JP4413252B2 - Nanostructure composite-coated structure and method for producing the same - Google Patents

Description

  In the present invention, a solid substrate surface having an arbitrary shape is densely coated with a nanostructure composite (composite nanofiber or composite nanoparticle) in which a polymer having a polyethyleneimine skeleton and silica are combined on the nanometer order. The present invention relates to a nanostructure composite-covered structure and a method for producing the structure.

  Silicon is the second most abundant existence after oxygen on the earth's crust, and natural quartz, quartz, opal, mica, diatoms, etc. are well-known oxides of silicon. The creation of a silica material having a regular spatial structure or pattern structure is a major research subject in the field of material science, and technological development related to this has progressed dramatically.

  As a method for expressing a certain structure in a silica material, a method in which a molecular organization is used as a template (template) and silica is fixed around the organization is widely used in the field. For this template, a surfactant (for example, see Non-Patent Document 1), a block polymer (for example, see Non-Patent Document 2), a virus, a bacterium (for example, see Non-Patent Document 3), or the like is used. Silica with nano cavities synthesized using these as templates, such as MCM-41 (Mesoporous) series materials, can be applied to catalysts, electronic materials, nanofilters, biotechnology, etc. Is done on a global scale. In particular, with regard to these mesoporous materials, studies have been conducted for more precise control of the structure, and the size and arrangement of the cavities or the control of cavities in spherical silica are being studied.

  On the other hand, in parallel with such control of nanocavities, attention has been paid to a technique for controlling the shape of silica itself from nano to micron to macro scale. This is partly due to the enlightenment of biosilica in ecosystems (see Non-Patent Document 4, for example). Diatoms can be taken up as natural biosilica. Diatoms are composed of silica and have complex and precise shapes and patterns. The construction of silica on the cell membrane of living organisms involves proteins or polypeptides (see, for example, Non-Patent Document 5), but these act as a catalyst for the reaction of depositing and immobilizing silica, or silica. Or provide a scaffold for shape growth. One of the indispensable chemical structures for the formation of such biological biosilica is a long-chain polyamine. The polyamine works by being incorporated into a peptide structure or works together with the polypeptide as a polyamine having a constant molecular weight by itself (see, for example, Non-Patent Document 6).

  As described above, it has been widely known in recent years that a silica source such as silicic acid, sodium silicate or alkoxysilane can be immobilized as silica gel at room temperature in the presence of polyamine. However, since they are usually made by dissolving polyamine in water and sol-gel reaction of silica source in the aqueous solution, even though silica gel can be formed, many of them cannot control the shape of silica gel. The realization of silica gel having a regular structure has been difficult.

  Unlike the above method, the present inventors have used silica nanofibers by using, as a reaction field for silica precipitation, a unique molecular aggregate in which a linear polyethyleneimine composed of a secondary amine is expressed in an aqueous medium. The present inventors have found silica-containing nanostructures having various complex shapes typified by (2) and methods for producing the same (see Patent Documents 1 to 4). In these inventions, when a polymer having a linear polyethyleneimine skeleton is spontaneously associated in water and then mixed with a silane compound of alkoxysilanes in the associated fluid, the silanes are selectively polymerized. The present invention has been completed by finding that a nanostructure in which a polymer and silica are combined is produced by hydrolytic condensation on the surface of the aggregate. This process is highly efficient for controlling the structure of the silica-based nanostructure, but it is only to deposit the silica nanomaterial in the solution.

  There is another important area for technology development through enlightenment of biosilica. That is to form a silica film on the surface of the solid material. The only basic method of mimicking biosilica is to fix polyamines that function as catalysts to the surface of the substrate by adsorption or chemical bonding, and then deposit silica. For example, a molecular residue having radical polymerization initiating ability is immobilized on the surface of gold, and a radical polymerizable monomer having an amino group (for example, N, N-dimethylaminoethyl methacrylate) is radically polymerized to obtain a large number of poly ( N, N-dimethylaminoethyl methacrylate) is formed on the gold surface in the form of a brush, and then a hydrolytic condensation reaction of alkoxysilane is allowed to proceed on the amine polymer brush to form a film composed of a composite of silica and polymer. It has been reported that it can be obtained (for example, see Non-Patent Document 7). The surface of the composite film thus obtained was not a flat structure, but an uneven structure formed by randomly gathering silica particles, and was not precisely patterned. In addition, for example, poly (L-lysine) is used as a polyamine, a copper plate is used as an anode, and planar indium tin oxide (ITO) is used as a cathode, an aqueous poly (L-lysine) solution is added between the two electrodes, and an electric field is applied from the electrode. It is reported that after poly (L-lysine) is adsorbed on the cathode ITO, the ITO is immersed in a silicic acid solution to deposit silica on the ITO surface (for example, Non-Patent Document 8). reference.). The silica on the ITO surface obtained by this method basically shows a scaly structure, but a uniform film cannot be obtained. Therefore, only a few specific places have a dense scaly structure. It was in a state where the flaky silica existed apart. In addition, a glass rod is immersed in a basic polymer solution such as poly (L-lysine), poly (L-lysine-tyrosine), poly (arylamine) hydrochloride, and adsorbed on the surface, and then the glass rod is silicic acid. It has been reported that silica is deposited on the surface of a glass rod by dipping in an aqueous solution (see, for example, Non-Patent Document 9). Although a rough silica film was formed on the surface of the glass rod obtained by this method, there was no feature indicating that a nanostructure was formed, and it was at a level where silica was applied.

  As described above, although polyamines can be fixed on the substrate surface and silica can be deposited thereon, coating with silica having a controlled structure has not yet been achieved. Furthermore, although a metal and glass are used as a base material, there is no silica film construction example which has a regular and complicated structure on the plastic surface. Therefore, development of a structure in which a complex nanostructure composite is constructed on a solid surface of an arbitrary shape and a method for producing the structure are very challenging tasks.

C. T.A. Kresge et al. , Nature, 1992, 359, p. 710 A. Monnier et al. Science, 1993, 261, p. 1299 S. A. Davis et al. , Nature, 1997, 385, p. 420 W. E. G. Muller Ed. , Silicon Biomineralization: Biology-Biotechnology-Molecular Biology-Biotechnology, 2003, Springer N. Kroger et al. Science, 1999, 286, p. 1129 N. Kroger et al. , Proc. Natl. Acad. Sci. USA, 2000, 97, p. 14133 Don Jin Kim et al. , Langmure, 2004, 20: 7904-7906. D. D. Glawe et al. Langmure, 2005, 21, 717720. S. D. Pogula et al. , Langmure, 2007, Vol. 23, 66766683. JP 2005-264421 A JP 2005-336440 A JP 2006-063097 A JP 2007-051056 A

  The problem to be solved by the present invention is a structure in which the surface of a solid substrate of an arbitrary shape is coated with silica, in particular, a polymer that is an organic substance and a silica that is an inorganic substance are combined in a nanometer order. A nanostructure composite-coated structure in which the nanostructure composite spreads over the entire surface of the substrate and forms a complex nanostructure on the substrate as a film that completely covers the substrate, and further An object of the present invention is to provide a structure in which metal ions, metal nanoparticles, and organic dye molecules are contained in the nanostructure composite, and a simple and efficient method for producing these structures.

  The present inventors have already used a crystalline aggregate in which a polymer having a linear polyethyleneimine skeleton grows in an aqueous medium in a self-organizing manner as a reaction field, and hydrolyzes alkoxysilane on the surface of the aggregate in a solution. By condensing decomposingly and precipitating silica, a complex nanosilica structure rich in shape change and a manufacturing method thereof were provided (see Patent Documents 1 to 4). The basic principle of this technique is to spontaneously grow a crystalline aggregate of a polymer containing a polyethyleneimine skeleton in a solution. Once a crystalline aggregate is formed, the dispersion of the crystalline aggregate is then simply used. A silica source is mixed therein, and the deposition of silica is allowed to occur naturally only on the surface of the crystalline aggregate (so-called sol-gel reaction). If the growth of the crystalline association of the polyethyleneimine skeleton-containing polymer in the solution proceeds on the surface of a solid substrate of an arbitrary shape and the layer of the crystalline association of the polymer can be formed on the substrate, the solid group It is considered that a nanostructure having a new interface in which silica and a polymer are combined on a material can be constructed. If this working model is further expanded, even if the layer formed on the solid substrate is not a crystalline aggregate of a polymer, but a stable layer consisting of an amorphous molecular aggregate of a polyethyleneimine skeleton-containing polymer, Similarly, it is considered that a new nanointerface in which the target silica and polymer are combined can be constructed.

