0.4 mm and placed in a chamber of a vacuum atmosphere of 15 Pa (a non-woven fabric whose surface is coated with a polyethylene film). ) An allophane film was formed by spraying on a substrate to prepare an allophane film-nonwoven fabric composite. The substrate was displaced by an XY stage at a speed of 10 mm/s to obtain a complex having a large film formation area of 350×350 mm ² .

The weight of the allophane film was calculated in the same manner as in Example 1 and was found to be 3.27 g. As a result of measuring the thickness of the allophane film in the same manner as in Example 1, it was about 19 μm. As a result of evaluating the surface hardness of the allophane film in the same manner as in Example 1, the allophane film had a surface hardness of H or higher. As a result of evaluating the adhesiveness of the allophane film in the same manner as in Example 1, the allophane film was not peeled off when bent once at 90°. As in Example 1, the cellophane adhesive tape was used to evaluate the adhesion of the allophane film to the substrate. As a result, it was found that the adhesion was 4.0 N/10 mm or more. When the allophane membrane composite was put into water in the same manner as in Example 1, the allophane membrane maintained its morphology without collapsing.

(Example 6)
An allophane film was formed in the same manner as in Example 1 except that the substrate was a glass plate and the film formation area was 30×20 mm ^{2. Thus} , an allophane film-glass composite was prepared.

As a result of evaluating the surface hardness of the allophane film in the same manner as in Example 1, the allophane film had a surface hardness of H or higher. As in Example 1, the cellophane adhesive tape was used to evaluate the adhesion of the allophane film to the substrate. As a result, it was found that the adhesion was 4.0 N/10 mm or more. When the allophane membrane composite was put into water in the same manner as in Example 1, the allophane membrane maintained its morphology without collapsing.

(Example 7)
The base material is a flexible aluminum sheet, and allophane powder is aerosolized with nitrogen gas at a flow rate of 3.5 L/min, and is sprayed through a nozzle with an opening width of 30 mm x 0.2 mm onto a base material placed in a chamber of a vacuum atmosphere of 20 Pa. Then, an allophane film was formed to produce an allophane film-aluminum composite. The base material was displaced back and forth with respect to the nozzle, and the film formation time was 50 seconds and the film formation area was 30×100 mm ² .

FIG. 4B shows a cross-sectional image of the allophane film-aluminum composite 20 in which the allophane film 13 is formed on the flexible aluminum sheet base material 21 of Example 7 using FIB. From FIG. 4B, it has been clarified that the allophane film 13 has a dense to sparse deposition state of the allophane particles from the base material 21 side toward the surface of the allophane film 13.

As a result of evaluating the surface hardness of the allophane film in the same manner as in Example 1, the allophane film had a surface hardness of H or higher. As a result of evaluating the adhesiveness of the allophane film in the same manner as in Example 1, the allophane film was not peeled off when bent once at 90°. As in Example 1, the cellophane adhesive tape was used to evaluate the adhesiveness of the allophane film to the substrate, and it was found that the adhesive strength was 4.0 N/10 mm or more. When the allophane membrane composite was put into water in the same manner as in Example 1, the allophane membrane maintained its morphology without collapsing.

(Example 8)
An allophane film was formed on the film surface in the same manner as in Example 1 except that the substrate was a flexible aluminum sheet coated with a silica-containing polyethylene film, and the film formation area was 11×22 mm ^2. It was made.

As a result of evaluating the surface hardness of the allophane film in the same manner as in Example 1, the allophane film had a surface hardness of H or higher. As a result of evaluating the adhesiveness of the allophane film in the same manner as in Example 1, the allophane film was not peeled off when bent once at 90°. As in Example 1, the cellophane adhesive tape was used to evaluate the adhesion of the allophane film to the substrate. As a result, it was found that the adhesion was 4.0 N/10 mm or more. When the allophane membrane composite was put into water in the same manner as in Example 1, the allophane membrane maintained its morphology without collapsing.

(Example 9)
An allophane film was formed in the same manner as in Example 1 except that the substrate was a polyethylene terephthalate (PET) sheet and the film formation area was 9×28 mm ² , to prepare an allophane film-PET composite.

