WO2019058912A1 - Allophane film complex, sheet using same, and method for producing allophane film complex - Google Patents

Allophane film complex, sheet using same, and method for producing allophane film complex Download PDF

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Publication number
WO2019058912A1
WO2019058912A1 PCT/JP2018/031994 JP2018031994W WO2019058912A1 WO 2019058912 A1 WO2019058912 A1 WO 2019058912A1 JP 2018031994 W JP2018031994 W JP 2018031994W WO 2019058912 A1 WO2019058912 A1 WO 2019058912A1
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Prior art keywords
allophane
film
substrate
membrane
complex
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PCT/JP2018/031994
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French (fr)
Japanese (ja)
Inventor
松本　泰治
鈴木　宗
一智 飯塚
佐伯　和彦
明渡　純
Original Assignee
国立研究開発法人産業技術総合研究所
品川ゼネラル株式会社
栃木県
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Application filed by 国立研究開発法人産業技術総合研究所, 品川ゼネラル株式会社, 栃木県 filed Critical 国立研究開発法人産業技術総合研究所
Priority to JP2019543512A priority Critical patent/JP6778863B2/en
Priority to CN201880058938.5A priority patent/CN111093966B/en
Publication of WO2019058912A1 publication Critical patent/WO2019058912A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles

Definitions

  • the present invention relates to an allophane membrane complex in which a clay mineral allophane membrane formed by an aerosol deposition method has adhesion to a substrate.
  • Allophane is a low crystalline aluminum silicate and an amorphous aluminum silicate, which are frequently present in soil derived from volcanic products such as pumice and volcanic ash. Allophane consists of silicon (Si), aluminum (Al), oxygen (O) and hydrogen (H) (hydroxyl group (OH)).
  • the structure is a hollow sphere with a diameter of 3.5 nm to 5 nm, a specific surface area (up to 900 m 2 / g), a single gibbsite octahedron sheet as a sphere wall, and a SiO 4 tetrahedron bonded to the inside. There are many through holes of 0.3 nm to 0.5 nm in the spherical wall.
  • allophane Because of such a characteristic structure, allophane has a large surface area and hydroxyl groups on the surface, and can adsorb water, organic substances, various gas components, and the like. Because of these characteristics, allophane is applied in various fields such as fuel storage media such as natural gas and humidity control materials that autonomously control the humidity of living environment.
  • allophane is nanoparticles, it is shaped and used in various shapes for easy handling in industrial use.
  • the main forms of the allophane product include powder, granules, tablets and films. Among them, powdery, granular and tablet-like allophane products need to be packaged in small portions or used in special cases. Therefore, extra space is required for each used space, and the usable area is limited.
  • membrane-like allophane without such limitation can be used in a wider area, and applications that have never been expected can also be expected.
  • allophane is coated on the packaging material, drying characteristics can be added to the packaging material itself, and there is no need to enclose a separate desiccant, and it is applied to various industrial fields as a free-form desiccant and adsorbent. it can.
  • Patent Document 1 describes a method in which a cold setting glass is applied to the surface of a solid phase coated body to which allophane is attached to form a composite in which voids of allophane are bonded with a glass to be coated.
  • Patent Document 2 describes a coating solution containing a white pigment, a silane compound and a solvent.
  • Patent Documents 3 and 4 describe a method for producing a weather-resistant / stain-resistant emulsion paint containing allophane-coated allophane-titanium oxide composite particles and a resin component.
  • Patent Document 5 describes a coating agent comprising allophane and a resin for forming a porous continuous film having humidity control and gas adsorptivity.
  • Patent Document 6 describes a coating film of a transparent coating material in which allophane particles are blended in an aqueous emulsion in which a synthetic resin is blended.
  • Patent Document 7 5 to 95% by weight of an inorganic moisture control agent, 1 to 25% by weight of a resin binder (solid content), and 0.1 to 15% by weight of a moisture permeability imparting agent (solid content) Paint wall materials are included.
  • moisture absorbing and releasing material particles are added to the surface of a moisture absorbing and releasing substrate containing allophane and a hydraulic material such as slag, cement, and / or organic reinforcing fiber and inorganic fiber.
  • a moisture absorbing and desorbing fire protection building material formed by forming a coating layer with a paint.
  • Patent Document 9 describes an allophane film uniformly formed on a flake or a treated substrate by mixing allophane with an aqueous binding medium such as latex or a film-forming paint.
  • 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 membrane.
  • Patent Document 12 describes that a coating agent containing allophane is applied to the surface of a structure made of synthetic fibers.
  • Patent Document 13 proposes a method of making allophane transparent to paper.
  • the allophane is buried in the inside of the binder, the fiber and the paper, and the pores are not a little blocked, so that the property deterioration such as adsorption can not be avoided.
  • the present invention has been made in view of the conventional disadvantages, and aims to provide an allophane membrane composite in which an allophane-only film is formed on a base material such as an aluminum base material and a non-woven fabric, and to increase the adhesion strength. I assume.
  • the present invention also provides a method for producing an allophane membrane complex. Further, the present invention provides a sheet using an allophane membrane composite in which an allophane-only film is formed on a base material such as an aluminum base material and a non-woven fabric.
  • An allophane film complex includes a substrate, and an allophane film in which an allophane having an average diameter of 3.5 nm or more and 10 nm or less is deposited on the substrate;
  • the adhesion test with the allophane film is 4 N / 10 mm or more, and the bending test at 90 degrees is repeated, and the number of times the allophane film peels from the substrate is one or more times.
  • the allophane film has a thickness of 5 ⁇ m to 70 ⁇ m, a moisture absorption rate of 10% to 30%, 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 allophane raw material fine particles are mixed with a carrier gas to be aerosolized and aerosolized
  • the raw material fine particles are accelerated through the nozzle together with the carrier gas and sprayed toward the surface of the substrate to form an allophane film on the substrate in the decompression chamber.
  • the water absorbent sheet comprises an allophane membrane composite in which the substrate is a non-woven fabric.
  • the adsorptive sheet comprises an allophane membrane composite in which the substrate is a non-woven fabric.
  • the humidity control sheet comprises an allophane membrane composite in which the substrate is a non-woven fabric.
  • the allophane membrane of the present invention is characterized in that it comprises allophane alone with no binder. Since there is no blockage of the allophane pore by the binder, there is no decrease in adsorption capacity. There is no loss of adsorption capacity of the allophane membrane as compared to the allophane powder. In addition, since it is in the form of a membrane, it has an advantage that the adsorption rate is faster than that of allophane alone.
  • FIG. 10 It is a schematic diagram which shows the allophane membrane complex 10 which concerns on one Embodiment of this invention, (a) shows the perspective view of the allophane membrane complex 10, (b) shows sectional drawing of the allophane membrane complex 10.
  • FIG. The allophane raw material microparticles
  • FIG. 10 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 membrane complex which concerns on one Embodiment of this invention.
  • the allophane membrane complex 10 which concerns on one Example of this invention is shown, (a) shows the field emission electron microscope image of the cross section of the allophane membrane complex 10, (b) is the allophane membrane complex 20 using FIB. Shows a cross-sectional image of It is a transmission electron microscope image of the allophane membrane 13 of the allophane membrane complex 10 which concerns on one Example of this invention. It is a correlation curve of relative humidity and moisture absorption rate of the allophane membrane concerning one example of the present invention.
  • the allophane membrane complex according to the present invention the sheet using the same, and the method for producing the allophane membrane complex will be described with reference to the drawings.
  • the allophane membrane complex of the present invention, the sheet using the same, and the method for producing the allophane membrane complex are not construed as being limited to the description of the embodiments and examples described below. Note that in the drawings referred to in this embodiment mode and the examples to be 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 view showing an allophane membrane complex 10 according to an embodiment of the present invention.
  • 1 (a) shows a perspective view of the allophane membrane complex 10
  • FIG. 1 (b) shows a cross-sectional view of the allophane membrane complex 10.
  • the allophane membrane complex 10 includes a substrate 11 and an allophane film 13 in which the allophane microparticles 15 are deposited on the substrate 11.
  • the allophane membrane complex 10 is provided with the allophane membrane 13 made of allophane single taste (only the allophane fine particles 15) containing no binder. For this reason, it has an unprecedented adsorption capacity comparable to the bulk body of allophane alone.
  • the allophane film 13 has a high adsorption rate as compared to the bulk body of allophane alone.
  • Allophane (also referred to as clay mineral allophane) can be one which is naturally produced from home and abroad. Allophane can also be synthesized by neutralization reaction of a solution of silicic acid and aluminum ion using an alkali such as sodium hydroxide. This synthetic allophane may be employed in the allophane membrane complex according to the present invention. Although natural allophane can be used as it is, preferably, the purity of the allophane film formed by using a raw material in which allophane purity is increased by a separation method such as water and the like, of impurities such as quartz and volcanic glass contained Can be enhanced.
  • Allophane raw material microparticles 17 are shown in FIG. FIG. 2 (a) is a schematic view of the allophane raw material fine particles 17, and FIG. 2 (b) is a scanning electron microscope (SEM) image of the allophane raw material fine particles 17.
  • the allophane raw material microparticles 17 have a structure in which a plurality of allophane microparticles 15 are aggregated.
  • Allophane raw material fine particles 17 are irregularly shaped particles having a particle diameter of several ⁇ m to several tens of ⁇ m.
  • the allophane film 13 has pores, and the allophane fine particles 15 have a dense to sparse deposition state from the substrate 11 side toward the surface of the allophane film 13 and in the dense state of the substrate 11 and the allophane film 13 is there.
  • the allophane film 13 has a thickness of 5 ⁇ m or more and 70 ⁇ m or less, a moisture absorption rate of 10% or more and 30% or less, and a surface hardness of H or more.
  • the allophane film 13 is in a state in which allophane fine particles 15 having a void of several tens of nm are dense on the substrate 11 side, and allophane fine particles 15 having a relatively large void of 1 ⁇ m or less near the surface. It is in a sparse state.
  • the allophane film 13 includes 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 is hygroscopic, and as the weight of the allophane film 13 increases, the amount of moisture absorption also increases. The allophane film 13 can retain its form even in water.
  • the substrate 11 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 When selecting a nonwoven as a substrate 11, 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, mass 65 g / m 2 or more and 80 g / m 2 or less, and the thickness is 0.14 mm or more and 0.25 mm or less.
  • FIG. 3 is a schematic diagram which shows an example of the manufacturing apparatus 1 by AD method used for the manufacturing method of the allophane membrane complex which concerns on one Embodiment of this invention.
  • Japanese Patent No. 3265481 can be referred to for the AD method.
  • the base 11 and the nozzle 4 are disposed in the decompression chamber 2.
  • the substrate 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.
  • allophane fine particles 15 are sprayed from the nozzle 4 onto the base material 11, and by this mechanical impact force acting on the allophane fine particles 15, a bonding state occurs between the allophane fine particles 15. is there.
  • the substrate 11 is attached to the substrate driving device 6 and driven by the substrate driving device 6 so as to be displaceable in the chamber 2.
  • the nozzle 4 may also be displaceable in the chamber.
  • Allophane raw material fine particles 17 are mixed with a carrier gas and aerosolized, and together with the carrier gas, allophane fine particles 15 are accelerated through the nozzle 4 and sprayed toward the surface of the deposition target substrate 11, thereby reducing pressure in the decompression chamber 2.
  • An allophane film 13 is formed on the substrate 11.
  • 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.
  • the pressure in the chamber 2 is preferably 100 Pa to 90 Pa.
  • the carrier gas for example, an inert gas such as nitrogen or argon, dried air or the like can be used.
  • the fracture strength such as mechanical strength (brittle fracture strength) of the allophane fine particle material to be used is easily crushed by the above-mentioned impact force.
  • the crack may be formed in advance by using a crusher such as a ball mill or jet mill for a long time.
  • allophane particle material By using such allophane particle material, it is possible to grind allophane raw material fine particles 17 to at least 100 nm or less, to form a clean new surface, to cause low temperature bonding, and to realize bonding of particles to each other at room temperature. .
  • the particle diameter of the original allophane raw material fine particles 17 to be used is 50 nm or less, it is considered that the above-mentioned impact pulverization hardly occurs.
  • substrate when particle diameter is too large, it will become difficult to give the impact force required for crushing. Therefore, it is believed that there is a suitable particle size range (approximately 50 nm to 5 ⁇ m) for each of the molding methods described above.
  • allophane differs from these clay minerals in its structure.
  • Common clay minerals such as zeolite, kaolinite and talc have a crystal structure with long-range order of atomic arrangement.
  • allophane has the above-described hollow spherical structure and has short-range order in atomic arrangement in spherical particles, but does not have long-range order in atomic arrangement like general crystals.
  • 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 the crystal contributes to the film forming mechanism, so that crystallinity such as allophane is obtained. Has not been applied to low (amorphous) materials.