  Therefore, the fundamental problem in solving the above problem is only how to form a stable layer (film) of the self-assembled aggregate of the polyethyleneimine skeleton-containing polymer on the surface of the solid substrate. An important feature of a polymer containing a polyethyleneimine skeleton is that it is basic and has a very high polarity. Accordingly, the polyethyleneimine skeleton-containing polymer is a metal substrate, a glass substrate, an inorganic metal oxide substrate, a plastic substrate having a polar surface, a cellulose substrate, a lot of electron acceptor substrates, and Lewis acidic substrates. It has a strong interaction force (adsorption force) with various surfaces such as acidic substrates, polar substrates and hydrogen bonding substrates. Taking advantage of this feature of the polyethyleneimine skeleton-containing polymer, the present inventors contacted (immersed) a molecular substrate solution of a solid substrate surface of an arbitrary shape and a polyethyleneimine skeleton-containing polymer having a constant concentration and a constant temperature to obtain a solution. It was found that the polymer therein was attracted to the surface of the solid substrate, and as a result, a layer composed of molecular aggregates of the polymer could be easily formed over the entire contacted portion of the surface of the solid substrate. Furthermore, by immersing the solid substrate coated with the polymer layer thus obtained in a silica source solution, the solid substrate can be coated with a silica / polymer composite having a complicated nanostructure. As a result, the present invention has been completed.

  That is, the present invention relates to a nanostructure composite-coated structure in which a solid substrate having an arbitrary shape is coated with a nanostructure composite, and the nanostructure composite is composed of a polymer having a polyethyleneimine skeleton and silica. The present invention provides a nanostructure-composite-covered structure characterized by being a composite formed in a metric order, and a method for producing the same.

  In addition, the present invention provides a nanostructure composite-covered structure characterized in that metal ions, metal nanoparticles or organic dye molecules are contained in the nanostructure composite, and a method for producing the same. It is.

  In the nanostructure composite-covered structure of the present invention, a composite containing a polymer and silica is formed on the surface of a solid base material such as metal, glass, inorganic metal oxide, plastic, and cellulose having an arbitrary shape. The structure itself may be in any form such as a complex plane, curved surface, rod shape, tubular shape, etc., and is limited or comprehensive in any of the inside, outside the tube, inside the container, and outside the container. Can be coated. In addition, since the nanostructure composite to be coated uses a polymer layer formed on the base material by contact between the polymer solution having a polyethyleneimine skeleton and the solid base material, only a part of the surface of the solid base material is used. It is easy to select and coat. Regardless of the size of the structure, since the nanostructure composite is formed on the surface, the surface area per unit area (specific surface area) becomes extremely large. Further, since the nanostructure composite on the surface of the solid substrate is basically silica, it can be suitably used in the application technical field related to silica. Furthermore, since it is easy to incorporate various functional parts such as metal ions, metal nanoparticles, or organic dye molecules into the composite, it can be used for various devices that express and use these functions. can do. Specifically, catalyst-provided microreactor, enzyme immobilization device, substance separation and purification device, chip, sensor, photonic device construction, insulator or semiconductor construction, sterilization / sterilization device construction, various micro battery construction, super hydrophilic / Can be used as a super-hydrophobic interface construction, liquid crystal display material member, etc., applied to technology for improving heat resistance, flame retardancy, wear resistance and solvent resistance of plastics, technology for adjusting refractive index of substrate surface, etc. Can be applied to a wide range of industries.

  In the structure of the present invention, the surface of the solid substrate (X) is coated with a nanostructure composite (Y) containing a polymer (A) having a polyethyleneimine skeleton (a) and silica (B). is there. Furthermore, the structure of the present invention also provides a structure characterized in that the nanostructure composite part contains metal ions, metal nanoparticles, or organic dye molecules. Accordingly, the structure of the present invention is composed of a solid substrate, polymer, silica, metal ions, metal nanoparticles, organic dye molecules, and the like. In the present invention, the nanostructure composite (Y) is a composite of a polymer (A) and silica (B), and metal ions, metal nanoparticles, organic dye molecules, etc. used in combination as necessary in nanometer order. It indicates an organic-inorganic composite having a certain shape such as a fiber shape or a particle shape. In addition, as described later, the metal nanoparticles indicate that the metal fine particles are present in a size of the order of nanometers, and need not be completely spherical, but are described as “particles” for convenience. To do. The present invention will be described in detail below.

[Solid substrate]
The solid substrate (X) used in the present invention is not particularly limited as long as the polymer (A) having a polyethyleneimine skeleton (a) described later can be adsorbed. For example, glass, metal, metal oxide, etc. Inorganic material base material, resin (plastic), organic material base material such as cellulose, etc. Furthermore, glass, metal, metal oxide surface etched substrate, resin substrate surface plasma treatment, ozone treatment Can be used.

  Although it does not specifically limit as an inorganic material type glass substrate, For example, glass, such as heat resistant glass (borosilicate glass), soda-lime glass, crystal glass, optical glass which does not contain lead and arsenic, is used suitably. Can do. In the use of a glass substrate, the surface can be used by etching with an alkaline solution such as sodium hydroxide, if necessary.

  Although it does not specifically limit as an inorganic material type metal base material, For example, the base material which consists of iron, copper, aluminum, stainless steel, zinc, silver, gold | metal | money, platinum, or these alloys etc. can be used suitably.

  Although it does not specifically limit as an inorganic material type metal oxide base material, For example, ITO (indium tin oxide), a tin oxide, copper oxide, a titanium oxide, a zinc oxide, an alumina etc. can be used suitably.

  As the resin base material, for example, processed products of various polymers such as polyethylene, polypropylene, polycarbonate, polyester, polystyrene, polymethacrylate, polyvinyl chloride, polyethylene alcohol, polyimide, polyamide, polyurethane, epoxy resin, and cellulose can be used. it can. In the use of various polymers, the surface may be treated with plasma or ozone, or treated with sulfuric acid or alkali, if necessary.

  The shape of the solid substrate (X) is not particularly limited, and may be a flat or curved plate or a film. In particular, a tubular tube, a spiral tube of a tubular tube, a microtube; a container having an arbitrary shape (for example, a spherical shape, a square shape, a triangular shape, a cylindrical shape); an arbitrary shape (for example, a cylindrical shape, (Rectangle, triangle, etc.) A rod or a solid substrate in a fiber state can also be suitably used.

[Polymer having Polyethyleneimine Skeleton (a) (A)]
In the present invention, it is essential to use a polymer (A) having a polyethyleneimine skeleton (a) for the polymer layer formed on the solid substrate (X). The polymer (A) having the polyethyleneimine skeleton (a) may be a linear, star-shaped or comb-shaped homopolymer, or a copolymer having other repeating units. In the case of a copolymer, the molar ratio of the polyethyleneimine skeleton (a) in the polymer (A) is preferably 20% or more from the viewpoint of forming a stable polymer layer. It is more preferable that it is a block copolymer having 10 or more repeating units.

  The polyethyleneimine skeleton (a) may be either branched or linear, but is more preferably a linear polyethyleneimine skeleton having a high ability to form a crystalline aggregate. Whether the polymer is a homopolymer or a copolymer, a stable polymer layer is formed on the substrate (X) when the molecular weight corresponding to the polyethyleneimine skeleton is in the range of 500 to 1,000,000. It is preferable because it can be formed. The polymer (A) having the polyethyleneimine skeleton (a) can be obtained from a commercially available product or a synthesis method already disclosed by the present inventors (see Patent Documents 1 to 4).

  As will be described later, the polymer (A) can be used by dissolving in various solutions. At this time, in addition to the polymer (A) having the polyethyleneimine skeleton (a), the polymer (A) is compatible with the polymer (A). It can be used by mixing with other polymers. Examples of the other polymer include polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, poly (N-isopropylacrylamide), polyhydroxyethyl acrylate, polymethyloxazoline, polyethyloxazoline, and polypropyleneimine. By using these other polymers, the thickness of the nanostructure composite layer on the surface of the resulting structure can be easily adjusted.