As a result of evaluating the surface hardness of the allophane film in the same manner as in Example 1, the allophane film had a surface hardness of H or higher. As a result of evaluating the adhesiveness of the allophane film in the same manner as in Example 1, the allophane film was not peeled off when bent once at 90°. As in Example 1, the cellophane adhesive tape was used to evaluate the adhesion of the allophane film to the substrate. As a result, it was found that the adhesion was 4.0 N/10 mm or more. When the allophane membrane composite was put into water in the same manner as in Example 1, the allophane membrane maintained its morphology without collapsing.

(Comparative Example 1)
A 30% slurry prepared by adding 70 ml of water to 30 g of the sized allophane powder is applied on a glass plate with a thickness of 50 μm using an applicator, and then dried at 130° C. for 1 hour to give an allophane film-glass composite. The body was made.

As a result of evaluating the surface hardness of the allophane film in the same manner as in Example 1, the surface hardness of the allophane film was 4B. As a result of evaluating the adhesion of the allophane film to the base material with the cellophane adhesive tape in the same manner as in Example 1, it was found that the allophane film adhered to the cellophane adhesive tape and was peeled from the base material, so that the adhesion force of 4.0 N/10 mm or less. Met. When the allophane membrane composite was put into water in the same manner as in Example 1, the allophane membrane collapsed.

(Comparative example 2)
A 30% slurry prepared by adding 70 ml of water to 30 g of sized allophane powder was applied on a non-woven fabric (non-woven fabric whose surface was coated with a polyethylene film) with a thickness of 50 μm, and then dried at 130° C. for 1 hour. By doing so, an allophane film-nonwoven fabric composite was produced.

As a result of evaluating the surface hardness of the allophane film in the same manner as in Example 1, the surface hardness of the allophane film was 4B. As a result of evaluating the adhesiveness of the allophane film in the same manner as in Example 1, the allophane film was peeled off when bent once at 90°. As a result of evaluating the adhesion of the allophane film to the base material with the cellophane adhesive tape in the same manner as in Example 1, it was found that the allophane film adhered to the cellophane adhesive tape and was peeled from the base material, so that the adhesion force of 4.0 N/10 mm or less. Met. When the allophane membrane composite was put into water in the same manner as in Example 1, the allophane membrane collapsed.

(Comparative example 3)
A 30% slurry prepared by adding 70 ml of ethyl alcohol to 30 g of sized allophane powder was applied on a non-woven fabric (non-woven fabric whose surface was coated with a polyethylene film) with a thickness of 50 μm, and then at 130° C. for 1 hour. An allophane film-nonwoven fabric composite was produced by drying.

As a result of evaluating the surface hardness of the allophane film in the same manner as in Example 1, the surface hardness of the allophane film was 4B. As a result of evaluating the adhesiveness of the allophane film in the same manner as in Example 1, the allophane film was peeled off when bent once at 90°. As a result of evaluating the adhesion of the allophane film to the base material with the cellophane adhesive tape in the same manner as in Example 1, it was found that the allophane film adhered to the cellophane adhesive tape and was peeled from the base material, so that the adhesion force of 4.0 N/10 mm or less. Met. When the allophane membrane composite was put into water in the same manner as in Example 1, the allophane membrane collapsed.

(Comparative Example 4)
A 30% slurry prepared by adding 70 ml of 2-propyl alcohol to 30 g of sized allophane powder was applied on a non-woven fabric (non-woven fabric whose surface was coated with a polyethylene film) with a thickness of 50 μm, and then at 130° C. The allophane film-nonwoven fabric composite was produced by drying for 1 hour.

As a result of evaluating the surface hardness of the allophane film in the same manner as in Example 1, the surface hardness of the allophane film was 4B. As a result of evaluating the adhesiveness of the allophane film in the same manner as in Example 1, the allophane film was peeled off when bent once at 90°. As a result of evaluating the adhesion of the allophane film to the base material with the cellophane adhesive tape in the same manner as in Example 1, the allophane film adhered to the cellophane adhesive tape and was peeled from the base material. Therefore, the adhesion force of less than 4.0 N/10 mm. Met. When the allophane membrane composite was put into water in the same manner as in Example 1, the allophane membrane collapsed.