  • the present inventors carried out film formation using zeolite, which is a crystalline porous material, as raw material fine particles, using a film formation method similar to the method for producing an allophane membrane composite according to the present invention. It can not be expected that film formation can be performed using allophane having a hollow spherical structure with a low particle size as a raw material fine particle, so it can not be anticipated so far, even if film formation is possible, the hollow structure collapses, moisture absorption characteristics, etc. Was expected to be lost. According to the present invention, film formation while maintaining the moisture absorption characteristics etc. is realized, and it is reported for the first time.
  • the allophane membrane complex exerts a significant effect in that allophane has hygroscopic properties under medium humidity conditions, while zeolite has hygroscopic properties under low humidity conditions. Furthermore, since allophane has an adsorption capacity for phosphoric acid and organic acids, the allophane membrane complex can be used as a deodorizing agent and the like.
  • Example 1 In Example 1, allophane raw material fine particles 17 were sprayed onto a non-woven fabric (non-woven fabric whose surface was coated with a polyethylene film) to form an allophane film by the AD method.
  • Non-woven fabric placed in a chamber with a vacuum atmosphere of 20 Pa through a nozzle with an opening width of 30 mm ⁇ 0.2 mm through aerosolization of sized allophane powder with nitrogen gas at a flow rate of 2.5 L / min (non-woven fabric whose surface is coated with polyethylene film) )
  • the substrate was sprayed to form an allophane film 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 nonwoven fabric before film formation. As a result, the weight of the allophane membrane was 0.09 g.
  • FIG. 4A shows a field emission electron microscope image of a cross section of the allophane film complex 10 according to Example 1.
  • FIG. 4A it can be confirmed that the allophane film 13 is formed on the non-woven fabric substrate 11.
  • the thickness of the allophane film 13 was about 22 ⁇ m.
  • FIG. 5 shows a transmission electron microscope image of the allophane film 13 of the allophane complex 10 according to Example 1. In FIG. 5, it was confirmed that the allophane film was compacted by spherical particles having a diameter of 5 to 10 nm, and the film was formed without collapsing the hollow structure of allophane.
  • 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-drawn pencil method). As a result, the allophane film had a surface hardness of H or more.
  • the allophane film-nonwoven fabric composite was folded to evaluate the adhesion of the allophane film to the non-woven fabric substrate. When bent once at 90 °, the allophane film did not peel off.
  • a cellophane adhesive tape having an adhesive strength 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 even when the cellophane adhesive tape was peeled off, and had an adhesion of 4.0 N / 10 mm or more.
  • the relationship between relative humidity and moisture absorption rate was verified for the allophane membrane-nonwoven fabric composite. After drying at 130 ° C., the relative humidity was changed at 40 ° C. to obtain correlation curves for the allophane membrane-nonwoven fabric composite and the allophane raw material fine particles (FIG. 6).
  • the allophane membrane-nonwoven fabric composite of the present example has the same moisture absorption performance as the allophane raw material fine particles. Further, the allophane membrane-nonwoven fabric composite after drying at 130 ° C. was allowed to stand in an atmosphere of temperature 40 ° C. and relative humidity 80% for 48 hours to evaluate moisture absorption characteristics.
  • the weight gain of the allophane membrane-nonwoven fabric composite was evaluated as the moisture absorption rate, and the moisture absorption rate per 1 g of allophane membrane-nonwoven fabric composite as the moisture absorption rate was 0.023 g, and the moisture absorption rate was 25.3%. there were.
  • Example 2 An allophane membrane-nonwoven fabric composite was produced in the same manner as in Example 1 except that the time for aerosol injection onto the substrate was about 100 seconds.
  • Example 1 As a result of calculating the weight of the allophane membrane in the same manner as in Example 1, it was 0.16 g.
  • the thickness of the allophane film was measured in the same manner as in Example 1. As a result, it was about 38 ⁇ m.
  • the surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film had a surface hardness of H or more.
  • the adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, when it was bent once at 90 °, the allophane film did not peel off.
  • Example 3 The film-forming sample was produced similarly to Example 1 except having made aerosol injection time to a base material into about 1250 second.
  • Example 1 As a result of calculating the weight of the allophane membrane 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 ⁇ m.
  • the surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film had a surface hardness of H or more.
  • the adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, when it was bent once at 90 °, the allophane film did not peel off.
  • Example 4 The film-forming sample was produced similarly to Example 1 except having made aerosol injection time to a base material about 1500 seconds.
  • Example 1 As a result of calculating the weight of the allophane membrane 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 ⁇ m. The surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film had a surface hardness of H or more. The adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, when it was bent once at 90 °, the allophane film did not peel off.
  • 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 is confirmed that the moisture absorption amount also increases as the weight of the allophane membrane increases.
  • Example 5 Non-woven fabric placed in a chamber with a vacuum atmosphere of 15 Pa through a nozzle with an opening width of 7 mm ⁇ 0.4 mm through aerosolization of sized allophane powder with compressed air at a flow rate of 2.1 L / min (non-woven fabric whose surface is coated with polyethylene film) )
  • the substrate was sprayed to form an allophane film 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 large-sized composite having a film formation area of 350 ⁇ 350 mm 2 .
  • Example 1 As a result of calculating the weight of the allophane membrane in the same manner as in Example 1, it was 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 ⁇ m.
  • the surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film had a surface hardness of H or more.
  • the adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, when it was bent once at 90 °, the allophane film did not peel off.
  • 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 , to prepare an allophane film-glass composite.
  • the surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film had a surface hardness of H or more. As a result of evaluating the adhesiveness to the base material of the allophane film with the cellophane adhesive tape similarly to Example 1, it turned out that there exists adhesiveness of 4.0 N / 10 mm or more. When the allophane membrane complex was introduced into water in the same manner as in Example 1, the allophane membrane retained its form without disintegration.
  • the substrate is a flexible aluminum sheet, and allophane powder is aerosolized with nitrogen gas at a flow rate of 3.5 L / min and sprayed through a nozzle with an opening width of 30 mm ⁇ 0.2 mm to a substrate placed in a chamber with a vacuum atmosphere of 20 Pa.
  • the allophane membrane was formed to prepare an allophane membrane-aluminum complex.
  • the substrate was displaced reciprocally 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 using an FIB of the allophane film-aluminum composite 20 in which the allophane film 13 is formed on the flexible aluminum sheet base 21 of Example 7. From FIG. 4 (b), it is clear that the allophane film 13 has a dense to sparse deposition state in which the allophane fine particles are directed from the substrate 21 side to the surface of the allophane film 13.
  • the surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film had a surface hardness of H or more.
  • the adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, when it was bent once at 90 °, the allophane film did not peel off. As a result of evaluating the adhesiveness to the base material of the allophane film with the cellophane adhesive tape similarly to Example 1, it turned out that there exists adhesiveness of 4.0 N / 10 mm or more. When the allophane membrane complex was introduced into water in the same manner as in Example 1, the allophane membrane retained its form without disintegration.
  • 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, and an allophane film-aluminum composite was obtained. Made.
  • the surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film had a surface hardness of H or more.
  • the adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, when it was bent once at 90 °, the allophane film did not peel off. As a result of evaluating the adhesiveness to the base material of the allophane film with the cellophane adhesive tape similarly to Example 1, it turned out that there exists adhesiveness of 4.0 N / 10 mm or more. When the allophane membrane complex was introduced into water in the same manner as in Example 1, the allophane membrane retained its form without disintegration.
  • 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.
  • PET polyethylene terephthalate
  • the surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film had a surface hardness of H or more.
  • the adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, when it was bent once at 90 °, the allophane film did not peel off. As a result of evaluating the adhesiveness to the base material of the allophane film with the cellophane adhesive tape similarly to Example 1, it turned out that there exists adhesiveness of 4.0 N / 10 mm or more. When the allophane membrane complex was introduced into water in the same manner as in Example 1, the allophane membrane retained its form without disintegration.
  • the surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the surface hardness of the allophane film was 4B. As a result of evaluating the adhesion of the allophane film to the substrate with the cellophane adhesive tape in the same manner as in Example 1, the allophane film was adhered to the cellophane adhesive tape and peeled from the substrate, so the adhesion of less than 4.0 N / 10 mm. Met. When the allophane membrane complex was introduced into water as in Example 1, the allophane membrane collapsed.
  • the surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the surface hardness of the allophane film was 4B.
  • the adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film peeled off when bent once at 90 °.
  • the allophane film was adhered to the cellophane adhesive tape and peeled from the substrate, so the adhesion of less than 4.0 N / 10 mm. Met.
  • the allophane membrane complex was introduced into water as in Example 1, the allophane membrane collapsed.
  • the surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the surface hardness of the allophane film was 4B.
  • the adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film peeled off when bent once at 90 °.
  • the allophane film was adhered to the cellophane adhesive tape and peeled from the substrate, so the adhesion of less than 4.0 N / 10 mm. Met.
  • the allophane membrane complex was introduced into water as in Example 1, the allophane membrane collapsed.
  • the surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the surface hardness of the allophane film was 4B.
  • the adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film peeled off when bent once at 90 °.
  • the allophane film was adhered to the cellophane adhesive tape and peeled from the substrate, so the adhesion of less than 4.0 N / 10 mm. Met.
  • the allophane membrane complex was introduced into water as in Example 1, the allophane membrane collapsed.
  • Example 10 For the allophane membrane complex, the adsorption ability of artificial contaminating liquid (a mixed solution of solvent naphtha, asphalt and oleic acid) was evaluated.
  • the non-woven fabric substrate was aerosolized with nitrogen gas at a flow rate of 2.1 L / min and sprayed through a nozzle having an opening width of 7 mm ⁇ 0.4 mm in a vacuum atmosphere chamber of 15 Pa to form an allophane film.
  • the weight of the allophane membrane was 0.4 g to make an allophane membrane complex of 100 ⁇ 80 mm 2 .
  • the fatty acid adsorption capacity was evaluated using oleic acid as the fatty acid of the contaminant.
  • the allophane membrane complex dried at 110 ° C. for 3 hours is impregnated with 100 ml of artificial contamination solution, stirred for 1 minute, allowed to stand for 72 hours in a incubator kept at 25 ° C., adsorbed, and filtered through quantitative filter paper to obtain a measurement sample.
  • the allophane powder of the raw material used for film-forming was used for comparison.
  • Oil adsorption capacity was evaluated using asphalt as the oil component of the contaminants.
  • the test solution was obtained after adsorption in the same manner as the fatty acid adsorption test, and the transmittance was measured.
  • the permeability of the test solution before the adsorption test was 0%, and the degree of adsorption capacity was evaluated by the permeability after the adsorption test. Measurement wavelength: 420 nm
  • 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 membrane complex of Example 10 has an ability of adsorbing the dirt component emitted from the human body or the natural environment more than allophane powder. In addition, it was also confirmed that the allophane membrane complex of Example 10 had high film adhesion to the substrate without peeling of the film even in a petroleum solvent. Furthermore, it was found that the adsorption performance is improved by film formation.
  • Example 11 The adsorption capacity of the odor component of the allophane membrane complex was evaluated.
  • the odorous components were ammonia, trimethylamine and acetic acid.
  • the allophane membrane complex (1 g as the weight of allophane membrane alone) prepared in the same manner as in Example 11 is put in a plastic bag, sealed, sealed with 9 L of air, and subjected to the test so that the set gas concentration is achieved. The gas was added, and the gas concentration after standing for 3 hours was measured. The results are shown in Table 1. The concentration after the test was below the lower limit of detection and determination, and it was confirmed that the allophane membrane complex had high adsorption ability for any odor component.
  • Example 12 The sized allophane powder is aerosolized with nitrogen gas at a flow rate of 2.5 L / min and sprayed onto an aluminum substrate placed in a chamber with a vacuum atmosphere of 20 Pa through a nozzle with an opening width of 30 mm ⁇ 0.2 mm. An allophane membrane complex with an area of 30 mm ⁇ 100 mm was obtained. The allophane membrane complex was immersed in a phosphate ion aqueous solution adjusted to a predetermined concentration for 6 hours at 23 ° C. and the result is shown in FIG. The amount of adsorbed phosphoric acid was calculated relative to the weight of the allophane film formed on the substrate.
  • the results of similar tests using 0.2 g of allophane powder are also shown in FIG.
  • the allophane membrane complex has phosphate ion adsorption ability equal to that of allophane powder.
  • Example 13 The humidity control performance of the allophane membrane complex prepared as in Example 1 was evaluated by performing a humidity control test.
  • FIG. 11 is a diagram showing the results of the humidity control test. After drying at 130 ° C, moisture was absorbed at 40 ° C and relative humidity 80%, and then moisture was released at 40 ° C and relative humidity 20%. As a result, it is found that the allophane membrane complex has a humidity control action.
  • Example 14 After drying the allophane membrane complex produced in the same manner as in Example 1 at 130 ° C., the change of the moisture absorption rate with respect to the 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 an allophane tablet was prepared by molding allophane powder. Allophane powder was uniaxially pressed at 0.6 MPa to 0.8 MPa using a molding machine (No. 8-F-3, Kikusui Manufacturing Co., Ltd.), diameter: 15 mm, height: 5.5 mm, weight: 1. 0 g of allophane tablets were made. The allophane tablet of Comparative Example 5 was also evaluated in the same manner as the allophane membrane complex of Example 14.