[Silica (B)]
A major feature of the substrate surface of the structure obtained by the present invention is that it is a nanostructure composite comprising a polymer and silica. As a silica source required for forming silica (B), for example, alkoxysilanes, water glass, hexafluorosilicon ammonium and the like can be used.

  As the alkoxysilanes, tetramethoxysilane, oligomers of methoxysilane condensates, tetraethoxysilane, oligomers of ethoxysilane condensates can be suitably used. Further, alkyl-substituted alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, etc., 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xylpropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptotriethoxysilane, 3,3 -Trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p -Chloromethylphenyltrimethoxysilane, p-chloromethylphenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane and the like can be used alone or in combination.

  In addition, other silica metal compounds may be mixed with the silica source. For example, tetrabutoxytitanium, tetraisopropoxytitanium, or an aqueous solution of titanium bis (ammonium lactate) dihydroxide stable in an aqueous medium, an aqueous solution of titanium bis (lactate), a propanol / water mixture of titanium bis (lactate), titanium (ethyl) Acetoacetate) diisopropoxide, titanium sulfate, hexafluorotitanium ammonium and the like can be used.

[Metal ion (C)]
The surface of the base material in the structure of the present invention is covered with the nanostructure composite (Y) composed of the polymer (A) having the above-mentioned polyethyleneimine skeleton (a) and silica (B). In this nanostructure composite (Y), the metal ion (C) can be stably taken in, and thus a nanostructure composite-coated structure containing the metal ion (C) can be obtained.

  Since the polyethyleneimine skeleton (a) in the polymer (A) has a strong coordination ability with respect to the metal ion (C), the metal ion (C) is coordinated with the ethyleneimine unit in the skeleton to form a metal. Ion complexes are formed. The metal ion complex is obtained by coordinating a metal ion (C) to an ethyleneimine unit. Unlike a process such as ionic bonding, the metal ion (C) is a cation, an anion, ethylene A complex can be formed by coordination to an imine unit. Accordingly, the metal species of the metal ion (C) is not limited as long as it can coordinate bond with the ethyleneimine unit in the polymer (A), and alkali metal, alkaline earth metal, transition metal, metalloid, lanthanum series Any of a metal, a metal compound of polyoxometalates, etc. may be sufficient, and it may be a single kind or a plurality of kinds may be mixed.

Examples of the alkali metal include Li, Na, K, Cs and the like, and examples of counter ions of the alkali metal ions include Cl, Br, I, NO ₃ , SO ₄ , PO ₄ , ClO ₄ , PF ₆ , Examples thereof include BF ₄ and F ₃ CSO ₃ .

  Examples of the alkaline earth metal include Mg, Ba, and Ca.

As a transition metal-based metal ion, even if it is a transition metal cation (M ^{n +} ), an acid group anion (MO _x ⁿ⁻ ) composed of a bond with oxygen, or an anion composed of a halogen bond ( ML _x ⁿ⁻ ) can also be suitably used. In the present specification, the transition metal refers to Sc, Y in Group 3 of the periodic table, and transition metal elements in Groups 4 to 12 in the 4th to 6th periods.

Examples of transition metal cations include cations of various transition metals (M ^{n +} ), such as Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Ru, Rh, Pd, and Ag. , Cd, W, Os, Ir, Pt, Au, Hg, monovalent, divalent, trivalent or tetravalent cations. Counteranion of these metal cations, Cl, NO 3, _SO 4 or polyoxometalate compound anion, or may be an organic anion of carboxylic _acids. However, for those that are easily reduced by the ethyleneimine skeleton, such as Ag, Au, and Pt, it is preferable to prepare an ionic complex by suppressing the reduction reaction, for example, by adjusting the pH to an acidic condition.

Examples of the transition metal anion include various transition metal anions (MO _x ⁿ⁻ ) such as MnO ₄ , MoO ₄ , ReO ₄ , WO ₃ , RuO ₄ , CoO ₄ , CrO ₄ , VO ₃ , NiO ₄ , UO _2. Anions and the like.

  As the metal ion (C) in the present invention, polyoxometalates in which the transition metal anion is fixed in silica (B) via a metal cation coordinated to an ethyleneimine unit in the polymer (A). It may be in the form of a metal compound. Specific examples of the polyoxometalates include molybdate, tungstate and vanadate in combination with a transition metal cation.

Furthermore, anions (ML _x ⁿ⁻ ) containing various metals, such as AuCl ₄ , PtCl ₆ , RhCl ₄ , ReF ₆ , NiF ₆ , CuF ₆ , RuCl ₆ , In ₂ Cl _6, etc. The coordinated anion can also be suitably used for forming an ion complex.

  Further, examples of the metalloid ions include ions of Al, Ga, In, Tl, Ge, Sn, Pb, Sb, and Bi. Among them, ions of Al, Ga, In, Sn, Pb, and Tl are preferable.

  Examples of the lanthanum metal ions include trivalent cations such as La, Eu, Gd, Yb, and Eu.

[Metal nanoparticles (D)]
As described above, in the present invention, the metal ion (C) can be incorporated into the nanostructure composite (Y) in the structure. Therefore, among these metal ions (C), metal ions that are easily reduced by the reduction reaction are converted into metal nanoparticles (D), whereby the metal nanoparticles (D) are converted into the composite (Y). It can be included.

  Examples of the metal species of the metal nanoparticles (D) include copper, silver, gold, platinum, palladium, manganese, nickel, rhodium, cobalt, ruthenium, rhenium, molybdenum, iron and the like in the composite (Y). These metal nanoparticles (D) may be one kind or two or more kinds. Among these metal species, silver, gold, platinum, and palladium are particularly preferable because the metal ions are spontaneously reduced at room temperature or in a heated state after being coordinated to the ethyleneimine unit.

  The magnitude | size of the metal nanoparticle (D) in a composite_body | complex (Y) is controllable in the range of 1-20 nm. The metal nanoparticles (D) can be fixed to the inside or the outer surface of the nanostructure composite (Y) of the polymer (A) and silica (B).

[Organic dye molecule (E)]
In the present invention, the polyethyleneimine skeleton (a) in the nanostructure composite (Y) covering the structure is composed of a compound having an amino group, a hydroxy group, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, a hydrogen bond, and A physical coupling structure can be formed by electrostatic attraction. Therefore, the organic dye molecule (E) having these functional groups can be contained in the complex (Y).

  As said organic pigment | dye molecule | numerator (E), a monofunctional acidic compound or a polyfunctional acidic compound more than bifunctional can be used suitably.

  Specifically, for example, aromatic acids such as tetraphenylporphyrin tetracarboxylic acid and pyrene dicarboxylic acid, naphthalene disulfonic acid, pyrene disulfonic acid, pyrene tetrasulfonic acid, anthraquinone disulfonic acid, tetraphenyl porphyrin tetrasulfonic acid, phthalocyanine tetra Aromatic or aliphatic sulfonic acids such as sulfonic acid and pipes (PIPES), acid yellow, acid blue, acid red, direct blue, direct yellow, direct red series azo dyes and the like can be mentioned. In addition, a dye having a xanthene skeleton, for example, rhodamine, erythrosine, and eosin dyes can be used.

[Nanostructure composite (Y) containing polymer (A) and silica (B)]
The nanostructure composite (Y) containing the polymer (A) and the silica (B) is basically a composite nanofiber (y1) or composite nanoparticle (y2) of the polymer (A) and the silica (B). Various patterns or morphologies are formed while constituting a state in which the aggregate covers the entire substrate surface. For example, the composite nanofabric (y1) has a turf-like shape (nano turf) in which the long axis of the fiber grows in a substantially vertical direction on the entire surface of the solid substrate, or the long axis of the fiber is relatively long. Rice field shape (nano rice field), composite nanofiber (y1), composite nanofiber (y1) or composite nanoparticle in which the composite nanofiber (y1) is lying down on the entire surface of the substrate. A wide variety of hierarchical structures such as a sponge (nano sponge) in which (y2) forms a network on the entire surface of the substrate can be formed.