(Example 10)
The adsorbability of artificial pollutants (mixed solution of solvent naphtha, asphalt and oleic acid) was evaluated for the allophane membrane complex. An allophane film was formed by aerosolizing with a nitrogen gas at a flow rate of 2.1 L/min, and spraying it onto a non-woven fabric substrate through a nozzle having an opening width of 7 mm×0.4 mm in a vacuum atmosphere chamber of 15 Pa. The weight of the allophane film was 0.4 g, and an allophane film composite of 100×80 mm ² was prepared.

[Fatty acid adsorption capacity]
The fatty acid adsorption capacity was evaluated using oleic acid as the contaminant fatty acid. An allophane membrane complex dried at 110° C. for 3 hours was impregnated with 100 ml of an artificial pollutant, stirred for 1 minute, allowed to stand for 72 hours in an incubator kept at 25° C., adsorbed, and filtered with a quantitative filter paper to obtain a measurement sample. It was Next, neutralization titration was performed with an ethanol solution of potassium hydroxide (0.02 mol/L) to calculate the defatty acid ratio. For comparison, the raw material allophane powder used for film formation was used.

[Oil adsorption capacity]
The oil adsorption capacity was evaluated using asphalt as the oil component of the pollutants. Similar to the fatty acid adsorption capacity test, a test solution was obtained after adsorption and the transmittance was measured. The transmittance of the test solution before the adsorption test was 0%, and the degree of adsorption ability was evaluated by the transmittance after the adsorption test.
Measurement wavelength: 420nm

The results of the fatty acid adsorption test are shown in FIG. The results of the oil adsorption test are shown in FIG. From these results, it was found that the allophane film composite of Example 10 has an ability of adsorbing the dirt component generated from the human body or the natural environment to be more than that of the allophane powder. It was also confirmed that the allophane film composite of Example 10 had high adhesion to the substrate without peeling of the film even in a petroleum solvent. Further, it was found that the film formation improves the adsorption performance.

(Example 11)
The ability of the allophane membrane composite to adsorb odorous components was evaluated. The odor components were ammonia, trimethylamine, and acetic acid. The allophane membrane composite prepared in the same manner as in Example 11 (1 g as the weight of the allophane membrane only) was put in a polybag, sealed, and sealed with 9 L of air so that the gas concentration was set to be a test object. Gas was added, and the gas concentration after standing for 3 hours was measured. The results are shown in Table 1. After the test, any concentration was below the lower limit of quantification of detection, and it was confirmed that the allophane membrane complex has high adsorption ability for any odorous component.

(Example 12)
The sized allophane powder is aerosolized with nitrogen gas at a flow rate of 2.5 L/min, and is sprayed through an nozzle with an opening width of 30 mm x 0.2 mm onto an aluminum base material placed in a chamber of a vacuum atmosphere of 20 Pa to form a film. An allophane membrane composite having an area of 30 mm×100 mm was obtained. FIG. 10 shows the results of the examination by immersing the allophane membrane complex in a phosphate ion aqueous solution adjusted to a predetermined concentration at 23° C. for 6 hours. The phosphate adsorption amount was calculated with respect to the weight of the allophane film formed on the substrate. For comparison, the results of the same test using 0.2 g of allophane powder are also shown in FIG. As shown in the results of FIG. 10, the allophane film composite has the same phosphate ion adsorption capacity as the allophane powder.

(Example 13)
The humidity control performance of the allophane film composite prepared in the same manner as in Example 1 was evaluated by performing a humidity control test. FIG. 11: is a figure which shows the result of a humidity control test. After drying at 130° C., after absorbing moisture at 40° C. and relative humidity of 80%, and then releasing moisture at 40° C. and 20% of relative humidity, it was found that the allophane membrane composite has a humidity control effect. It was

(Example 14)
After drying the allophane film composite produced in the same manner as in Example 1, the change in moisture absorption rate with respect to moisture absorption time was evaluated in a moisture absorption test at a temperature of 40° C. and a relative humidity of 40%.

(Comparative example 5)
Further, as Comparative Example 5, an allophane tablet formed by molding allophane powder was produced. Using a molding machine (Kikusui Seisakusho, No. 8-F-3), uniaxially pressurizing the allophane powder at 0.6 MPa to 0.8 MPa, diameter: 15 mm, height: 5.5 mm, weight: 1. 0 g allophane tablets were made. The allophane tablet of Comparative Example 5 was also evaluated in the same manner as the allophane film composite of Example 14.