  • the allophane membrane composite has an extremely thin thickness and can be easily cut with a scissors or a cutter knife, in addition to having strong adhesion with a strong substrate and high freedom (deformability), so it has a shape (including a bag-like shape) and a large size. Because it can be selected freely, the required amount, the number of sheets, etc. can be selected freely, it can be used in any space including narrow spaces, gaps etc., and packaging materials that can be used in the shape according to the packaging shape, water absorbent It is used to dry medicine, food, machinery, gas, organic solvents and so on.
  • sanitary paper that adsorbs sebum and oil, wallpaper that adsorbs harmful chemical molecules in the room and also has humidity control function, bacteria adsorption mask formed on the lining of mask, window Anti-condensing film, anti-fogging film, inner sheet for car interior that adsorbs humidity control and harmful components in car interior, attached to the inside and / or both of car air conditioner, let air pass and take off unpleasant odor Adsorptive filter, air cleaning film used for air conditioning in the room, adsorption film for fish rearing that adsorbs ammonia and odorous substances discharged from fish in liquid phase, vegetable storage sheet / bag, masking of characters and pictures by film formation Functional private sheet and functional crime prevention sheet, functional tape, function from being able to obtain appropriate transparency by applying to functional interior expressed and transparent vinyl Protective sheets, stacked fuel storage membranes in which combustible substances are stored in membrane molecules and in the pores of membrane

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Abstract

The purpose of the present invention is to: provide an allophane film complex in which a plain allophane film is formed on an aluminum substrate or a substrate made of a nonwoven fabric or the like; and to improve the adhesiveness and peeling strength of the allophane film complex. Provided are a method for producing an allophane film complex, and a sheet using the allophane film complex in which a plain allophane film is formed on an aluminum substrate or a substrate made of a nonwoven fabric or the like. The allophane film complex according to one embodiment of the present invention comprises a substrate and an allophane film deposited on the substrate, wherein the average diameter of the allophane of the film is 3.5 to 10 nm, the adhesiveness between the substrate and the allophane film is 4N/10 mm or higher, and when a 90 degree bending test is repeated, the allophane film separates from the substrate at least once.

Description

アロフェン膜複合体、それを用いたシート、及びアロフェン膜複合体の製造方法Allophane membrane complex, sheet using the same, and method of producing allophane membrane complex
本発明は、エアロゾルデポジション法により形成させた粘土鉱物アロフェン膜が基材との密着性を備えるアロフェン膜複合体に関する。 The present invention relates to an allophane membrane complex in which a clay mineral allophane membrane formed by an aerosol deposition method has adhesion to a substrate.
アロフェンは、軽石や火山灰など火山噴出物に由来する土壌に多く賦存する低結晶性アルミニウムケイ酸塩および非晶質アルミニウムケイ酸塩である。アロフェンはケイ素（Ｓｉ）、アルミニウム（Ａｌ）、酸素（Ｏ）および水素（Ｈ）（水酸基（ＯＨ））からなる。その形態は直径３．５ｎｍ～５ｎｍの中空球で、比表面積（～９００ｍ2／ｇ）を有し、１層のギブサイト八面体シートを球壁とし、ＳｉＯ4四面体がその内側に結合した構造を有し、球壁に０．３ｎｍ～０．５ｎｍの貫通孔が多く存在する。このような特徴的構造のためアロフェンは大きな表面積を持ち、表面に水酸基を持つことから、水、有機物質、各種ガス成分等を吸着できる。これらの特性から、アロフェンは、天然ガス等の燃料貯蔵媒体や生活環境の湿度を自律的に制御する湿度調整材等の様々な分野で応用されている。 Allophane is a low crystalline aluminum silicate and an amorphous aluminum silicate, which are frequently present in soil derived from volcanic products such as pumice and volcanic ash. Allophane consists of silicon (Si), aluminum (Al), oxygen (O) and hydrogen (H) (hydroxyl group (OH)). The structure is a hollow sphere with a diameter of 3.5 nm to 5 nm, a specific surface area (up to 900 m 2 / g), a single gibbsite octahedron sheet as a sphere wall, and a SiO 4 tetrahedron bonded to the inside. There are many through holes of 0.3 nm to 0.5 nm in the spherical wall. Because of such a characteristic structure, allophane has a large surface area and hydroxyl groups on the surface, and can adsorb water, organic substances, various gas components, and the like. Because of these characteristics, allophane is applied in various fields such as fuel storage media such as natural gas and humidity control materials that autonomously control the humidity of living environment.
しかしながら、アロフェンはナノ粒子であるため、工業的な利用にあたってはハンドリングを容易にするため、様々な形状に成形されて使用されている。アロフェン製品の主な形状には、粉末状、顆粒状、タブレット状、膜状がある。このうち、粉末状、顆粒状、タブレット状のアロフェン製品は、使用の際に小分けに包装するか、専用のケースに充填する必要がある。そのため、それぞれの使用空間に余分な容積が必要となり、使用できる領域が限られる。 However, since allophane is nanoparticles, it is shaped and used in various shapes for easy handling in industrial use. The main forms of the allophane product include powder, granules, tablets and films. Among them, powdery, granular and tablet-like allophane products need to be packaged in small portions or used in special cases. Therefore, extra space is required for each used space, and the usable area is limited.
一方、そのような制限がない膜状のアロフェンは、より広い領域で使用でき、これまで無かった応用も期待できる。例えば、包装資材にアロフェンをコーティングすれば、包装資材自体に乾燥特性を付加できるため、別途の乾燥剤を同封する必要がなくなるなど、自由な形状の乾燥剤、吸着剤として様々な産業分野に応用できる。 On the other hand, membrane-like allophane without such limitation can be used in a wider area, and applications that have never been expected can also be expected. For example, if allophane is coated on the packaging material, drying characteristics can be added to the packaging material itself, and there is no need to enclose a separate desiccant, and it is applied to various industrial fields as a free-form desiccant and adsorbent. it can.
膜状にアロフェンを成形する方法として、以下のような結合材を用いた塗料・コーティング材が提案されている。例えば、特許文献１には、アロフェンの付着した固相被覆体の表面に常温硬化性ガラスを塗布して、アロフェンの空隙をガラスで結合した複合体を形成して被覆する方法が記載されている。また、特許文献２には、白色顔料、シラン化合物および溶媒を含有する塗布液が記載されている。 As a method of forming allophane in the form of a film, paints and coatings using the following binders have been proposed. For example, Patent Document 1 describes a method in which a cold setting glass is applied to the surface of a solid phase coated body to which allophane is attached to form a composite in which voids of allophane are bonded with a glass to be coated. . Patent Document 2 describes a coating solution containing a white pigment, a silane compound and a solvent.
特許文献３及び４には、アロフェンがコーティングされたアロフェン－酸化チタン複合粒子と樹脂成分とを含む耐候性・耐汚染性エマルション塗料を製造する方法が記載されている。また、特許文献５には、調湿・ガス吸着性を有する多孔質の連続皮膜を形成するためのアロフェンと樹脂からなるコーティング剤が記載されている。また、特許文献６には、合成樹脂が配合された水性エマルジョンにアロフェン粒子が配合された透明塗材の塗膜が記載されている。また、特許文献７には、無機調湿材を５～９５重量％と、樹脂バインダー（固形分）を１～２５重量％と、透湿性付与剤（固形分）を０．１～１５重量％と含む塗壁材が記載されている。特許文献８には、アロフェンとスラグ、セメント等の水硬性物質ならびに有機質補強繊維および無機質繊維の何れか一方または双方を含む吸放湿性基材の表面に、吸放湿性材料粒粉が添加された塗料による塗膜層を形成してなる吸放湿性防火建材が記載されている。また、特許文献９には、アロフェンをラテックス等の水性結合媒体や膜形成性のある塗料等と混合し、薄片又は処理基材上に均一に形成されたアロフェン膜が記載されている。 Patent Documents 3 and 4 describe a method for producing a weather-resistant / stain-resistant emulsion paint containing allophane-coated allophane-titanium oxide composite particles and a resin component. Further, Patent Document 5 describes a coating agent comprising allophane and a resin for forming a porous continuous film having humidity control and gas adsorptivity. In addition, Patent Document 6 describes a coating film of a transparent coating material in which allophane particles are blended in an aqueous emulsion in which a synthetic resin is blended. Further, in Patent Document 7, 5 to 95% by weight of an inorganic moisture control agent, 1 to 25% by weight of a resin binder (solid content), and 0.1 to 15% by weight of a moisture permeability imparting agent (solid content) Paint wall materials are included. In Patent Document 8, moisture absorbing and releasing material particles are added to the surface of a moisture absorbing and releasing substrate containing allophane and a hydraulic material such as slag, cement, and / or organic reinforcing fiber and inorganic fiber. There is described a moisture absorbing and desorbing fire protection building material formed by forming a coating layer with a paint. Further, Patent Document 9 describes an allophane film uniformly formed on a flake or a treated substrate by mixing allophane with an aqueous binding medium such as latex or a film-forming paint.
アロフェンを練り込んだ繊維を布上に加工する、以下のような方法も提案されている。例えば、特許文献１０及び１１には、アロフェンを合成繊維中に練り込まれ、繊維構造体として膜体の形態で利用することが記載されている。また、特許文献１２には、合成繊維からなる構造体の表面に、アロフェンを含有するコーティング剤を付与することが記載されている。 The following methods have also been proposed for processing allophane-kneaded fibers onto cloth. 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 membrane. In addition, Patent Document 12 describes that a coating agent containing allophane is applied to the surface of a structure made of synthetic fibers.
また、特許文献１３には、アロフェンを紙への透き込む方法が提案されている。 In addition, Patent Document 13 proposes a method of making allophane transparent to paper.
特開２０１４－２２６６３２号公報JP 2014-226632 A 特開２０１４－１４１６２６号公報JP, 2014-141626, A 特開２０１０－１５０４３４号公報Unexamined-Japanese-Patent No. 2010-150434 特開２０１０－０５８９９４号公報JP, 2010-058994, A 特開２００８－１３８１６７号公報JP 2008-138167 A 特開２００７－０６３７７９号公報Japanese Patent Application Publication No. 2007-063779 特開２００６－００２４０７号公報JP, 2006-002407, A 特開２００３－１５５７８６号公報Japanese Patent Application Publication No. 2003-155786 特開２００１－０４７４９３号公報JP, 2001-047493, A 特開２００６－２１８４０３号公報JP, 2006-218403, A 特開２００５－１０５４４７号公報JP 2005-105447 A 特開２００５－１０５４４８号公報JP, 2005-105448, A 特開２００３－０７３９９７号公報Japanese Patent Application Publication No. 2003-073997
これら膜状アロフェンを提供する先行技術は、結合材や繊維・紙の内部にアロフェンが埋没し、その細孔が少なからず閉塞することで、吸着等の特性低下が避けられない。本発明は、従来の欠点を鑑みてなされたもので、アルミ基材、不織布等の基材にアロフェン単味の膜を形成したアロフェン膜複合体を提供するとともに、その密着強度を高めることを目的とする。また、アロフェン膜複合体の製造方法を提供する。さらに、アルミ基材、不織布等の基材にアロフェン単味の膜を形成したアロフェン膜複合体を用いたシートを提供する。 In the prior art for providing these membranous allophane, the allophane is buried in the inside of the binder, the fiber and the paper, and the pores are not a little blocked, so that the property deterioration such as adsorption can not be avoided. The present invention has been made in view of the conventional disadvantages, and aims to provide an allophane membrane composite in which an allophane-only film is formed on a base material such as an aluminum base material and a non-woven fabric, and to increase the adhesion strength. I assume. The present invention also provides a method for producing an allophane membrane complex. Further, the present invention provides a sheet using an allophane membrane composite in which an allophane-only film is formed on a base material such as an aluminum base material and a non-woven fabric.
本発明の一実施形態に係るアロフェン膜複合体は、基材と、平均直径が３．５ｎｍ以上１０ｎｍ以下を備えるアロフェンが前記基材上に堆積したアロフェン膜と、を備え、前記基材と前記アロフェン膜との密着力が４Ｎ／１０ｍｍ以上、９０度の曲げ試験を繰り返して前記アロフェン膜が前記基材から剥離する回数が１回以上である。 An allophane film complex according to an embodiment of the present invention includes a substrate, and an allophane film in which an allophane having an average diameter of 3.5 nm or more and 10 nm or less is deposited on the substrate; The adhesion test with the allophane film is 4 N / 10 mm or more, and the bending test at 90 degrees is repeated, and the number of times the allophane film peels from the substrate is one or more times.
前記アロフェン膜は、厚さが５μｍ以上７０μｍ以下、吸湿率が１０％以上３０％以下、表面硬度がＨ以上を備える。 The allophane film has a thickness of 5 μm to 70 μm, a moisture absorption rate of 10% to 30%, and a surface hardness of H or more.
前記基材は、ガラス、アルミニウム、アルミナ、不織布、ポリエチレンフィルムでコーティングされた不織布又はアルミナシート、シリカ含有ポリエチレンフィルムでコーティングされたアルミナシート、及びＰＥＴシートの群から選ばれる１つである。 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.