  The thickness of the composite nanofiber (y1) of the basic unit in the higher order structure such as the nano turf shape, the nano rice field shape, the nano tatami shape, or the nano sponge shape is in the range of 10 to 100 nm. The length (major axis direction) of the composite nanofiber (y1) in the nano turf shape or the nano rice field shape can be controlled in the range of 50 nm to 10 μm.

  When a network is formed on a solid substrate, that is, when a three-dimensional network structure is constructed over the entire coating layer, the basic structure is composed only of the composite nanofiber (y1). Alternatively, the composite nanoparticle (y2) alone may be used, or both may be combined. At this time, the average particle diameter of the composite nanoparticles (y2) is preferably controlled to 20 nm or less.

  The thickness from the substrate when coating on the solid substrate is related to the aggregate structure of the composite nanofiber (y1) and / or composite nanoparticle (y2), but can be varied in the range of about 50 nm to 20 μm. . In the nano-turf shape, the composite nanofiber (y1) has a strong tendency to stand up straight, the length of the fiber basically constitutes the thickness, and the length of each individual fiber is fairly uniform. It is a feature. In the nano rice field, the composite nanofiber (y2) has a strong tendency to extend obliquely, and the thickness of the coating layer is smaller than the length of the fiber. Further, the thickness of the nano rice field layer is characterized by being determined by the overlapping state of the composite nanofiber (y2). The thickness of the nanosponge-like layer is characterized in that it is determined by the degree to which the composite nanofiber (y2) swells with a complex entanglement having regularity. When a network is formed, the thickness is determined by the overlapping state, the existence ratio of the composite nanofiber (y1) and the composite nanoparticle (y2), and the like.

  In the nanostructure composite (Y), the component of the polymer (A) can be adjusted at 5 to 30% by mass. By changing the content of the polymer (A) component, the aggregate structure (higher order structure) can be changed.

  In addition, when a metal ion (C), a metal nanoparticle (D), or an organic dye molecule (E) is contained in the nanostructure composite (Y), it is possible to control the higher order structure depending on the type. It is. Even in this case, the basic unit is the composite nanofiber (y1) and / or the composite nanoparticle (y2) as described above, which are combined to form a complex shape.

  The amount of the metal ion (C) incorporated when the metal ion (C) is incorporated is preferably prepared in the range of 1/4 to 1/200 equivalent per 1 equivalent of the ethyleneimine unit in the polymer (A). By changing this ratio, the thickness of the coating layer can be changed. In addition, the coating layer at this time may develop color depending on the metal species.

  The amount of metal nanoparticles (D) incorporated when incorporating metal nanoparticles (D) should be adjusted within a range of 1/4 to 1/200 equivalents per 1 equivalent of ethyleneimine units in polymer (A). Preferably, the thickness of the coating layer can be changed by changing this ratio. In addition, the coating layer at this time may develop color depending on the metal species.

  The amount of the organic dye molecule (E) incorporated when the organic dye molecule (E) is incorporated should be prepared in the range of 1/2 to 1/1200 equivalent per 1 equivalent of the ethyleneimine unit in the polymer (A). Preferably, the thickness and shape pattern of the coating layer can be changed by changing this ratio.

  Moreover, 2 or more types of a metal ion (C), a metal nanoparticle (D), and an organic pigment | dye molecule | numerator (E) can also be taken in into a nanostructure composite_body | complex (Y) simultaneously.

[Method for producing nanostructure composite-coated structure]
The method for producing a structure of the present invention comprises a solution of a polymer (A) having a polyethyleneimine skeleton (a), a mixed solution of a polymer (A) having a polyethyleneimine skeleton (a) and a metal ion (C), polyethyleneimine A mixed solution of a polymer (A) having a skeleton (a) and an organic dye molecule (E), or a polymer (A) having a polyethyleneimine skeleton (a), a metal ion (C), and an organic dye molecule (E). After bringing the mixed solution into contact with the surface of the solid substrate (X), the substrate (X) is taken out and used together with the polymer (A) having a polyethyleneimine skeleton (a) on the surface of the substrate (X). Step (1) for obtaining a base material adsorbed with a polymer layer composed of metal ions (C) and / or organic dye molecules (D), a base material adsorbed with the polymer layer, and a silica source liquid (B ′) Contact Due to the catalytic function of the polyethyleneimine skeleton (a) in the polymer layer adsorbed on the substrate surface, silica (B) is deposited thereon to form a nanostructure composite (Y) and coat the substrate. A manufacturing method comprising the step (2). By this method, a nanointerface consisting of polymer (A) and silica (B), a nanointerface consisting of polymer (A) / metal ion (C) / silica (B), polymer (A) on the surface of solid substrate (X) ) / Organic dye molecule (E) / silica (B), a nano-interface coating layer can be easily formed.

  As the polymer (A) having the polyethyleneimine skeleton (a) used in the step (1), the aforementioned polymer can be used. In addition, the solvent that can be used for obtaining the solution of the polymer (A) is not particularly limited as long as the polymer (A) can be dissolved, and examples thereof include water, organic solvents such as methanol and ethanol, These mixed solvents can be used as appropriate.

  The concentration of the polymer (A) in the solution is not particularly limited as long as the polymer layer can be formed on the solid substrate (X), but the desired pattern formation and the density of the polymer adsorbed on the substrate surface are increased. In this case, the range is preferably 0.5% by mass to 50% by mass, and more preferably 5% by mass to 50% by mass.

  In the solution of the polymer (A) having a polyethyleneimine skeleton (a), the above-mentioned other polymers that are soluble in the solvent and compatible with the polymer (A) can be mixed. The mixing amount of the other polymer may be higher or lower than the concentration of the polymer (A) having the polyethyleneimine skeleton (a).

  In the case of forming a coating layer composed of the nanostructure composite (Y) containing the metal ion (C), the metal ion (C) is added to the solution of the polymer (A) having the polyethyleneimine skeleton (a). Mix. The concentration of the metal ion (C) is preferably adjusted to ¼ equivalent or less of the ethyleneimine unit in the polyethyleneimine skeleton (a).

  Moreover, when forming the coating layer which consists of nanostructure composite_body | complex (Y) containing an organic pigment | dye molecule | numerator (E), the said organic pigment | dye molecule | numerator (in the solution of the polymer (A) which has a polyethyleneimine skeleton (a) E) is mixed. The concentration of the organic dye molecule (E) is preferably adjusted to ½ equivalent or less of the ethyleneimine unit in the polyethyleneimine skeleton (a).

  Moreover, in order to produce a polymer layer in a process (1), a solid base material (X) is made to contact with the solution of a polymer (A). As the contact method, it is preferable to immerse the desired solid substrate (X) in the solution of the polymer (A).

  In the dipping method, the substrate and the solution can be brought into contact with each other in such a manner that the substrate (non-container shape) is placed in the solution or the solution is placed in the substrate (container shape) depending on the state of the substrate. During the immersion, the temperature of the polymer (A) solution is preferably in a heated state, and a temperature of about 50 to 90 ° C. is suitable. The time for bringing the solid substrate (X) into contact with the solution of the polymer (A) is not particularly limited, and is preferably selected within a few seconds to 1 hour according to the material of the substrate (X). When the material of the base material has a strong binding ability with polyethyleneimine, for example, it may be several seconds to several minutes for glass, metal, etc. good.

  After contacting the solid substrate (X) with the polymer (A) solution, the substrate is taken out of the polymer (A) solution and allowed to stand at room temperature (around 25 ° C.). A body layer is formed on the surface of the substrate (X). Alternatively, the substrate (X) is taken out from the solution of the polymer (A), and then immediately put into distilled water at 4 to 30 ° C. or an aqueous ammonia solution at a room temperature to a freezing temperature, whereby the spontaneous polymer (A) An aggregate layer may be formed.

  As a method of contacting the surface of the solid substrate (X) with the solution of the polymer (A), for example, a method such as printing or printing with a jet printer can be used in addition to coating with a spin coater, bar coater, applicator or the like. In particular, when the contact is made in a fine pattern, a method using a jet printer is suitable.

  In the step (2), the polymer layer formed in the step (1) and the silica source liquid (B ′) are brought into contact with each other to deposit silica (B) on the surface of the polymer layer, and the polymer (A) and silica (B). And a nanostructure composite (Y) is formed. Even when the polymer layer contains a metal ion (C) and / or an organic dye molecule (E), the target nanostructure composite (Y) can be formed by precipitating silica (B) by the same method. .