The result of plotting the moisture absorption rate against the moisture absorption time is shown in FIG. It was confirmed that the allophane film composite of Example 14 had a property of having a higher moisture absorption rate than the allophane tablet of Comparative Example 5.

The allophane film composite has a strong adhesion to the substrate and a high degree of freedom (deformability). In addition, it is extremely thin and can be easily cut with scissors or a cutter knife. Since it can be freely selected and processed, the required amount, the number of sheets, etc. can be freely selected, it can be used in all spaces including narrow spaces and gaps, and packaging materials and water-absorbing agents that can be used in a shape that matches the packing shape. It is used for drying medicines, foods, machinery, gas bodies, organic solvents, etc. In addition, in fields of application that utilize the characteristics of adsorption and humidity control, hygiene paper that adsorbs sebum and oil, wallpaper that also has a humidity control function by adsorbing harmful chemical molecules in the room, bacteria adsorption mask formed on the mask lining, window Anti-condensation film, anti-fog film, humidity control inside the car interior and a sheet for the interior of the car that adsorbs harmful components, inside or outside the car air conditioner or both, and let air pass to remove unpleasant odor Adsorption filter, air purification film used for indoor air conditioning equipment, adsorption film for fish breeding that adsorbs ammonia and fishy odor substances discharged from fish in liquid phase, vegetable preservation sheet/bag, masking during film formation Expressed functional interior, because it can obtain appropriate permeability by applying it to transparent vinyl, it is functional private sheet and functional crime prevention sheet, functional tape, functional protective sheet, flammable substance inside film or film Examples of the laminated fuel storage film stored in the voids, ion- and ligand-exchange membranes, radioactive element removal membranes, water absorption sheets, adsorption sheets, humidity control sheets, and the like.

1 Manufacturing Equipment, 2 Chambers, 4 Nozzles, 6 Substrate Driving Device, 10 Allophane Film Complex, 11 Base Material, 12 Allophane Fine Particle Compact, 13 Allophane Film, 15 Allophane Fine Particles, 17 Allophane Raw Material Fine Particles, 19 Protective Film for Observation , 20 Allophane membrane composite, 21 Substrate

Claims (8)

A base material, and an allophane film having an average diameter of 3.5 nm or more and 10 nm or less and allophane deposited on the base material,
An allophane film composite, wherein the adhesive force between the base material and the allophane film is 4 N/10 mm or more, and the allophane film is peeled from the base material at least once after repeating a 90-degree bending test. body. The allophane film composite according to claim 1, wherein the allophane film has a thickness of 50 μm or more and 70 μm or less, a moisture absorption rate of 10% or more and 30% or less, and a surface hardness of H or more. The substrate is one selected from the group consisting of glass, aluminum, alumina, non-woven fabric, non-woven fabric or alumina sheet coated with polyethylene film, alumina sheet coated with silica-containing polyethylene film, and PET sheet. The allophane membrane composite according to claim 1. It said substrate is a nonwoven, the nonwoven fabric is 24 hours of moisture permeability 9500 g / m ² or more 1100 g / m ² or less, air permeability 10 ml / cm ² or more 25 ml / cm ² or less, a density of 65 g / m ² or 80 g / m ² or less, allophane film composite according to claim 3 having a thickness, characterized in that it comprises the following 0.25mm or 0.14 mm. The method for producing an allophane membrane composite according to any one of claims 1 to 4,
Allophane raw material fine particles are mixed with a carrier gas to form an aerosol,
An allophane film is formed on the base material in a decompression chamber by accelerating the aerosolized raw material fine particles together with the carrier gas through a nozzle to jet them toward the surface of the base material. Method for producing composite. A water absorbent sheet comprising the allophane film composite according to claim 4, wherein the base material is a non-woven fabric. An adsorption sheet comprising the allophane film composite according to claim 4, wherein the base material is a non-woven fabric. A humidity control sheet comprising the allophane film composite according to claim 4, wherein the base material is a non-woven fabric.