前記不織布は、２４時間での透湿度が９５００ｇ／ｍ2以上１１００ｇ／ｍ2以下、通気度が１０ｍｌ／ｃｍ2以上２５ｃｃ／ｃｍ2以下、密度が６５ｇ／ｍ2以上８０ｇ／ｍ2以下、厚さが０．１４ｍｍ以上０．２５ｍｍ以下を備える。 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.
本発明の一実施形態に係るアロフェン膜複合体の製造方法は、前記何れか１項に記載のアロフェン膜複合体の製造方法において、アロフェン原料微粒子を搬送ガスと混合してエアロゾル化し、エアロゾル化した原料微粒子を、該搬送ガスと共に、ノズルを通して加速して前記基材の表面に向けて噴射せしめることにより、減圧チャンバ内で前記基材にアロフェン膜を形成する。 In the method for producing an allophane membrane complex according to one embodiment of the present invention, in the method for producing an allophane membrane complex according to any one of the above, the allophane raw material fine particles are mixed with a carrier gas to be aerosolized and aerosolized The raw material fine particles are accelerated through the nozzle together with the carrier gas and sprayed toward the surface of the substrate to form an allophane film on the substrate in the decompression chamber.
本発明の一実施形態において、吸水シートは、前記基材が不織布であるアロフェン膜複合体を備える。 In one embodiment of the present invention, the water absorbent sheet comprises an allophane membrane composite in which the substrate is a non-woven fabric.
本発明の一実施形態において、吸着シートは、前記基材が不織布であるアロフェン膜複合体を備える。 In one embodiment of the present invention, the adsorptive sheet comprises an allophane membrane composite in which the substrate is a non-woven fabric.
本発明の一実施形態において、調湿シートは、前記基材が不織布であるアロフェン膜複合体を備える。 In one embodiment of the present invention, the humidity control sheet comprises an allophane membrane composite in which the substrate is a non-woven fabric.
本発明のアロフェン膜は、結合材を含まないアロフェン単味からなることに特徴がある。結合材によるアロフェン細孔の閉塞がないことから吸着能の低下がない。アロフェン粉末と比較して、アロフェン膜の吸着能の低下がない。また、膜状であるためアロフェン単味のバルク体と比較して、吸着速度が速いという優位点も発現した。 The allophane membrane of the present invention is characterized in that it comprises allophane alone with no binder. Since there is no blockage of the allophane pore by the binder, there is no decrease in adsorption capacity. There is no loss of adsorption capacity of the allophane membrane as compared to the allophane powder. In addition, since it is in the form of a membrane, it has an advantage that the adsorption rate is faster than that of allophane alone.
本発明の一実施形態に係るアロフェン膜複合体１０を示す模式図であり、（ａ）はアロフェン膜複合体１０の斜視図を示し、（ｂ）はアロフェン膜複合体１０の断面図を示す。It is a schematic diagram which shows the allophane membrane complex 10 which concerns on one Embodiment of this invention, (a) shows the perspective view of the allophane membrane complex 10, (b) shows sectional drawing of the allophane membrane complex 10. As shown in FIG. 本発明の一実施形態に係るアロフェン原料微粒子１７を示し、（ａ）はアロフェン原料微粒子１７の模式図であり、（ｂ）はアロフェン原料微粒子１７のＳＥＭ像である。The allophane raw material microparticles | fine-particles 17 which concern on one Embodiment of this invention are shown, (a) is a schematic diagram of the allophane raw material microparticles | fine-particles 17, (b) is a SEM image of the allophane raw material microparticles | fine-particles 17. FIG. 本発明の一実施形態に係るアロフェン膜複合体の製造方法に用いるＡＤ法による製造装置１の一例を示す模式図である。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 membrane complex which concerns on one Embodiment of this invention. 本発明の一実施例に係るアロフェン膜複合体１０を示し、（ａ）はアロフェン膜複合体１０の断面の電界放射型電子顕微鏡像を示し、（ｂ）はＦＩＢを用いたアロフェン膜複合体２０の断面像を示す。The allophane membrane complex 10 which concerns on one Example of this invention is shown, (a) shows the field emission electron microscope image of the cross section of the allophane membrane complex 10, (b) is the allophane membrane complex 20 using FIB. Shows a cross-sectional image of 本発明の一実施例に係るアロフェン膜複合体１０のアロフェン膜１３の透過型電子顕微鏡像である。It is a transmission electron microscope image of the allophane membrane 13 of the allophane membrane complex 10 which concerns on one Example of this invention. 本発明の一実施例に係るアロフェン膜の相対湿度と吸湿率との相関曲線である。It is a correlation curve of relative humidity and moisture absorption rate of the allophane membrane concerning one example of the present invention. 本発明の一実施例に係るアロフェン膜の重量に対して吸湿量をプロットした図である。It is the figure which plotted the amount of moisture absorption with respect to the weight of the allophane membrane which concerns on one Example of this invention. 本発明の一実施例に係るアロフェン膜複合体の脂肪酸吸着試験の結果を示す。The result of the fatty acid adsorption test of the allophane membrane complex concerning one example of the present invention is shown. 本発明の一実施例に係るアロフェン膜複合体の油分吸着試験の結果を示す。The result of the oil adsorption test of the allophane membrane complex concerning one example of the present invention is shown. 本発明の一実施例に係るアロフェン膜複合体のリン酸イオンの吸着試験結果を示す。The adsorption test result of the phosphate ion of the allophane membrane complex which concerns on one Example of this invention is shown. 本発明の一実施例に係るアロフェン膜複合体の調湿試験の結果を示す。The result of the humidity control test of the allophane membrane complex which concerns on one Example of this invention is shown. 本発明の一実施例に係るアロフェン膜複合体の吸湿時間に対して吸湿率をプロットした図である。It is the figure which plotted the moisture absorption rate to the moisture absorption time of the allophane membrane complex which concerns on one Example of this invention.
　以下、図面を参照して本発明に係るアロフェン膜複合体、それを用いたシート、及びアロフェン膜複合体の製造方法について説明する。なお、本発明のアロフェン膜複合体、それを用いたシート、及びアロフェン膜複合体の製造方法は、以下に示す実施の形態及び実施例の記載内容に限定して解釈されるものではない。なお、本実施の形態及び後述する実施例で参照する図面において、同一部分又は同様な機能を有する部分には同一の符号を付し、その繰り返しの説明は省略する。 Hereinafter, the allophane membrane complex according to the present invention, the sheet using the same, and the method for producing the allophane membrane complex will be described with reference to the drawings. The allophane membrane complex of the present invention, the sheet using the same, and the method for producing the allophane membrane complex are not construed as being limited to the description of the embodiments and examples described below. Note that in the drawings referred to in this embodiment mode and the examples to be described later, the same portions or portions having similar functions are denoted by the same reference numerals, and repeated description thereof will be omitted.
図１は、本発明の一実施形態に係るアロフェン膜複合体１０を示す模式図である。図１（ａ）はアロフェン膜複合体１０の斜視図を示し、図１（ｂ）はアロフェン膜複合体１０の断面図を示す。アロフェン膜複合体１０は、基材１１と、基材１１上にアロフェン微粒子１５が堆積されたアロフェン膜１３と、を備える。アロフェン膜複合体１０は、結合材を含まないアロフェン単味（アロフェン微粒子１５のみ）からなるアロフェン膜１３を備える。このため、アロフェン単味のバルク体に匹敵する従来にない吸着能の有する。また、アロフェン膜１３は、アロフェン単味のバルク体と比較して、吸着速度が速い。 FIG. 1 is a schematic view showing an allophane membrane complex 10 according to an embodiment of the present invention. 1 (a) shows a perspective view of the allophane membrane complex 10, and FIG. 1 (b) shows a cross-sectional view of the allophane membrane complex 10. As shown in FIG. The allophane membrane complex 10 includes a substrate 11 and an allophane film 13 in which the allophane microparticles 15 are deposited on the substrate 11. The allophane membrane complex 10 is provided with the allophane membrane 13 made of allophane single taste (only the allophane fine particles 15) containing no binder. For this reason, it has an unprecedented adsorption capacity comparable to the bulk body of allophane alone. In addition, the allophane film 13 has a high adsorption rate as compared to the bulk body of allophane alone.
アロフェン（粘土鉱物アロフェンとも称する。）は、国内外から天然に産するものを採用することができる。また、アロフェンはケイ酸とアルミニウムイオンの共存溶液を水酸化ナトリウムなどのアルカリを用いた中和反応により合成することもできる。本発明に係るアロフェン膜複合体には、この合成アロフェンを採用してもよい。天然のアロフェンをそのまま使用することもできるが、好ましくは、含まれる石英や火山ガラスなどの不純物を水ヒ等の分離方法をもってアロフェン純度を高めた原料を用いることで、形成されるアロフェン膜の純度を高めることができる。 Allophane (also referred to as clay mineral allophane) can be one which is naturally produced from home and abroad. Allophane can also be synthesized by neutralization reaction of a solution of silicic acid and aluminum ion using an alkali such as sodium hydroxide. This synthetic allophane may be employed in the allophane membrane complex according to the present invention. Although natural allophane can be used as it is, preferably, the purity of the allophane film formed by using a raw material in which allophane purity is increased by a separation method such as water and the like, of impurities such as quartz and volcanic glass contained Can be enhanced.
図２にアロフェン原料微粒子１７を示す。図２（ａ）はアロフェン原料微粒子１７の模式図であり、図２（ｂ）はアロフェン原料微粒子１７の走査型電子顕微鏡（ＳＥＭ）像である。アロフェン原料微粒子１７は、複数のアロフェン微粒子１５が凝集した構造を有する。アロフェン原料微粒子１７は数μｍ～数十μｍの粒径を有する不定形の粒子である。 Allophane raw material microparticles 17 are shown in FIG. FIG. 2 (a) is a schematic view of the allophane raw material fine particles 17, and FIG. 2 (b) is a scanning electron microscope (SEM) image of the allophane raw material fine particles 17. As shown in FIG. The allophane raw material microparticles 17 have a structure in which a plurality of allophane microparticles 15 are aggregated. Allophane raw material fine particles 17 are irregularly shaped particles having a particle diameter of several μm to several tens of μm.
アロフェン膜１３は、空孔を備え、基材１１側からアロフェン膜１３の表面に向けてアロフェン微粒子１５が密から疎の堆積状態を備え、かつ基材１１とアロフェン膜１３との密な状態である。アロフェン膜１３は、厚さが５μｍ以上７０μｍ以下、吸湿率が１０％以上３０％以下、表面硬度がＨ以上を備える。一実施形態において、アロフェン膜１３は、基材１１側では数十ｎｍの空隙が存在するアロフェン微粒子１５が密な状態であり、表面近傍では１μｍ以下の比較的大きな空隙が存在するアロフェン微粒子１５が疎となる状態である。 The allophane film 13 has pores, and the allophane fine particles 15 have a dense to sparse deposition state from the substrate 11 side toward the surface of the allophane film 13 and in the dense state of the substrate 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, the allophane film 13 is in a state in which allophane fine particles 15 having a void of several tens of nm are dense on the substrate 11 side, and allophane fine particles 15 having a relatively large void of 1 μm or less near the surface. It is in a sparse state.
アロフェン膜１３は、中空状のアルミニウムシリケート（ＳｉＯ2／Ａｌ2Ｏ3）であるアロフェンを備える。アロフェンは、平均直径が３．５ｎｍ以上１０ｎｍ以下である。アロフェン膜１３は、吸湿性があり、アロフェン膜１３の重量が増えると吸湿量も増える。アロフェン膜１３は、水中においても、その形態を保持することができる。 The allophane film 13 includes 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 is hygroscopic, and as the weight of the allophane film 13 increases, the amount of moisture absorption also increases. The allophane film 13 can retain its form even in water.
基材１１は、ガラス、アルミニウム、アルミナ、不織布、ポリエチレンフィルムでコーティングしてなる不織布又はアルミナシート、シリカ含有ポリエチレンフィルムでコーティングしてなるアルミナシート及びＰＥＴシートの群から選ばれる１つである。 The substrate 11 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.
基材１１として不織布を選択する場合、不織布は、２４時間での透湿度が９５００ｇ／ｍ2以上１１００ｇ／ｍ2以下、通気度が１０ｍｌ／ｃｍ2以上２５ｍｌ／ｃｍ2以下、質量が６５ｇ／ｍ2以上８０ｇ／ｍ2以下、厚さが０．１４ｍｍ以上０．２５ｍｍ以下を備える。 When selecting a nonwoven as a substrate 11, 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, mass 65 g / m 2 or more and 80 g / m 2 or less, and the thickness is 0.14 mm or more and 0.25 mm or less.