  As the silica source liquid (B ′) used at this time, the above-mentioned various silica source aqueous solutions, alcohol solvents, for example, aqueous organic solvent solutions such as methanol, ethanol and propanol, or mixed solvents of these with water A solution can be used. Moreover, the water glass aqueous solution which adjusted the pH value to the range of 9-11 can also be used. The silica source liquid (B ′) to be used can be mixed with a metal alkoxide other than silica.

  Moreover, the alkoxysilane compound as a silica source can be used even in a solvent-free bulk liquid.

  As a method for bringing the solid substrate adsorbed with the polymer layer into contact with the silica source liquid (B ′), an immersion method can be preferably used. It is sufficient that the immersion time is 5 to 60 minutes, but the time can be further increased as necessary. The temperature of the silica source liquid (B ′) may be room temperature or a heated state. In the case of heating, it is desirable to set the temperature to 70 ° C. or lower in order to regularly deposit silica (B) on the surface of the solid substrate (X).

  By selecting the type and concentration of the silica source, the structure of the nanostructure composite (Y) of the precipitated silica (B) and the polymer (A) can be adjusted. Depending on the purpose, the type of the silica source It is preferable to select an appropriate concentration.

  Polyethyleneimine can reduce noble metal ions such as gold, platinum, silver, palladium, etc. to metal nanoparticles. Therefore, by passing the structure coated with the nanostructure composite (Y) obtained in the above step with the aqueous solution of the noble metal ion, the noble metal ion is converted into the nanostructure composite ( Y) can be converted into metal nanoparticles (D), and a nanostructure composite-coated structure having metal nanoparticles (D) can be obtained.

  In the step (3), a dipping method can be preferably used as the method of contacting with an aqueous solution of noble metal ions. As the aqueous solution of noble metal ions, aqueous solutions of chloroauric acid, sodium chloroaurate, chloroplatinic acid, sodium chloroplatinate, silver nitrate and the like can be suitably used, and the aqueous solution concentration of noble metal ions is 0.1 to 5 mol. % Is preferred.

  The temperature of the aqueous solution of noble metal ions is not particularly limited, and may be in the range of room temperature to 90 ° C. However, in order to promote the reduction reaction, it is preferable to use a heated aqueous solution of 50 to 90 ° C. Moreover, the time for immersing the structure in the aqueous solution of metal ions may be 0.5 to 3 hours, and about 30 minutes is sufficient when immersed in the heated aqueous solution.

  In the case of a metal ion that is difficult to reduce with polyethyleneimine alone, the metal ion (C) in the structure having the metal ion (C) obtained above is reduced with a reducing agent, particularly a low molecular weight reducing agent solution or hydrogen. By combining the step (4) of contacting with gas and reducing the metal ion (C), a nanostructure composite-covered structure containing the metal nanoparticles (D) can be obtained.

  Examples of the reducing agent that can be used at this time include ascorbic acid, aldehyde, hydrazine, sodium borohydride, ammonium borohydride, hydrogen, and the like. When reducing a metal ion using a reducing agent, the reaction can be performed in an aqueous medium, a method of immersing a structure containing the metal ion (C) in a reducing agent solution, or hydrogen gas A method of leaving in an atmosphere can be used. At this time, the temperature of the reducing agent aqueous solution may be in the range of room temperature to 90 ° C., and the concentration of the reducing agent is preferably 1 to 5 mol%.

  The metal species of the metal ion (C) that can be applied to the step (4) is not particularly limited, but may be copper, manganese, chromium, nickel, tin, vanadium, or palladium because the reduction reaction proceeds quickly. preferable.

  When the coated structure is immersed in the reducing agent aqueous solution, the temperature of the reducing agent aqueous solution is suitable even at room temperature or in a heated state of 90 ° C. or less, and a concentration of the reducing agent of about 1 to 5% is sufficient.

  Various structures obtained by the above-described method can be used for various applications described above by removing the solvent and water by leaving them at room temperature (25 ° C.) to about 60 ° C.

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” represents “mass%”.

[Shape analysis of nanostructures by scanning electron microscope]
The isolated and dried nanostructure was fixed to a sample support with a double-sided tape, and observed with a surface observation device VE-9800 manufactured by Keyence.

Synthesis example 1
<Synthesis of linear polyethyleneimine (L-PEI)>
3 g of commercially available polyethyloxazoline (number average molecular weight 50,000, average polymerization degree 5,000, manufactured by Aldrich) was dissolved in 15 mL of 5 mol / L hydrochloric acid. The solution was heated to 90 ° C. in an oil bath and stirred at that temperature for 10 hours. Acetone 50 mL was added to the reaction solution to completely precipitate the polymer, which was filtered and washed three times with methanol to obtain a white polyethyleneimine powder. When the obtained powder was identified by ¹ H-NMR (heavy water, manufactured by JEOL Ltd., AL300, 300 MHz), the peak derived from the side chain ethyl group of polyethyloxazoline was 1.2 ppm (CH ₃ ) and 2. It was confirmed that 3 ppm (CH ₂ ) disappeared completely. That is, it was shown that polyethyloxazoline was completely hydrolyzed and converted to polyethyleneimine.

  The powder was dissolved in 5 mL of distilled water, and 50 mL of 15% aqueous ammonia was added dropwise to the solution while stirring. The mixture was allowed to stand overnight, and then the precipitated polymer aggregate powder was filtered, and the polymer aggregate powder was washed three times with cold water. The crystal powder after washing was dried in a desiccator at room temperature to obtain linear polyethyleneimine (L-PEI). The yield was 2.2 g (including crystal water). In polyethyleneimine obtained by hydrolysis of polyoxazoline, only the side chain reacts and the main chain does not change. Therefore, the polymerization degree of L-PEI is the same as 5,000 before hydrolysis.

Synthesis example 2
<Synthesis of star-shaped polyethyleneimine (B-PEI) centered on benzene ring>
Jin, J .; Mater. Chem. , 13, 672-675 (2003), a star-shaped polymethyloxazoline in which six polymethyloxazoline arms were bonded to the center of the benzene ring as a precursor polymer was synthesized as follows.

Put 0.021 g (0.033 mmol) of hexakis (bromomethyl) benzene as a polymerization initiator in a test tube set with a magnetic stirrer, attach a three-way cock to the test tube, and then put it in a vacuum state. Was replaced with nitrogen. Under a nitrogen stream, 2.0 ml (24 mmol) of 2-methyl-2-oxazoline and 4.0 ml of N, N-dimethylacetamide were sequentially added from the inlet of the three-way cock using a syringe. When the test tube was heated to 60 ° C. on an oil bath and kept for 30 minutes, the mixture became transparent. The transparent mixture was further heated to 100 ° C. and stirred at that temperature for 20 hours to obtain a precursor polymer. From this mixture the ¹ H-NMR measurement of the liquid, the conversion of monomer is 98 mol%, the yield was 1.8 g. When the average degree of polymerization of the polymer was estimated based on this conversion, the average degree of polymerization of each arm was 115. Moreover, in the molecular weight measurement by GPC, the mass average molecular weight of the polymer was 22,700, and the molecular weight distribution was 1.6.

Using this precursor polymer, polymethyloxazoline was hydrolyzed in the same manner as in Synthesis Example 1 to obtain star-shaped polyethyleneimine B-PEI in which 6 polyethyleneimines were bonded to the benzene ring core. ^{As a result of 1} H-NMR (TMS external standard, heavy water) measurement, it was confirmed that the peak of 1.98 ppm derived from the side chain methyl of the precursor polymer before hydrolysis completely disappeared.

  The powder was dissolved in 5 mL of distilled water, and 50 mL of 15% aqueous ammonia was added dropwise to the solution while stirring. The mixture was allowed to stand overnight, and then the precipitated crystal powder was filtered, and the crystal powder was washed three times with cold water. The washed crystal powder was dried in a desiccator at room temperature (25 ° C.) to obtain star-shaped polyethyleneimine (B-PEI) in which six polyethyleneimines were bonded to the benzene ring core. The yield was 1.3 g (including crystal water).