［製造方法］
本発明の一実施形態に係るアロフェン膜複合体１０の形成には、エアロゾルデポジション法（ＡＤ法）を使用することが好ましい。図３は、本発明の一実施形態に係るアロフェン膜複合体の製造方法に用いるＡＤ法による製造装置１の一例を示す模式図である。ＡＤ法については、例えば、特許第３２６５４８１号を参照することができる。製造装置１は、例えば、減圧チャンバ２内に基材１１と、ノズル４とを配設している。基材１１は形成されたアロフェン膜１３を支持する。 [Production method]
It is preferable to use an aerosol deposition method (AD method) for formation of the allophane membrane complex 10 which concerns on one Embodiment of this invention. FIG. 3: is a schematic diagram which shows an example of the manufacturing apparatus 1 by AD method used for the manufacturing method of the allophane membrane complex which concerns on one Embodiment of this invention. For example, Japanese Patent No. 3265481 can be referred to for the AD method. In the manufacturing apparatus 1, for example, the base 11 and the nozzle 4 are disposed in the decompression chamber 2. The substrate 11 supports the formed allophane film 13.
ノズル４はアロフェン原料微粒子１７を基材１１上に供給し、アロフェン微粒子圧粉体１２を形成するものである。アロフェン微粒子圧粉体１２はノズル４からアロフェン微粒子１５が基材１１上に吹き付けられ、この吹き付けによってアロフェン微粒子１５に機械的衝撃力が作用してアロフェン微粒子１５の間に接合状態が生じた状態である。基材１１は基板駆動装置６に取り付けられ、基板駆動装置６に駆動されてチャンバ２内で変位可能である。ノズル４もチャンバ内で変位可能に構成してもよい。 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. In the allophane fine particle powder compact 12, allophane fine particles 15 are sprayed from the nozzle 4 onto the base material 11, and by this mechanical impact force acting on the allophane fine particles 15, a bonding state occurs between the allophane fine particles 15. is there. The substrate 11 is attached to the substrate driving device 6 and driven by the substrate driving device 6 so as to be displaceable in the chamber 2. The nozzle 4 may also be displaceable in the chamber.
アロフェン原料微粒子１７を搬送ガスと混合してエアロゾル化し、該搬送ガスと共に、アロフェン微粒子１５を、ノズル４を通して加速して被堆積基材１１の表面に向けて噴射せしめることにより、減圧チャンバ２内で基材１１にアロフェン膜１３を形成させる。このとき、搬送ガスの流量は、２Ｌ／ｍｉｎ～７Ｌ／ｍｉｎ程度とすることが好ましく、基板駆動装置６のスピードは４ｍｍ／ｓｅｃ～１０ｍｍ／ｓｅｃとすることが好ましい。また、チャンバ２内の圧力を１００Ｐａ～９０Ｐａであることが好ましい。搬送ガスとしては、例えば、窒素やアルゴン等の不活性ガスや乾燥した空気等を用いることができる。 Allophane raw material fine particles 17 are mixed with a carrier gas and aerosolized, and together with the carrier gas, allophane fine particles 15 are accelerated through the nozzle 4 and sprayed toward the surface of the deposition target substrate 11, thereby reducing pressure in the decompression chamber 2. An allophane film 13 is formed on the substrate 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 in the chamber 2 is preferably 100 Pa to 90 Pa. As the carrier gas, for example, an inert gas such as nitrogen or argon, dried air or the like can be used.
また、一実施形態において、ノズル４からの吹き付けによる衝撃力に応じて、使用するアロフェン微粒子材料の機械的強度（脆性破壊強度）などの破壊強度を上述の衝撃力で粉砕が容易に起こるように、長時間ボールミルやジェットミルなどの粉砕機にかけ、クラックなどを予め形成しておいてもよい。 Further, in one embodiment, in response to the impact force by the spray from the nozzle 4, the fracture strength such as mechanical strength (brittle fracture strength) of the allophane fine particle material to be used is easily crushed by the above-mentioned impact force. The crack may be formed in advance by using a crusher such as a ball mill or jet mill for a long time.
この様なアロフェン粒子材料を使用することで、アロフェン原料微粒子１７を少なくとも１００ｎｍ以下に粉砕し、清浄な新生表面を形成し、低温接合を生じさせ、室温で微粒子同士の接合を実現することができる。この時、使用する元のアロフェン原料微粒子１７の粒子径が、５０ｎｍ以下の場合は、上述した衝撃粉砕は生じにくいと考えられる。また、基板に吹き付ける方法の場合、粒子径が大きすぎると、粉砕に必要な衝撃力を与えることが困難になる。従って、上述したそれぞれの成形方法に対して、適切な粒径範囲（おおよそ、５０ｎｍ～５μｍ）が存在するものと考えられる。 By using such allophane particle material, it is possible to grind allophane raw material fine particles 17 to at least 100 nm or less, to form a clean new surface, to cause low temperature bonding, and to realize bonding of particles to each other at room temperature. . At this time, when the particle diameter of the original allophane raw material fine particles 17 to be used is 50 nm or less, it is considered that the above-mentioned impact pulverization hardly occurs. Moreover, in the case of the method of spraying on a board | substrate, when particle diameter is too large, it will become difficult to give the impact force required for crushing. Therefore, it is believed that there is a suitable particle size range (approximately 50 nm to 5 μm) for each of the molding methods described above.
粘土鉱物としては、ゼオライト、カオリナイト、タルク等が知られているが、アロフェンは、これらの粘土鉱物とはその構造が大きく異なる。ゼオライト、カオリナイト、タルク等の一般的な粘土鉱物は原子配列の長距離秩序を持つ結晶構造を有する。一方、アロフェンは、上述した中空状の球形の構造を有し、球形粒子内の原子配列における短距離秩序を持つものの、一般的な結晶のように原子配列に長距離秩序は有していない。上述したＡＤ法は、従来、結晶性の高い原料微粒子を用いる成膜方法であり、その成膜機構には結晶の塑性変形が寄与していると考えられているため、アロフェンのような結晶性が低い（非晶質）材料に適用することがなかった。 As clay minerals, zeolite, kaolinite, talc and the like are known, but allophane differs from these clay minerals in its structure. Common clay minerals such as zeolite, kaolinite and talc have a crystal structure with long-range order of atomic arrangement. On the other hand, allophane has the above-described hollow spherical structure and has short-range order in atomic arrangement in spherical particles, but does not have long-range order in atomic arrangement like general crystals. 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 the crystal contributes to the film forming mechanism, so that crystallinity such as allophane is obtained. Has not been applied to low (amorphous) materials.
本発明者らは、本発明に係るアロフェン膜複合体の製造方法に類似した成膜方法を用いて、結晶性の多孔質材料であるゼオライトを原料微粒子とする成膜を行ったが、結晶性が低い中空状の球形の構造を有するアロフェンを原料微粒子とする成膜が可能であることは、これまでに予期することはできず、仮に成膜出来たとしても中空構造が潰れ、吸湿特性等が失われると予期された。本発明により吸湿特性等を保持したままの成膜を実現し、初めて報告するものである。 The present inventors carried out film formation using zeolite, which is a crystalline porous material, as raw material fine particles, using a film formation method similar to the method for producing an allophane membrane composite according to the present invention. It can not be expected that film formation can be performed using allophane having a hollow spherical structure with a low particle size as a raw material fine particle, so it can not be anticipated so far, even if film formation is possible, the hollow structure collapses, moisture absorption characteristics, etc. Was expected to be lost. According to the present invention, film formation while maintaining the moisture absorption characteristics etc. is realized, and it is reported for the first time.
また、ゼオライトが低湿度条件下での吸湿特性を有するのに対して、アロフェンは中湿度条件下での吸湿特性を有する点で、アロフェン膜複合体は有意な効果を奏する。さらに、アロフェンは、リン酸や有機酸の吸着能を有することから、アロフェン膜複合体を脱臭剤等に利用することができる。 In addition, the allophane membrane complex exerts a significant effect in that allophane has hygroscopic properties under medium humidity conditions, while zeolite has hygroscopic properties under low humidity conditions. Furthermore, since allophane has an adsorption capacity for phosphoric acid and organic acids, the allophane membrane complex can be used as a deodorizing agent and the like.
以下、実施例に基づいて本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
（実施例１）
実施例１として、不織布（表面をポリエチレンフィルムでコートした不織布）基材にアロフェン原料微粒子１７を噴射してアロフェン膜をＡＤ法で形成した。整粒したアロフェン粉末を流量２．５Ｌ／ｍｉｎの窒素ガスでエアロゾル化し、開口幅３０ｍｍ×０．２ｍｍのノズルを通して、２０Ｐａの真空雰囲気のチャンバ内に置いた不織布（表面をポリエチレンフィルムでコートした不織布）基材に噴射してアロフェン膜を形成し、アロフェン膜－不織布複合体を作製した。基材はノズルに対して４ｍｍ／ｓのスピードで変位させながら往復させ、成膜時間５００秒、成膜面積は３０×１００ｍｍ2とした。 Example 1
In Example 1, allophane raw material fine particles 17 were sprayed onto a non-woven fabric (non-woven fabric whose surface was coated with a polyethylene film) to form an allophane film by the AD method. Non-woven fabric placed in a chamber with a vacuum atmosphere of 20 Pa through a nozzle with an opening width of 30 mm × 0.2 mm through aerosolization of sized allophane powder with nitrogen gas at a flow rate of 2.5 L / min (non-woven fabric whose surface is coated with polyethylene film) ) The substrate was sprayed to form an allophane film 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 .
アロフェン膜－不織布複合体の重さを測定し、成膜前の不織布の重さとの差からアロフェン膜の重さを算出した。その結果、アロフェン膜の重さは０．０９ｇであった。 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 nonwoven fabric before film formation. As a result, the weight of the allophane membrane was 0.09 g.
アロフェン膜－不織布複合体の断面をクロスセクションポリッシャで作製し、電界放射型電子顕微鏡で観察した。図４（ａ）は、実施例１に係るアロフェン膜複合体１０の断面の電界放射型電子顕微鏡像を示す。図４（ａ）において、不織布基材１１上にアロフェン膜１３が形成されていることが確認できた。アロフェン膜１３の厚みは２２μｍ程度であった。
　装置：
　クロスセクションポリッシャ：ＳＭ－０９０１０
　電界放射型電子顕微鏡：ＪＳＭ－７４００Ｆ The 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 complex 10 according to Example 1. FIG. In FIG. 4A, it can be confirmed that the allophane film 13 is 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
アロフェン膜－不織布複合体を透過型電子顕微鏡で観察した。図５は、実施例１に係るアロフェン複合体１０のアロフェン膜１３の透過型電子顕微鏡像を示す。図５において、アロフェン膜は、直径５～１０ｎｍの球状粒子が緻密化しており、アロフェンの中空構造が潰れることなく膜化していることが確認できた。
　装置：
　透過型電子顕微鏡：ＪＥＭ－２０１０ The allophane membrane-nonwoven fabric complex was observed by a transmission electron microscope. FIG. 5 shows a transmission electron microscope image of the allophane film 13 of the allophane complex 10 according to Example 1. In FIG. 5, it was confirmed that the allophane film was compacted by spherical particles having a diameter of 5 to 10 nm, and the film was formed without collapsing the hollow structure of allophane.
apparatus:
Transmission electron microscope: JEM-2010
アロフェン膜－不織布複合体のアロフェン膜の表面硬度を引っかき硬度試験（手掻き鉛筆法）で評価した。その結果、アロフェン膜はＨ以上の表面硬度を有していた。 The surface hardness of the allophane film of the allophane film-nonwoven fabric composite was evaluated by a scratch hardness test (hand-drawn pencil method). As a result, the allophane film had a surface hardness of H or more.
アロフェン膜－不織布複合体を折り曲げ、アロフェン膜の不織布基材に対する密着性を評価した。９０°に一回折り曲げたときアロフェン膜は剥離しなかった。 The allophane film-nonwoven fabric composite was folded to evaluate the adhesion of the allophane film to the non-woven fabric substrate. When bent once at 90 °, the allophane film did not peel off.
アロフェン膜－不織布複合体に粘着力４．０１Ｎ／１０ｍｍのセロハン粘着テープを貼り付けて剥がし、膜の密着性を評価した。その結果、アロフェン膜はセロハン粘着テープを剥がしても剥離せず、４．０Ｎ／１０ｍｍ以上の密着力があることが分かった。 A cellophane adhesive tape having an adhesive strength 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 even when the cellophane adhesive tape was peeled off, and had an adhesion of 4.0 N / 10 mm or more.
アロフェン膜－不織布複合体について、相対湿度と吸湿率の関係を検証した。１３０℃で乾燥後、４０℃において、相対湿度を変更して、アロフェン膜－不織布複合体及びアロフェン原料微粒子について相関曲線を得た（図６）。本実施例のアロフェン膜－不織布複合体は、アロフェン原料微粒子と同等の吸湿性能を有している。また、１３０℃で乾燥後のアロフェン膜－不織布複合体を温度４０℃、相対湿度８０％の雰囲気に４８時間静置し、吸湿特性を評価した。アロフェン膜－不織布複合体の重量増加分を吸湿量、アロフェン膜－不織布複合体のアロフェン１ｇあたりの吸湿量を吸湿率として評価した結果、吸湿量は０．０２３ｇ、吸湿率は２５．３％であった。 The relationship between relative humidity and moisture absorption rate was verified for the allophane membrane-nonwoven fabric composite. After drying at 130 ° C., the relative humidity was changed at 40 ° C. to obtain correlation curves for the allophane membrane-nonwoven fabric composite and the allophane raw material fine particles (FIG. 6). The allophane membrane-nonwoven fabric composite of the present example has the same moisture absorption performance as the allophane raw material fine particles. Further, the allophane membrane-nonwoven fabric composite after drying at 130 ° C. was allowed to stand in an atmosphere of temperature 40 ° C. and relative humidity 80% for 48 hours to evaluate moisture absorption characteristics. The weight gain of the allophane membrane-nonwoven fabric composite was evaluated as the moisture absorption rate, and the moisture absorption rate per 1 g of allophane membrane-nonwoven fabric composite as the moisture absorption rate was 0.023 g, and the moisture absorption rate was 25.3%. there were.
アロフェン膜－不織布複合体を水中に投入したところ、アロフェン膜は崩壊することなく形態を保持していた。 When the allophane membrane-nonwoven fabric composite was put into water, the allophane membrane retained its form without disintegration.
（実施例２）
基材へのエアロゾル噴射時間を１００秒程度とした以外は実施例１と同様にアロフェン膜－不織布複合体を作製した。 (Example 2)
An allophane membrane-nonwoven fabric composite was produced in the same manner as in Example 1 except that the time for aerosol injection onto the substrate was about 100 seconds.
実施例１と同様にアロフェン膜の重さを算出した結果、０．１６ｇであった。実施例１と同様にアロフェン膜の厚みを測定した結果、３８μｍ程度であった。実施例１と同様にアロフェン膜の表面硬度を評価した結果、アロフェン膜はＨ以上の表面硬度を有していた。実施例１と同様にアロフェン膜の密着性を評価した結果、９０°に一回折り曲げたときアロフェン膜は剥離しなかった。実施例１と同様にセロハン粘着テープでアロフェン膜の基材への密着性を評価した結果、４．０Ｎ／１０ｍｍ以上の密着力があることが分かった。実施例１と同様にアロフェン膜－不織布複合体の吸湿特性を評価した結果、吸湿量は０．０３３ｇ、吸湿率は２０．６％であった。実施例１と同様にアロフェン膜複合体を水中に投入したところ、アロフェン膜は崩壊することなく形態を保持していた。 As a result of calculating the weight of the allophane membrane in the same manner as in Example 1, it was 0.16 g. The thickness of the allophane film was measured in the same manner as in Example 1. As a result, it was about 38 μm. The surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film had a surface hardness of H or more. The adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, when it was bent once at 90 °, the allophane film did not peel off. As a result of evaluating the adhesiveness to the base material of the allophane film with the cellophane adhesive tape similarly to Example 1, it turned out that there exists adhesiveness of 4.0 N / 10 mm or more. As a result of evaluating the moisture absorption characteristics of the allophane membrane-nonwoven fabric composite in the same manner as in Example 1, the moisture absorption amount was 0.033 g, and the moisture absorption rate was 20.6%. When the allophane membrane complex was introduced into water in the same manner as in Example 1, the allophane membrane retained its form without disintegration.
（実施例３）
基材へのエアロゾル噴射時間を１２５０秒程度とした以外は実施例１と同様に成膜試料を作製した。 (Example 3)
The film-forming sample was produced similarly to Example 1 except having made aerosol injection time to a base material into about 1250 second.
実施例１と同様にアロフェン膜の重さを算出した結果、０．２１ｇであった。実施例１と同様にアロフェン膜の厚みを測定した結果、５０μｍ程度であった。実施例１と同様にアロフェン膜の表面硬度を評価した結果、アロフェン膜はＨ以上の表面硬度を有していた。実施例１と同様にアロフェン膜の密着性を評価した結果、９０°に一回折り曲げたときアロフェン膜は剥離しなかった。実施例１と同様にセロハン粘着テープでアロフェン膜の基材への密着性を評価した結果、４．０Ｎ／１０ｍｍ以上の密着力があることが分かった。実施例１と同様にアロフェン膜－不織布複合体の吸湿特性を評価した結果、吸湿量は０．０４１ｇ、吸湿率は１９．５％であった。実施例１と同様にアロフェン膜複合体を水中に投入したところ、アロフェン膜は崩壊することなく形態を保持していた。 As a result of calculating the weight of the allophane membrane 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. The surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film had a surface hardness of H or more. The adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, when it was bent once at 90 °, the allophane film did not peel off. As a result of evaluating the adhesiveness to the base material of the allophane film with the cellophane adhesive tape similarly to Example 1, it turned out that there exists adhesiveness of 4.0 N / 10 mm or more. As a result of evaluating the moisture absorption characteristics of the allophane membrane-nonwoven fabric composite in the same manner as in Example 1, the moisture absorption amount was 0.041 g, and the moisture absorption rate was 19.5%. When the allophane membrane complex was introduced into water in the same manner as in Example 1, the allophane membrane retained its form without disintegration.
（実施例４）
基材へのエアロゾル噴射時間を１５００秒程度とした以外は実施例１と同様に成膜試料を作製した。 (Example 4)
The film-forming sample was produced similarly to Example 1 except having made aerosol injection time to a base material about 1500 seconds.
実施例１と同様にアロフェン膜の重さを算出した結果、０．２６ｇであった。実施例１と同様にアロフェン膜の厚みを測定した結果、６２μｍ程度であった。実施例１と同様にアロフェン膜の表面硬度を評価した結果、アロフェン膜はＨ以上の表面硬度を有していた。実施例１と同様にアロフェン膜の密着性を評価した結果、９０°に一回折り曲げたときアロフェン膜は剥離しなかった。実施例１と同様にセロハン粘着テープでアロフェン膜の基材への密着性を評価した結果、４．０Ｎ／１０ｍｍ以上の密着力があることが分かった。実施例１と同様にアロフェン膜－不織布複合体の吸湿特性を評価した結果、吸湿量は０．０５３ｇ、吸湿率は２０．４％であった。実施例１と同様にアロフェン膜複合体を水中に投入したところ、アロフェン膜は崩壊することなく形態を保持していた。 As a result of calculating the weight of the allophane membrane 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. The surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film had a surface hardness of H or more. The adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, when it was bent once at 90 °, the allophane film did not peel off. As a result of evaluating the adhesiveness to the base material of the allophane film with the cellophane adhesive tape similarly to Example 1, it turned out that there exists adhesiveness of 4.0 N / 10 mm or more. As a result of evaluating the moisture absorption characteristics of the allophane membrane-nonwoven fabric composite in the same manner as in Example 1, the moisture absorption amount was 0.053 g, and the moisture absorption rate was 20.4%. When the allophane membrane complex was introduced into water in the same manner as in Example 1, the allophane membrane retained its form without disintegration.
実施例１～５のアロフェン膜複合体の吸湿量を評価した。図７は、アロフェン膜の重量に対して吸湿量をプロットした図である。図７より、アロフェン膜の重量が増加するとともに、吸湿量も増加することが確認された。 The moisture absorption of the allophane membrane complex of Examples 1 to 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 is confirmed that the moisture absorption amount also increases as the weight of the allophane membrane increases.
（実施例５）
整粒したアロフェン粉末を流量２．１Ｌ／ｍｉｎの圧縮空気でエアロゾル化し、開口幅７ｍｍ×０．４ｍｍのノズルを通して、１５Ｐａの真空雰囲気のチャンバ内に置いた不織布（表面をポリエチレンフィルムでコートした不織布）基材に噴射してアロフェン膜を形成し、アロフェン膜－不織布複合体を作製した。基材をＸＹステージにより１０ｍｍ／ｓのスピードで変位させ、成膜面積は３５０×３５０ｍｍ2の大面積化した複合体を得た。 (Example 5)
Non-woven fabric placed in a chamber with a vacuum atmosphere of 15 Pa through a nozzle with an opening width of 7 mm × 0.4 mm through aerosolization of sized allophane powder with compressed air at a flow rate of 2.1 L / min (non-woven fabric whose surface is coated with polyethylene film) ) The substrate was sprayed to form an allophane film 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 large-sized composite having a film formation area of 350 × 350 mm 2 .
実施例１と同様にアロフェン膜の重さを算出した結果、３．２７ｇであった。実施例１と同様にアロフェン膜の厚みを測定した結果、１９μｍ程度であった。実施例１と同様にアロフェン膜の表面硬度を評価した結果、アロフェン膜はＨ以上の表面硬度を有していた。実施例１と同様にアロフェン膜の密着性を評価した結果、９０°に一回折り曲げたときアロフェン膜は剥離しなかった。実施例１と同様にセロハン粘着テープでアロフェン膜の基材への密着性を評価した結果、４．０Ｎ／１０ｍｍ以上の密着力があることが分かった。実施例１と同様にアロフェン膜複合体を水中に投入したところ、アロフェン膜は崩壊することなく形態を保持していた。 As a result of calculating the weight of the allophane membrane in the same manner as in Example 1, it was 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. The surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film had a surface hardness of H or more. The adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, when it was bent once at 90 °, the allophane film did not peel off. As a result of evaluating the adhesiveness to the base material of the allophane film with the cellophane adhesive tape similarly to Example 1, it turned out that there exists adhesiveness of 4.0 N / 10 mm or more. When the allophane membrane complex was introduced into water in the same manner as in Example 1, the allophane membrane retained its form without disintegration.
（実施例６）
基材をガラス板、成膜面積を３０×２０ｍｍ2とした以外は実施例１と同様にアロフェン膜を成膜し、アロフェン膜－ガラス複合体を作製した。 (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 , to prepare an allophane film-glass composite.
実施例１と同様にアロフェン膜の表面硬度を評価した結果、アロフェン膜はＨ以上の表面硬度を有していた。実施例１と同様にセロハン粘着テープでアロフェン膜の基材への密着性を評価した結果、４．０Ｎ／１０ｍｍ以上の密着力があることが分かった。実施例１と同様にアロフェン膜複合体を水中に投入したところ、アロフェン膜は崩壊することなく形態を保持していた。 The surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film had a surface hardness of H or more. As a result of evaluating the adhesiveness to the base material of the allophane film with the cellophane adhesive tape similarly to Example 1, it turned out that there exists adhesiveness of 4.0 N / 10 mm or more. When the allophane membrane complex was introduced into water in the same manner as in Example 1, the allophane membrane retained its form without disintegration.
（実施例７）
基材をフレキシブルアルミニウムシートとし、アロフェン粉末を流量３．５Ｌ／ｍｉｎの窒素ガスでエアロゾル化し、開口幅３０ｍｍ×０．２ｍｍのノズルを通して、２０Ｐａの真空雰囲気のチャンバ内に置いた基材に噴射してアロフェン膜を形成し、アロフェン膜－アルミニウム複合体を作製した。基材はノズルに対して往復に変位させ、成膜時間５０秒、成膜面積は３０×１００ｍｍ2とした。 (Example 7)
The substrate is a flexible aluminum sheet, and allophane powder is aerosolized with nitrogen gas at a flow rate of 3.5 L / min and sprayed through a nozzle with an opening width of 30 mm × 0.2 mm to a substrate placed in a chamber with a vacuum atmosphere of 20 Pa. The allophane membrane was formed to prepare an allophane membrane-aluminum complex. The substrate was displaced reciprocally with respect to the nozzle, and the film formation time was 50 seconds, and the film formation area was 30 × 100 mm 2 .
図４（ｂ）に、実施例７のフレキシブルアルミニウムシート基材２１上にアロフェン膜１３を成膜したアロフェン膜－アルミニウム複合体２０のＦＩＢを用いた断面像を示す。図４（ｂ）から、アロフェン膜１３が、基材２１側からアロフェン膜１３の表面に向けてアロフェン微粒子が密から疎の堆積状態を備えることが明らかとなった。 FIG. 4B shows a cross-sectional image using an FIB of the allophane film-aluminum composite 20 in which the allophane film 13 is formed on the flexible aluminum sheet base 21 of Example 7. From FIG. 4 (b), it is clear that the allophane film 13 has a dense to sparse deposition state in which the allophane fine particles are directed from the substrate 21 side to the surface of the allophane film 13.
実施例１と同様にアロフェン膜の表面硬度を評価した結果、アロフェン膜はＨ以上の表面硬度を有していた。実施例１と同様にアロフェン膜の密着性を評価した結果、９０°に一回折り曲げたときアロフェン膜は剥離しなかった。実施例１と同様にセロハン粘着テープでアロフェン膜の基材への密着性を評価した結果、４．０Ｎ／１０ｍｍ以上の密着力があることが分かった。実施例１と同様にアロフェン膜複合体を水中に投入したところ、アロフェン膜は崩壊することなく形態を保持していた。 The surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film had a surface hardness of H or more. The adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, when it was bent once at 90 °, the allophane film did not peel off. As a result of evaluating the adhesiveness to the base material of the allophane film with the cellophane adhesive tape similarly to Example 1, it turned out that there exists adhesiveness of 4.0 N / 10 mm or more. When the allophane membrane complex was introduced into water in the same manner as in Example 1, the allophane membrane retained its form without disintegration.