Synthesis example 3
<Synthesis of Porphyrin-Centered Star Polyethylenimine (P-PEI)>
Jin et al. , J .; Porphyrin & Phthalocyanine, 3, 60-64 (1999); Jin, Macromol. Chem. Phys. , 204, 403-409 (2003), a precursor polymer, a porphyrin-centered star-type polymethyloxazoline, was synthesized as follows.

After replacing a 50 ml two-necked flask equipped with a three-way cock with argon gas, 0.0352 g of tetra (p-iodomethylphenyl) porphyrin (TIMPP) and 8.0 ml of N, N-dimethylacetamide were added at room temperature. Stir to dissolve TIMPP completely. To this solution, 3.4 ml (3.27 g) of 2-methyl-2-oxazoline corresponding to 1280 times the number of moles of porphyrin was added, and then the temperature of the reaction solution was brought to 100 ° C. and stirred for 24 hours. The reaction solution temperature was lowered to room temperature, 10 ml of methanol was added, and the mixture solution was concentrated under reduced pressure. The residue was dissolved in 15 ml of methanol and the solution was poured into 100 ml of tetrahydrofuran to precipitate the polymer. In the same manner, the polymer was re-precipitated, and after suction filtration, the obtained polymer was put into a desiccator in which P ₂ O ₅ was placed and sucked and dried with an aspirator for 1 hour. Furthermore, the pressure was reduced with a vacuum pump, and the precursor polymer (TPMO-P) was obtained by drying under vacuum for 24 hours. The yield was 3.05 g, and the yield was 92.3%.

The number average molecular weight by GPC (HLC-8000, manufactured by Tosoh Corporation) of the obtained precursor polymer (TPMO-P) was 28,000, and the molecular weight distribution was 1.56. Further, the ^{1 H-NMR,} processing of calculating the integral ratio of the pyrrole ring protons of the porphyrin in polymer core ethylene protons in the polymer arm, average degree of polymerization of each arm was 290. Therefore, the number average molecular weight by ¹ H-NMR was estimated to be 99,900. ^{The fact that the} number average molecular weight value by ¹ H-NMR greatly exceeds the number average molecular weight value by GPC is consistent with a general feature in star polymers.

Using this precursor polymer, polymethyloxazoline was hydrolyzed in the same manner as in Synthesis Example 1 to obtain star-shaped polyethyleneimine (P-PEI) in which four polyethyleneimines were bonded to the porphyrin center. ¹ H-NMR (TMS external standard, heavy water) As a result of the measurement, the peak of 1.98ppm derived from the side chain methyl of the precursor polymer before hydrolysis completely disappeared.

Examples 1-1 to 1-4
[Structure in which inner wall of glass tube is coated with polymer / silica nanostructure composite]
Polymer L-PEI obtained in Synthesis Example 1 was added to distilled water and heated to 90 ° C. to prepare a 4% aqueous solution. After connecting a glass tube made of soda lime (inner diameter 1 mm, length 5 cm) and a syringe with a rubber tube, sucking the heated polymer aqueous solution up to a certain standard in the glass tube, and then allowing it to stand for 30 seconds The polymer aqueous solution was discharged by a pushing force of a syringe. By this operation, an L-PEI polymer layer was formed on the inner wall of the glass tube. The glass tube was allowed to stand at room temperature for 5 minutes, and then the glass tube was immersed in various silica source solutions described in Table 1 for 30 minutes. After the glass tube was taken out and the inner wall of the glass tube was washed with ethanol, it was dried at room temperature. After this operation, a light blue reflected color was seen on the glass tube.

  The glass tube end obtained through the above process was slightly crushed, and the fragments were observed with SEM. 1-4 show the results of SEM photographs of the inner surface of the glass tube produced with different silica source solutions. In either case, a dense array film having nanofibers as a unit structure was formed on the inner wall. For comparison, a glass tube without a polymer layer was immersed in a silica source solution, but nothing was observed.

Footnotes in Table 1 MS51: Tetramethoxysilane tetramer (manufactured by Colcoat)
MS53: Tetramethoxysilane hexamer (manufactured by Colcoat)

Examples 2-1 to 2-3
[Structure in which inner wall of glass tube is coated with polymer / silica nanostructure composite]
In Example 1, a glass inner wall was used in the same manner as in Example 1 except that a soda-lime glass tube (inner diameter 6 mm, length 5 cm) was used instead of a soda-lime glass tube (inner diameter 1 mm, length 5 cm). A structure coated with was obtained.

  The glass tube end obtained through the above process was slightly crushed, and the fragments were observed with SEM. 5 to 7 show the results of SEM photographs of the inner surface of the glass tube produced with different silica source solutions. In either case, a dense array film having nanofibers as a unit structure was formed on the inner wall.

Footnotes in Table 2 TMOS: Tetramethoxysilane

Example 3
[Structure in which inner wall of glass tube is coated with polymer / porphyrin / silica nanostructure composite]
4.5 mg of tetra (sulfonate phenyl) porphyrin was dissolved in 2 g of distilled water, 60 mg of L-PEI was added to the solution, and the mixture was heated to 90 ° C. to prepare a mixed solution. The molar ratio of the (CH ₂ CH ₂ NH) unit of the polymer in the solution to the porphyrin is 300/1. This solution was sucked into a glass tube (inner diameter: 6 mm, length: 5 cm) in the same manner as in Example 1, and allowed to stand for 30 seconds, and then the solution was extruded. The glass tube was allowed to stand at room temperature for 5 minutes, and then immersed in a mixed solution of MS-51 / water / isopropyl alcohol (0.2 / 3/3 volume ratio) for 20 minutes. After the glass tube was taken out and the inner wall of the glass tube was washed with ethanol, it was dried at room temperature. After this operation, a light purple-colored porphyrin-derived color was visible in the glass tube.

  When the glass tube was observed with a fluorescence microscope (Olympus BX-60, manufactured by Olympus Corporation), intense red fluorescence appeared. This red fluorescence originates from porphyrin residues being incorporated into the coating layer. The glass tube end obtained through the above process was slightly crushed, and the fragments were observed with SEM. The results are shown in FIG. From the photographic image, it was confirmed that it was covered with a band-like nanofiber having a width of around 100 nm.

Examples 4-1 to 4-4
[Structure in which inner wall of glass tube is coated with polymer / copper ion / silica nanostructure composite]
A certain amount of copper nitrate was dissolved in distilled water to prepare a Cu (NO ₃ ) ₂ aqueous solution having a concentration of 0.014 mol%. 60 mg of the polymer (L-PEI) is added to a certain amount of the aqueous solution, and a mixed solution in which the molar ratio of (CH ₂ CH ₂ NH) / Cu is 50/1, 100/1, 200/1, 600/1 Was prepared. These mixed solutions were heated at 90 ° C., and the inner surface of the glass tube was coated with the nanostructure composite in the same manner as in Example 3 above.

The glass tube end obtained through the above process was slightly crushed, and the fragments were observed with SEM. The results are shown in FIGS. FIG. 13 shows a photograph of only the coating layer formed with the (CH ₂ CH ₂ NH) / Cu molar ratio. It was confirmed that the thickness of the coating layer increased from 200 nm to about 1000 nm as the (CH ₂ CH ₂ NH) / Cu molar ratio increased (copper ion content decreased).

Footnotes in Table 3:
IPA: isopropyl alcohol

Example 5
[Structure in which inner wall of glass tube is coated with polymer / gold nanoparticles / silica nanostructure composite]
The glass tube, which is the structure produced in Example 1-1, was immersed in 2 mL of an aqueous solution (1%) of NaAuCl ₄ .2H ₂ O and heated at 80 ° C. for 1 hour. The glass tube was taken out, washed with distilled water and ethanol in this order, and then dried at room temperature. A thin wine-red color appeared in the glass tube thus obtained. This wine red color is derived from plasmon absorption indicating the presence of gold nanoparticles in the layer covering the inner wall of the glass tube. Plasmon absorption derived from gold nanoparticles having a peak top of 520 nm was also observed from a reflection spectrum (manufactured by Hitachi, Ltd., UV-3500). From this, it can be seen that gold nanoparticles having a size of several nanometers were formed in the coating layer.