（実施例８）
基材をシリカ含有ポリエチレンフィルムでコートされたフレキシブルアルミニウムシート、成膜面積を１１×２２ｍｍ2とした以外は実施例１と同様にフィルム面にアロフェン膜を成膜し、アロフェン膜－アルミニウム複合体を作製した。 (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, and an allophane film-aluminum composite was obtained. Made.
実施例１と同様にアロフェン膜の表面硬度を評価した結果、アロフェン膜はＨ以上の表面硬度を有していた。実施例１と同様にアロフェン膜の密着性を評価した結果、９０°に一回折り曲げたときアロフェン膜は剥離しなかった。実施例１と同様にセロハン粘着テープでアロフェン膜の基材への密着性を評価した結果、４．０Ｎ／１０ｍｍ以上の密着力があることが分かった。実施例１と同様にアロフェン膜複合体を水中に投入したところ、アロフェン膜は崩壊することなく形態を保持していた。 The surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film had a surface hardness of H or more. The adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, when it was bent once at 90 °, the allophane film did not peel off. As a result of evaluating the adhesiveness to the base material of the allophane film with the cellophane adhesive tape similarly to Example 1, it turned out that there exists adhesiveness of 4.0 N / 10 mm or more. When the allophane membrane complex was introduced into water in the same manner as in Example 1, the allophane membrane retained its form without disintegration.
（実施例９）
基材をポリエチレンテレフタレート（ＰＥＴ）シート、成膜面積を９×２８ｍｍ2とした以外は実施例１と同様にアロフェン膜を成膜し、アロフェン膜－ＰＥＴ複合体を作製した。 (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.
実施例１と同様にアロフェン膜の表面硬度を評価した結果、アロフェン膜はＨ以上の表面硬度を有していた。実施例１と同様にアロフェン膜の密着性を評価した結果、９０°に一回折り曲げたときアロフェン膜は剥離しなかった。実施例１と同様にセロハン粘着テープでアロフェン膜の基材への密着性を評価した結果、４．０Ｎ／１０ｍｍ以上の密着力があることが分かった。実施例１と同様にアロフェン膜複合体を水中に投入したところ、アロフェン膜は崩壊することなく形態を保持していた。 The surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film had a surface hardness of H or more. The adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, when it was bent once at 90 °, the allophane film did not peel off. As a result of evaluating the adhesiveness to the base material of the allophane film with the cellophane adhesive tape similarly to Example 1, it turned out that there exists adhesiveness of 4.0 N / 10 mm or more. When the allophane membrane complex was introduced into water in the same manner as in Example 1, the allophane membrane retained its form without disintegration.
（比較例１）
整粒したアロフェン粉末３０ｇに、水７０ｍｌを加えて調製した３０％スラリーを、ガラス板上にアプリケーターを用いて厚さ５０μｍ塗布した後、１３０℃で１時間乾燥することで、アロフェン膜－ガラス複合体を作製した。 (Comparative example 1)
A 30% slurry prepared by adding 70 ml of water to 30 g of sized allophane powder is coated on a glass plate with a thickness of 50 μm using an applicator and then dried at 130 ° C. for 1 hour to obtain allophane film-glass composite The body was made.
実施例１と同様にアロフェン膜の表面硬度を評価した結果、アロフェン膜の表面硬度は４Ｂであった。実施例１と同様にセロハン粘着テープでアロフェン膜の基材への密着性を評価した結果、アロフェン膜はセロハン粘着テープに付着し基材から剥離したことから、４．０Ｎ／１０ｍｍ未満の密着力であった。実施例１と同様にアロフェン膜複合体を水中に投入したところ、アロフェン膜は崩壊した。 The surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the surface hardness of the allophane film was 4B. As a result of evaluating the adhesion of the allophane film to the substrate with the cellophane adhesive tape in the same manner as in Example 1, the allophane film was adhered to the cellophane adhesive tape and peeled from the substrate, so the adhesion of less than 4.0 N / 10 mm. Met. When the allophane membrane complex was introduced into water as in Example 1, the allophane membrane collapsed.
（比較例２）
整粒したアロフェン粉末３０ｇに、水７０ｍｌを加えて調製した３０％スラリーを、不織布（表面をポリエチレンフィルムでコートした不織布）上にアプリケーターを用いて厚さ５０μｍ塗布した後、１３０℃で１時間乾燥することで、アロフェン膜－不織布複合体を作製した。 (Comparative example 2)
A 30% slurry prepared by adding 70 ml of water to 30 g of sized allophane powder is coated on a non-woven fabric (non-woven fabric coated on the surface with a polyethylene film) using an applicator to a thickness of 50 μm and then dried at 130 ° C. for 1 hour By doing this, an allophane membrane-nonwoven fabric composite was produced.
実施例１と同様にアロフェン膜の表面硬度を評価した結果、アロフェン膜の表面硬度は４Ｂであった。実施例１と同様にアロフェン膜の密着性を評価した結果、９０°に一回折り曲げたときアロフェン膜は剥離した。実施例１と同様にセロハン粘着テープでアロフェン膜の基材への密着性を評価した結果、アロフェン膜はセロハン粘着テープに付着し基材から剥離したことから、４．０Ｎ／１０ｍｍ未満の密着力であった。実施例１と同様にアロフェン膜複合体を水中に投入したところ、アロフェン膜は崩壊した。 The surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the surface hardness of the allophane film was 4B. The adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film peeled off when bent once at 90 °. As a result of evaluating the adhesion of the allophane film to the substrate with the cellophane adhesive tape in the same manner as in Example 1, the allophane film was adhered to the cellophane adhesive tape and peeled from the substrate, so the adhesion of less than 4.0 N / 10 mm. Met. When the allophane membrane complex was introduced into water as in Example 1, the allophane membrane collapsed.
（比較例３）
整粒したアロフェン粉末３０ｇに、エチルアルコール７０ｍｌを加えて調製した３０％スラリーを、不織布（表面をポリエチレンフィルムでコートした不織布）上にアプリケーターを用いて厚さ５０μｍ塗布した後、１３０℃で１時間乾燥することで、アロフェン膜－不織布複合体を作製した。 (Comparative example 3)
A 30% slurry prepared by adding 70 ml of ethyl alcohol to 30 g of sized allophane powder is coated on a non-woven fabric (non-woven fabric coated on the surface with a polyethylene film) using an applicator to a thickness of 50 μm and then 1 hour at 130 ° C. By drying, an allophane membrane-nonwoven fabric composite was produced.
実施例１と同様にアロフェン膜の表面硬度を評価した結果、アロフェン膜の表面硬度は４Ｂであった。実施例１と同様にアロフェン膜の密着性を評価した結果、９０°に一回折り曲げたときアロフェン膜は剥離した。実施例１と同様にセロハン粘着テープでアロフェン膜の基材への密着性を評価した結果、アロフェン膜はセロハン粘着テープに付着し基材から剥離したことから、４．０Ｎ／１０ｍｍ未満の密着力であった。実施例１と同様にアロフェン膜複合体を水中に投入したところ、アロフェン膜は崩壊した。 The surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the surface hardness of the allophane film was 4B. The adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film peeled off when bent once at 90 °. As a result of evaluating the adhesion of the allophane film to the substrate with the cellophane adhesive tape in the same manner as in Example 1, the allophane film was adhered to the cellophane adhesive tape and peeled from the substrate, so the adhesion of less than 4.0 N / 10 mm. Met. When the allophane membrane complex was introduced into water as in Example 1, the allophane membrane collapsed.
（比較例４）
整粒したアロフェン粉末３０ｇに、２－プロピルアルコール７０ｍｌを加えて調製した３０％スラリーを、不織布（表面をポリエチレンフィルムでコートした不織布）上にアプリケーターを用いて厚さ５０μｍ塗布した後、１３０℃で１時間乾燥することで、アロフェン膜－不織布複合体を作製した。 (Comparative example 4)
A 30% slurry prepared by adding 70 ml of 2-propyl alcohol to 30 g of sized allophane powder is coated on a non-woven fabric (non-woven fabric whose surface is coated with a polyethylene film) using an applicator at 50 μm thickness and then at 130 ° C. By drying for 1 hour, an allophane membrane-nonwoven fabric composite was produced.
実施例１と同様にアロフェン膜の表面硬度を評価した結果、アロフェン膜の表面硬度は４Ｂであった。実施例１と同様にアロフェン膜の密着性を評価した結果、９０°に一回折り曲げたときアロフェン膜は剥離した。実施例１と同様にセロハン粘着テープでアロフェン膜の基材への密着性を評価した結果、アロフェン膜はセロハン粘着テープに付着し基材から剥離したことから、４．０Ｎ／１０ｍｍ未満の密着力であった。実施例１と同様にアロフェン膜複合体を水中に投入したところ、アロフェン膜は崩壊した。 The surface hardness of the allophane film was evaluated in the same manner as in Example 1. As a result, the surface hardness of the allophane film was 4B. The adhesion of the allophane film was evaluated in the same manner as in Example 1. As a result, the allophane film peeled off when bent once at 90 °. As a result of evaluating the adhesion of the allophane film to the substrate with the cellophane adhesive tape in the same manner as in Example 1, the allophane film was adhered to the cellophane adhesive tape and peeled from the substrate, so the adhesion of less than 4.0 N / 10 mm. Met. When the allophane membrane complex was introduced into water as in Example 1, the allophane membrane collapsed.
（実施例１０）
アロフェン膜複合体について人工汚染液（ソルベントナフサ、アスファルト、オレイン酸の混合溶液）の吸着能の評価を行った。流量２．１Ｌ／ｍｉｎの窒素ガスでエアロゾル化し、開口幅７ｍｍ×０．４ｍｍのノズルを通して、１５Ｐａの真空雰囲気のチャンバ内で不織布基材に噴射してアロフェン膜を形成した。アロフェン膜の重さは０．４ｇ、１００×８０ｍｍ2のアロフェン膜複合体を作成した。 (Example 10)
For the allophane membrane complex, the adsorption ability of artificial contaminating liquid (a mixed solution of solvent naphtha, asphalt and oleic acid) was evaluated. The non-woven fabric substrate was aerosolized with nitrogen gas at a flow rate of 2.1 L / min and sprayed through a nozzle having an opening width of 7 mm × 0.4 mm in a vacuum atmosphere chamber of 15 Pa to form an allophane film. The weight of the allophane membrane was 0.4 g to make an allophane membrane complex of 100 × 80 mm 2 .
［脂肪酸吸着能］
汚染物の脂肪酸としてオレイン酸を用いて脂肪酸吸着能を評価した。１１０℃で３時間乾燥したアロフェン膜複合体を人工汚染液１００ｍｌに含浸させ１分間攪拌後、２５℃に保持したインキュベータ内で７２時間放置・吸着させ、定量濾紙で濾過することで測定試料を得た。次に、水酸化カリウムのエタノール溶液（０．０２ｍｏｌ／Ｌ）により中和滴定を行い、脱脂肪酸率を算出した。また、比較には成膜に用いた原料のアロフェン粉体を使用した。 [Fatty acid adsorption ability]
The fatty acid adsorption capacity was evaluated using oleic acid as the fatty acid of the contaminant. The allophane membrane complex dried at 110 ° C. for 3 hours is impregnated with 100 ml of artificial contamination solution, stirred for 1 minute, allowed to stand for 72 hours in a incubator kept at 25 ° C., adsorbed, and filtered through quantitative filter paper to obtain a measurement sample. The Next, neutralization titration was carried out with an ethanol solution (0.02 mol / L) of potassium hydroxide to calculate the percentage of fatty acid removal. Moreover, the allophane powder of the raw material used for film-forming was used for comparison.
［油分吸着能］
汚染物の油分としてアスファルトを用いて油分吸着能を評価した。脂肪酸吸着能の試験と同様に吸着後に試験液を得て、透過率測定を行った。吸着試験前の試験液の透過率は０％で、吸着試験後の透過率によって吸着能の程度を評価した。
　測定波長：４２０ｎｍ [Oil adsorption capacity]
The oil adsorption capacity was evaluated using asphalt as the oil component of the contaminants. The test solution was obtained after adsorption in the same manner as the fatty acid adsorption test, and the transmittance was measured. The permeability of the test solution before the adsorption test was 0%, and the degree of adsorption capacity was evaluated by the permeability after the adsorption test.
Measurement wavelength: 420 nm
脂肪酸吸着試験の結果を図８に示す。また、油分吸着試験の結果を図９に示す。これらの結果から、実施例１０のアロフェン膜複合体が人体や自然環境から出る汚れ成分を吸着する能力がアロフェン粉体以上であることがわかった。また、実施例１０のアロフェン膜複合体は石油系溶媒中でも膜の剥離がなく基板と密着性が高いことも確認できた。更に、成膜することで吸着性能が向上することが判明した。 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 membrane complex of Example 10 has an ability of adsorbing the dirt component emitted from the human body or the natural environment more than allophane powder. In addition, it was also confirmed that the allophane membrane complex of Example 10 had high film adhesion to the substrate without peeling of the film even in a petroleum solvent. Furthermore, it was found that the adsorption performance is improved by film formation.
（実施例１１）
アロフェン膜複合体の臭い成分の吸着能について評価した。臭い成分は、アンモニア、トリメチルアミン、および酢酸とした。実施例１１と同様に作成したアロフェン膜複合体（アロフェン膜のみの重量として１ｇ）をポリ袋に入れ、シールを施した後、９Ｌの空気を封入し、設定したガス濃度になるように試験対象ガスを添加し、３時間静置後のガス濃度を測定した。この結果を表１に示す。試験後の濃度はいすれも検出定量下限以下となり、いずれの臭い成分においてもアロフェン膜複合体は吸着能が高いことを確認できた。
Figure JPOXMLDOC01-appb-T000001
 (Example 11)
The adsorption capacity of the odor component of the allophane membrane complex was evaluated. The odorous components were ammonia, trimethylamine and acetic acid. The allophane membrane complex (1 g as the weight of allophane membrane alone) prepared in the same manner as in Example 11 is put in a plastic bag, sealed, sealed with 9 L of air, and subjected to the test so that the set gas concentration is achieved. The gas was added, and the gas concentration after standing for 3 hours was measured. The results are shown in Table 1. The concentration after the test was below the lower limit of detection and determination, and it was confirmed that the allophane membrane complex had high adsorption ability for any odor component.
Figure JPOXMLDOC01-appb-T000001
（実施例１２）
整粒したアロフェン粉末を流量２．５Ｌ／ｍｉｎの窒素ガスでエアロゾル化し、開口幅３０ｍｍ×０．２ｍｍのノズルを通して、２０Ｐａの真空雰囲気のチャンバ内に置いたアルミ基材に噴射して、成膜面積３０ｍｍ×１００ｍｍのアロフェン膜複合体を得た。所定濃度に調整したリン酸イオン水溶液中に、アロフェン膜複合体を２３℃で６時間浸漬して調べた結果を図１０に示す。リン酸吸着量は、基材上に成膜したアロフェン膜の重量に対して算出した。また比較として、アロフェン粉末０．２ｇを用いて同様に試験した結果も図１０に示す。図１０の結果のとおり、アロフェン膜複合体は、アロフェン粉末と同等のリン酸イオン吸着能を有する。 (Example 12)
The sized allophane powder is aerosolized with nitrogen gas at a flow rate of 2.5 L / min and sprayed onto an aluminum substrate placed in a chamber with a vacuum atmosphere of 20 Pa through a nozzle with an opening width of 30 mm × 0.2 mm. An allophane membrane complex with an area of 30 mm × 100 mm was obtained. The allophane membrane complex was immersed in a phosphate ion aqueous solution adjusted to a predetermined concentration for 6 hours at 23 ° C. and the result is shown in FIG. The amount of adsorbed phosphoric acid was calculated relative to the weight of the allophane film formed on the substrate. Also, as a comparison, the results of similar tests using 0.2 g of allophane powder are also shown in FIG. As shown in FIG. 10, the allophane membrane complex has phosphate ion adsorption ability equal to that of allophane powder.
（実施例１３）
実施例１と同様に作成したアロフェン膜複合体の調湿性能について、調湿試験を行うことにより評価した。図１１は、調湿試験の結果を示す図である。１３０℃で乾燥後に、４０℃、相対湿度８０％で吸湿した後、４０℃、相対湿度２０％で放湿を行った結果、アロフェン膜複合体は、調湿作用を有していることが分かった。 (Example 13)
The humidity control performance of the allophane membrane complex prepared as in Example 1 was evaluated by performing a humidity control test. FIG. 11 is a diagram showing the results of the humidity control test. After drying at 130 ° C, moisture was absorbed at 40 ° C and relative humidity 80%, and then moisture was released at 40 ° C and relative humidity 20%. As a result, it is found that the allophane membrane complex has a humidity control action The
（実施例１４）
実施例１と同様に作製したアロフェン膜複合体を１３０℃で乾燥した後、温度４０℃、相対湿度４０％における吸湿試験において、吸湿時間に対する吸湿率の変化を評価した。 (Example 14)
After drying the allophane membrane complex produced in the same manner as in Example 1 at 130 ° C., the change of the moisture absorption rate with respect to the moisture absorption time was evaluated in a moisture absorption test at a temperature of 40 ° C. and a relative humidity of 40%.
（比較例５）
また、比較例５として、アロフェン粉体を成形したアロフェン錠剤を作製した。成形機（株式会社菊水製作所、Ｎｏ．８－Ｆ－３）を用い、アロフェン粉体を０．６ＭＰａ～０．８ＭＰａで一軸加圧し、直径：１５ｍｍ、高さ：５．５ｍｍ、重量：１．０ｇのアロフェン錠剤を作製した。比較例５のアロフェン錠剤についても、実施例１４のアロフェン膜複合体と同様の評価を行った。 (Comparative example 5)
Further, as Comparative Example 5, an allophane tablet was prepared by molding allophane powder. Allophane powder was uniaxially pressed at 0.6 MPa to 0.8 MPa using a molding machine (No. 8-F-3, Kikusui Manufacturing Co., Ltd.), diameter: 15 mm, height: 5.5 mm, weight: 1. 0 g of allophane tablets were made. The allophane tablet of Comparative Example 5 was also evaluated in the same manner as the allophane membrane complex of Example 14.
吸湿時間に対して吸湿率をプロットした結果を図１２に示す。実施例１４のアロフェン膜複合体は、比較例５のアロフェン錠剤と比較して、吸湿速度が速い特性を有することが確認できた。 The results of plotting the moisture absorption rate against the moisture absorption time are shown in FIG. It has been confirmed that the allophane membrane complex of Example 14 has faster moisture absorption characteristics as compared to the allophane tablet of Comparative Example 5.
アロフェン膜複合体は、強い基板との密着力と高い自由度（変形性）を持つことに加え、極薄で手軽に鋏やカッターナイフで切断ができるので形状（袋状なども含む）、大きさを自由に選択加工、必要量、枚数なども自由に選ぶことができることから、狭い空間、隙間などを含めたあらゆる空間での使用、及び梱包形状に合わせた形状で使用できる包装材、吸水剤であり、薬、食品、機械装置、ガス体、有機溶媒などの乾燥に用いる。また、吸着及び調湿の特性を活かした利用分野では、皮脂や油を吸着する衛生紙、室内の有害化学分子を吸着し調湿機能も有する壁紙、マスクの内張りに成膜した菌吸着マスク、窓の結露防止膜、曇り防止膜、自動車室内の調湿及び有害成分を吸着する自動車室内用内貼りシート、カーエアコンの内部又は外部又はその両方に装着し、エアーを通過させて不快な臭いを取る吸着フィルター、室内の空調設備に用いる空気清浄膜、液相において魚類から排出されるアンモニアや生臭物質を吸着する魚類飼育用吸着膜、野菜保存シート・袋、成膜時のマスキングにより文字や絵を表現した機能性インテリア、透明なビニールに塗布することで適度な透過性を得られることから機能性プライベートシート及び機能性防犯シート、機能性テープ、機能性保護シート、可燃物質を膜分子内や膜の空隙に貯蔵させた積層型燃料貯蔵膜、更にはイオン及び配位子交換膜、放射能元素除去膜、吸水シート、吸着シート、調湿シートなどが上げられる。 The allophane membrane composite has an extremely thin thickness and can be easily cut with a scissors or a cutter knife, in addition to having strong adhesion with a strong substrate and high freedom (deformability), so it has a shape (including a bag-like shape) and a large size. Because it can be selected freely, the required amount, the number of sheets, etc. can be selected freely, it can be used in any space including narrow spaces, gaps etc., and packaging materials that can be used in the shape according to the packaging shape, water absorbent It is used to dry medicine, food, machinery, gas, organic solvents and so on. Moreover, in the field of application that utilizes the characteristics of adsorption and humidity control, sanitary paper that adsorbs sebum and oil, wallpaper that adsorbs harmful chemical molecules in the room and also has humidity control function, bacteria adsorption mask formed on the lining of mask, window Anti-condensing film, anti-fogging film, inner sheet for car interior that adsorbs humidity control and harmful components in car interior, attached to the inside and / or both of car air conditioner, let air pass and take off unpleasant odor Adsorptive filter, air cleaning film used for air conditioning in the room, adsorption film for fish rearing that adsorbs ammonia and odorous substances discharged from fish in liquid phase, vegetable storage sheet / bag, masking of characters and pictures by film formation Functional private sheet and functional crime prevention sheet, functional tape, function from being able to obtain appropriate transparency by applying to functional interior expressed and transparent vinyl Protective sheets, stacked fuel storage membranes in which combustible substances are stored in membrane molecules and in the pores of membranes, ion and ligand exchange membranes, radioactive element removal membranes, water absorption sheets, adsorption sheets, humidity control sheets, etc. It is raised.
１　製造装置、２　チャンバ、４　ノズル、６　基板駆動装置、１０　アロフェン膜複合体、１１　基材、１２　アロフェン微粒子圧粉体、１３　アロフェン膜、１５　アロフェン微粒子、１７　アロフェン原料微粒子、１９　観察用保護膜、２０　アロフェン膜複合体、２１　基材 Reference Signs List 1 manufacturing apparatus, 2 chambers, 4 nozzles, 6 substrate driving devices, 10 allophane membrane complex, 11 base materials, 12 allophane fine particle compacted powder, 13 allophane membranes, 15 allophane fine particles, 17 allophane raw material fine particles, 19 protective film for observation , 20 allophane membrane complex, 21 base material

Claims (8)

  1. 基材と、平均直径が３．５ｎｍ以上１０ｎｍ以下を備えるアロフェンが前記基材上に堆積したアロフェン膜と、を備え、
    前記基材と前記アロフェン膜との密着力が４Ｎ／１０ｍｍ以上、９０度の曲げ試験を繰り返して前記アロフェン膜が前記基材から剥離する回数が１回以上であることを特徴とするアロフェン膜複合体。     A substrate, and an allophane film in which allophane having an average diameter of 3.5 nm or more and 10 nm or less is deposited on the substrate;
    Allophane film composite characterized in that the adhesion test between the substrate and the allophane film is repeated 4 N / 10 mm or more at a 90 degree bending test and the allophane film peels off the substrate once or more. body.
  2. 前記アロフェン膜は、厚さが５０μｍ以上７０μｍ以下、吸湿率が１０％以上３０％以下、表面硬度がＨ以上を備えることを特徴とする請求項１記載のアロフェン膜複合体。 The allophane film composite according to claim 1, wherein the allophane film has a thickness of 50 μm to 70 μm, a moisture absorption rate of 10% to 30%, and a surface hardness of H or more.
  3. 前記基材は、ガラス、アルミニウム、アルミナ、不織布、ポリエチレンフィルムでコーティングされた不織布又はアルミナシート、シリカ含有ポリエチレンフィルムでコーティングされたアルミナシート、及びＰＥＴシートの群から選ばれる１つであることを特徴とする請求項１に記載のアロフェン膜複合体。 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 allophane membrane complex according to claim 1.
  4. 前記基材は、不織布であり、前記不織布は、２４時間での透湿度が９５００ｇ／ｍ2以上１１００ｇ／ｍ2以下、通気度が１０ｍｌ／ｃｍ2以上２５ｍｌ／ｃｍ2以下、密度が６５ｇ／ｍ2以上８０ｇ／ｍ2以下、厚さが０．１４ｍｍ以上０．２５ｍｍ以下を備えることを特徴とする請求項３に記載のアロフェン膜複合体。 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.
  5. 請求項１乃至４のいずれか１項に記載のアロフェン膜複合体の製造方法において、
    アロフェン原料微粒子を搬送ガスと混合してエアロゾル化し、
    エアロゾル化した原料微粒子を、該搬送ガスと共に、ノズルを通して加速して前記基材の表面に向けて噴射せしめることにより、減圧チャンバ内で前記基材にアロフェン膜を形成することを特徴とするアロフェン膜複合体の製造方法。     In the method for producing an allophane membrane complex according to any one of claims 1 to 4,
    Allophane raw material particles are mixed with carrier gas and aerosolized,
    An allophane film characterized in that an allophane film is formed on the substrate in a decompression chamber by accelerating aerosolized raw material fine particles together with the carrier gas through a nozzle and accelerating them toward the surface of the substrate. Method of manufacturing a complex.
  6. 前記基材が不織布である請求項４に記載のアロフェン膜複合体を備えることを特徴とする吸水シート。 The water absorbing sheet comprising the allophane membrane composite according to claim 4, wherein the base material is a non-woven fabric.
  7. 前記基材が不織布である請求項４に記載のアロフェン膜複合体を備えることを特徴とする吸着シート。 The adsorptive sheet comprising the allophane membrane composite according to claim 4, wherein the base material is a non-woven fabric.
  8. 前記基材が不織布である請求項４に記載のアロフェン膜複合体を備えることを特徴とする調湿シート。 The humidity control sheet comprising the allophane membrane composite according to claim 4, wherein the base material is a non-woven fabric.
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