  In FIG. 14, the SEM photograph of the structure in which the gold nanoparticle was contained was shown. It was confirmed that even if gold nanoparticles were formed in the coating layer, no structural change occurred in the nanofiber, which is the basic unit of the nanostructure composite.

Example 6
[Structure in which inner wall of polystyrene test tube is coated with polymer / silica nanostructure composite]
6 mL of concentrated sulfuric acid was added to a commercially available polystyrene test tube (16 × 100 mm, 10 mL volume), and the mixture was stirred with a shaker at room temperature for 3 hours. After removing the concentrated sulfuric acid solution, the test tube was washed with distilled water and methanol. After adding 6 mL of an aqueous solution of 3% L-PEI (80 ° C.) to the dried test tube, the entire aqueous solution was taken out after 30 seconds, and the test tube was allowed to stand at room temperature for 5 minutes. Thereafter, 6 mL of a mixed solution of silica source (MS51 / distilled water / IPA = 0.5 / 3/3 volume ratio) was added to the test tube and allowed to stand at room temperature for 20 minutes. The liquid was taken out, the inside of the test tube was washed with ethanol, and dried at room temperature to obtain a structure. Using the fragments of the obtained structure, SEM observation of the inner wall portion was performed. FIG. 15 shows a photograph of the interface portion (lateral surface) composed of the fragment surface, polystyrene, and the coating layer.

Example 7
[Structure in which polystyrene rod surface is coated with polymer / silica nanostructure composite]
A polystyrene rod having a thickness of about 1.8 mm was immersed in a concentrated sulfuric acid solution for 3 hours, then the surface was washed with water and methanol, and dried at room temperature for 5 minutes. Thereafter, the polystyrene rod was immersed in a 4% aqueous solution of L-PEI (80 ° C. solution) and allowed to stand for 30 seconds. The rod was taken out and allowed to stand at room temperature for 5 minutes, and then applied to a mixed liquid of silica source (MS51 / distilled water / IPA = 0.5 / 3/3 volume ratio), and then allowed to stand at room temperature for 20 minutes. The rod was taken out of the liquid, the surface was washed with ethanol, and dried at room temperature to obtain a rod-like structure. The surface of the obtained rod was observed with SEM. FIG. 16 shows a structure photograph of the nanofiber covering the rod surface. From the figure, it was confirmed that the entire surface of the rod was covered with a nanostructure composite having nanofibers as basic units.

Example 8
[Structure in which polystyrene plate surface is coated with polymer / silica nanostructure composite]
A 2 × 2 cm polystyrene plate was immersed in a concentrated sulfuric acid solution for 3 hours, and then the surface was washed with water and methanol and dried at room temperature for 5 minutes. Thereafter, the polystyrene plate was immersed in a 4% aqueous solution of L-PEI (80 ° C.) and allowed to stand for 30 seconds. The plate was taken out and allowed to stand at room temperature for 5 minutes, then applied to a silica source mixture (MS51 / water / IPA = 0.5 / 3/3 volume ratio) and then allowed to stand at room temperature for 20 minutes. The plate was taken out from the liquid, the surface was washed with ethanol, and dried at room temperature to obtain a plate-like structure. The surface of the obtained plate was observed with SEM. FIG. 17 is a structural photograph of nanofibers covering the plate surface. It was confirmed that the surface of the plate was a "nano rice field" like rice ears flowing in the wind.

Example 9
[Structure in which copper plate surface is coated with polymer / silica nanostructure composite]
A 1 × 1 cm size copper plate was dipped in a 4% aqueous solution of L-PEI (80 ° C. solution) and allowed to stand for 30 seconds. The plate was taken out and allowed to stand at room temperature for 5 minutes, after being put on a mixed solution of silica source (MS51 / water / IPA = 0.5 / 3/3), and then allowed to stand at room temperature for 20 minutes. The plate was taken out from the liquid, the surface was washed with ethanol, and dried at room temperature to obtain a plate-like structure. The surface of the obtained plate was observed with SEM. In FIG. 18, it was confirmed that the copper plate surface was covered with a nanostructure composite having nanofibers as basic units. From the low-magnification photograph, it was confirmed that the entire coating layer was composed of nanofibers although there were grains on the surface.

Example 10
[Structure in which inner wall of glass tube is coated with star polymer / silica nanostructure composite]
In Example 1-1, a glass tube having an inner diameter of 6 mm was used, the polymer was B-PEI obtained in Synthesis Example 2, and the silica source liquid was further (TMOS / distilled water = 1/1 volume ratio). A structure was obtained in the same manner as in Example 1-1 except that it was used. The obtained glass tube end was crushed a little, and the surface of the broken piece was observed with SEM. FIG. 19 shows a surface photograph of the inner wall of the glass tube. From the SEM observation photograph, it was confirmed that high-density nanofibers grew on the inner wall of the glass tube.

Example 11
[A structure in which the inner wall of a glass tube is coated with a porphyrin star polymer / silica nanostructure composite]
In Example 10, a structure was obtained in the same manner as in Example 10 except that P-PEI obtained in Synthesis Example 3 was used as the polymer. The obtained glass tube end was crushed a little, and the surface of the broken piece was observed with SEM. FIG. 20 shows a surface photograph of the inner wall of the glass tube. From the SEM observation photograph, it was confirmed that the tips of the nanofibers lined up were rounded particles.

Example 12
[Structure with glass plate surface covered with polymer / silica nanostructure composite]
A 2 × 2 cm soda lime glass plate was immersed in an aqueous solution of 4% L-PEI (80 ° C. solution) and allowed to stand for 30 seconds. The plate was taken out and allowed to stand at room temperature for 5 minutes, and then immersed in a mixed solution of silica source (MS51 / distilled water / IPA = 0.5 / 3/3 volume ratio) at room temperature for 20 minutes. The plate was taken out from the liquid, the surface was washed with ethanol, and dried at room temperature to obtain a structure. The surface of the obtained plate was observed with SEM. FIG. 21 shows a structural photograph showing that the basic unit of the nanostructure composite covering the plate surface is a nanofiber. From this photograph, it was confirmed that the nanostructure composite on the plate surface formed a network with a horizontal line.

Example 13
[Structure in which inner wall of glass tube is coated with polymer / silica nanostructure composite]
A commercially available multi-branched polyethyleneimine (SP200, manufactured by Nippon Shokubai Co., Ltd.) was added to distilled water to prepare a 4% aqueous solution. A glass tube (inner diameter 6 mm, length 5 cm) made of soda lime and a syringe are connected with a rubber tube, and the polymer aqueous solution is sucked up to a certain standard in the glass tube, and then left to stand for 30 seconds. Was discharged by the pushing force of the syringe. By this operation, a polymer adsorption layer was formed on the inner wall of the glass tube. The glass tube was allowed to stand at room temperature for 5 minutes, and then immersed in a silica source solution (TMOS / distilled water = 1/1 volume ratio) for 30 minutes. The glass tube was taken out and the inner wall of the glass tube was washed with ethanol and then dried at room temperature to obtain a structure. The obtained glass tube end was crushed a little, and the surface of the broken piece was observed with SEM. FIG. 22 shows a surface photograph of the inner wall of the glass tube. From the SEM observation photograph, it was confirmed that about 20 nm nanoparticles spread densely on the entire inner wall of the glass tube to form a network.

Example 14
[Structure in which inner wall of glass tube is coated with polymer / copper nanoparticles / silica nanostructure composite]
The glass tube coated on the inner wall with the nanostructure composite containing copper ions obtained in Example 4-1 was immersed in 6 mL of 1% aqueous solution of ammonium borohydride and allowed to stand at room temperature for 3 hours. The reduction reaction was performed. After washing the sample tube in distilled water and ethanol solution, the absorption spectrum was measured with a diffuse reflection spectrometer. Absorption at 630 nm in the copper ion state disappeared, and plasmon absorption derived from copper nanoparticles appeared at 590 nm instead. This suggests that copper ions were converted into copper nanoparticles, and the copper nanoparticles were included in the composite covering the inner wall of the glass tube.

It is a scanning electron micrograph of the structure obtained in Example 1-1. a: Photograph of broken glass tube b: Photograph from lateral direction (interface between glass and composite) c: Enlarged view (observation of nanofiber) It is a scanning electron micrograph of the structure obtained in Example 1-2. a: Photograph of broken glass tube b: Partial enlarged view of a c: Partial expanded view of b It is a scanning electron micrograph of the structure obtained in Example 1-3. a: Photograph of broken glass tube b: Photograph from the lateral direction (interface between glass and composite) c: Enlarged view (observation from directly below, surface of composite) d: Enlarged view of c It is a scanning electron micrograph of the structure obtained in Example 1-4. a: Photograph of broken glass tube b: Photograph from lateral direction (interface between glass and composite) c: Enlarged view (observation of nanofiber) It is a scanning electron micrograph of the structure obtained in Example 2-1. a: Photograph of broken glass tube b: Enlarged view of a c: Enlarged view of b d: Enlarged view of the composite surface It is a scanning electron micrograph of the structure obtained in Example 2-2. a: Photograph of broken glass tube b: Photograph from lateral direction (interface between glass and composite) c: Enlarged view in the lateral direction d: Enlarged view of the surface portion of c It is a scanning electron micrograph of the structure obtained in Example 2-3. a: Photograph of broken glass tube b: Enlarged view of the surface c: Enlarged view in the horizontal direction d: Enlarged view of a part of c 4 is a scanning electron micrograph of the structure obtained in Example 3. a: Photograph of broken glass tube b: Enlarged view of the surface of a c: Enlarged view of b d: Enlarged view of a part of c It is a scanning electron micrograph of the structure obtained in Example 4-1. a: Photograph of broken glass tube b: Enlarged view of the surface of a c: Enlarged view of b d: Enlarged view in the horizontal direction It is a scanning electron micrograph of the structure obtained in Example 4-2. a: Photograph of broken glass tube b: Enlarged view of the surface of a c: Enlarged view of b d: Enlarged view in the horizontal direction It is a scanning electron micrograph of the structure obtained in Example 4-3. a: Photograph of broken glass tube b: Enlarged view of the surface of a c: Enlarged view of b d: Enlarged view in the horizontal direction It is a scanning electron micrograph of the structure obtained in Example 4-4. a: Photograph of broken glass tube b: Enlarged view of the surface of a c: Enlarged view of b d: Enlarged view in the horizontal direction 4 is a scanning electron micrograph in the horizontal direction of the structure obtained in Example 4. FIG. (CH ₂ CH ₂ NH) / Cu = 50/1 (a), 100/1 (b), 200/1 (c), 600/1 (d) It is the photograph of the real thing of the structure obtained in Example 5, and a scanning electron micrograph. a: Photograph of broken glass tube b: Enlarged view of the surface of a 6 is a scanning electron micrograph of the structure obtained in Example 6. FIG. a: Photograph of broken glass tube b: Enlarged view of the surface of a c: Enlarged view of b d: Enlarged view in the horizontal direction 6 is a scanning electron micrograph of the structure obtained in Example 7. FIG. a: Photograph of a stick b: Enlarged view of the surface of a c: Enlarged view of b d: Enlarged view of c 6 is a scanning electron micrograph of the structure obtained in Example 8. a: Photo of the plate b: Enlarged view of the surface of a c: Enlarged view of b 6 is a scanning electron micrograph of the structure obtained in Example 9. a: Photograph of the board b: Enlarged view of the circled portion of a c: Enlarged view of b 2 is a scanning electron micrograph of the structure obtained in Example 10. FIG. a: surface photograph b: enlarged view of a c: enlarged view in the lateral direction d: enlarged view of c 2 is a scanning electron micrograph of the structure obtained in Example 11. FIG. a: Photograph of the surface b: Enlarged view of a c: Enlarged view of b 4 is a scanning electron micrograph of the structure obtained in Example 12. a: surface photo b: enlarged view of a c: enlarged view of b d: enlarged view of c 4 is a scanning electron micrograph of the structure obtained in Example 13. a: Photograph of the surface b: Enlarged view of a c: Enlarged view of b

Claims (12)

Selected from the group consisting of a glass substrate, a metal substrate, a metal oxide substrate, a substrate obtained by etching glass, a resin substrate, and a substrate obtained by treating the resin substrate surface with plasma, ozone, sulfuric acid or alkali. A nanostructure composite-coated structure in which the surface of one kind of solid substrate (X) is coated with a nanostructure composite (Y) having a thickness of 50 nm to 20 μm, the nanostructure composite (Y ) Is an aggregate having a composite nanofiber (y1) or composite nanoparticle (y2) containing a polymer (A) having a polyethyleneimine skeleton (a) and silica (B) as a basic unit. Nanostructure composite coated structure. The nanostructure composite-coated structure according to claim 1, wherein the nanostructure composite (Y) further contains a metal ion (C). The nanostructure composite-coated structure according to claim 1, wherein the nanostructure composite (Y) further contains metal nanoparticles (D). The nanostructure composite-covered structure according to claim 1, wherein the nanostructure composite (Y) further contains an organic dye molecule (E). The nanostructure composite (Y) has a composite nanofiber (y1) as a basic unit, and a long axis of the composite nanofiber is oriented in a direction substantially perpendicular to the surface of the solid substrate (X). The nanostructure composite-coated structure according to any one of 1 to 4. The nanostructure composite-coated structure according to claim 5, wherein the thickness of the composite nanofiber (y1) is in the range of 10 to 100 nm and the length is 50 nm to 10 µm. The nanostructure composite (Y) has composite nanoparticles (y2) as a basic unit, and the composite nanoparticles (y2) form a network to cover the solid substrate ( X ). The nanostructure composite-coated structure according to claim 1. The nanostructure composite-covered structure according to claim 7, wherein the composite nanoparticle (y2) has an average particle size of 20 nm or less. A glass substrate, a metal substrate, a metal oxide substrate, a substrate obtained by etching glass, a resin substrate, and a resin substrate surface in a solution containing a polymer (A) having a polyethyleneimine skeleton (a) plasma, ozone, a step of forming a polymer layer on the surface of the take-out after immersion one solid substrate (X) is selected from the group consisting of substrate treated with sulfuric acid or alkali, the solid substrate (X) (1) and
The solid substrate (X) having the polymer layer obtained in the step (1) is brought into contact with the silica source liquid (B ′), and the silica (B) is incorporated into the polymer layer on the surface of the solid substrate (X). The nanostructure composite (Y) which is an aggregate having the composite nanofiber (y1) or the composite nanoparticle (y2) as a basic unit is formed on the solid substrate (X) with a thickness of 50 nm to 20 μm. Step (2);
A method for producing a nanostructure composite-coated structure characterized by comprising: The nanostructure composite-covered structure obtained by the manufacturing method according to claim 9 is further immersed in an ion aqueous solution of a noble metal selected from the group consisting of gold, silver, and platinum, so that the noble metal ions are nanostructured. Metal nano-particles characterized in that the noble metal metal nanoparticles (D) are made to penetrate into the body (Y) and spontaneously reduce by the polyethyleneimine skeleton (a) in the nanostructure composite (Y). A method for producing a nanostructure composite-covered structure containing particles. A glass substrate, a metal substrate, a metal oxide substrate, a substrate obtained by etching glass in a solution containing a polymer (A) having a polyethyleneimine skeleton (a) and a metal ion (C), a resin substrate The surface of the solid substrate (X) is taken out after immersing one solid substrate (X) selected from the group consisting of a substrate treated with plasma, ozone, sulfuric acid or alkali on the surface of the resin substrate. Forming a polymer layer containing metal ions (C) in (1 ′),
The solid substrate (X) having the polymer layer obtained in the step (1 ′) is brought into contact with the silica source liquid (B ′), and silica (B) is contained in the polymer layer on the surface of the solid substrate (X). ) And depositing the nanostructure composite (Y), which is an assembly having the composite nanofiber (y1) or composite nanoparticle (y2) containing metal ions as a basic unit, with a thickness of 50 nm to 20 μm. X) forming on (2 ′),
A method for producing a nanostructure composite-covered structure containing a metal ion, comprising: A nanostructure composite-coated structure containing a metal ion obtained by the production method according to claim 11 is further immersed in a reducing agent solution to reduce the metal ion in the nanostructure composite (Y), A method for producing a nanostructure-composite-covered structure containing metal nanoparticles, wherein the structure is converted into nanoparticles.