JP5041360B2 - Metal fine particle array film and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing process of a metal particle-aligned film in which metal particles are aligned in a polymer in layers with a specific interval in parallel with a substrate. <P>SOLUTION: The manufacturing process of the metal particle-aligned film comprises (A) a step of forming a polymer film containing a metal component on a reflection substrate and (B) a step of irradiating the polymer film with a light having a specific wavelength. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a method for arranging metal fine particles in an orderly manner, and more particularly, to a method for arranging metal fine particles in a polymer film in a direction parallel to the film.

In recent years, there are many examples of research on organic / inorganic composites, and the functional properties of polymers can be modified. Therefore, organic / inorganic composite materials in which inorganic materials are combined with organic polymers have been actively developed. . Among them, active research has been conducted on a method for dispersing metal fine particles in a polymer with a certain regularity. For example, when a metal complex is used as a precursor of metal fine particles, sublimated, and contacted with a block copolymer having different metal reducing ability under nitrogen, the complex is selectively reduced only in one phase, and the metal The arrangement | sequence at the nano level of microparticles | fine-particles is implement | achieved (for example, refer nonpatent literature 1-3).
Langmuir, No. 19, 2963 (2003) Advanced Materials, No. 12, p. 1507 (2000) Nature 414, p.735 (2001)

  However, with regard to the arrangement of the metal fine particles in the reported polymer, the distribution (arrangement form) of each polymer of the copolymer is determined in a self-organizing manner, and an example in which the arrangement of the metal fine particles is completely controlled is as follows. Not reported. In particular, a method for arranging metal fine particles in a polymer film in a layered direction in a direction parallel to the film has not been known.

  An object of the present invention is to provide a method for producing a novel alignment film of metal fine particles by a simple method. Another object of the present invention is to provide a novel arrangement film of metal fine particles. It is a further object of the present invention to provide a wavelength selective reflective film.

  The present invention relates to the following matters.

1. Forming a polymer film containing a metal component on the reflective substrate (A);
And (B) irradiating the polymer film with light having a specific wavelength.

  2. 3. The production method according to 1 or 2 above, wherein the metal fine particle array film has a structure in which a layer in which metal fine particles are densely present periodically as a multilayer in the film thickness direction of the polymer film.

  3. 2. The production according to 1 above, wherein the polymer film-forming step (A) comprises a sub-step of forming a polymer solution containing a metal component on a reflective substrate and a sub-step of distilling off the solvent. Method.

4). Prior to the step (A), a step of providing on the reflective substrate a release layer that transmits light having a wavelength irradiated in the subsequent step (B),
In the step (A), a polymer film containing a metal component is formed on the release layer,
Furthermore, after the said process (B), it has the process of peeling the said polymer film after light irradiation from the said reflective substrate, The manufacturing method in any one of said 1-3 characterized by the above-mentioned.

  5). 5. The method according to claim 4, wherein the step of peeling the polymer film from the reflective substrate includes the step of removing the release layer.

  6). 6. The method according to 5 above, wherein the release layer is removed by dissolving the release layer.

  7). The manufacturing method according to any one of the above items 1 to 6, wherein the metal component includes a metal compound that is reduced by light of the specific wavelength to generate metal fine particles.

  8). The manufacturing method according to any one of 1 to 6, wherein the metal component includes metal fine particles.

  9. 8. The production method according to 7 above, wherein the metal compound is at least one selected from silver perchlorate, silver nitrate, and chloroauric acid.

  10. 10. The production method according to any one of 1 to 9, wherein the polymer constituting the polymer film is transparent at least at the specific wavelength.

  11. 1 to 10 above, wherein the polymer is at least one selected from the group consisting of polymethacrylic acid, polyacrylic acid, a copolymer containing methacrylic acid or an acrylic acid monomer unit, and polyvinyl alcohol. The manufacturing method in any one.

  12 12. The production method according to any one of 1 to 11 above, wherein in the step (B), the repetition distance of the metal fine particle layer in the metal fine particle array film is adjusted by changing the wavelength of the irradiated light.

  13. 12. In the step (B), the repetition distance of the metal fine particle layer in the metal fine particle array film is adjusted by changing the angle of the irradiated light with respect to the reflective substrate. Manufacturing method.

  14 A metal particle array film having a structure in which a layer in which metal particles are densely present in a polymer film periodically exists as a multilayer in the film thickness direction.

  15. 14. A metal fine particle array film produced by the method according to any one of 1 to 13 above, wherein the polymer film has a structure in which metal fine particle dense layers are periodically present as multilayers in the film thickness direction.

  16. 14. A metal fine particle array film comprising the steps of manufacturing a metal fine particle array film by the manufacturing method according to any one of 1 to 13, and laminating a plurality of the obtained metal fine particle array films. A method for producing a multilayer laminate.

  17. A multilayer laminate comprising a polymer film having a structure in which metal fine particles are densely present in the direction of film thickness as a multilayer, and produced by the production method described in 16 above.

  18. 16. A wavelength-selective reflective film using the metal fine particle array film according to 14 or 15, or the multilayer laminate according to 17 above.

  According to the present invention, a novel metal fine particle array film having a structure in which metal fine particle layers are periodically laminated can be produced by a simple method. The resulting metal fine particle array film is lightweight and excellent in transportability, impact resistance, and mechanical flexibility, and thus can be used in various applications. Further, in order to selectively reflect light of a specific wavelength, the reflective film can be widely applied to various optical elements, optical components, and the like.

  In the production method of the present invention, a polymer film containing a metal component is formed on a reflective substrate and irradiated with light having a specific wavelength λ. Hereinafter, the present invention will be described in detail.

<Reflective substrate>
The “reflective substrate” that can be used in the present invention is not particularly limited as long as the surface of the substrate can reflect light having a specific wavelength λ. For example, a reflecting mirror (mirror) in which a single layer film or a multilayer film is formed on the surface of the substrate using a material selected from various metals such as aluminum and silver and metal oxides. Among these, a film obtained by sequentially forming aluminum and silica on a glass substrate is preferable. This is because aluminum can form a film having a high reflectance stably in the ultraviolet to visible region. The silica layer is effective in preventing aluminum from being oxidized.

  The thickness (film thickness) of aluminum in the reflective substrate is, for example, about 100 to 2000 nm, preferably about 150 to 1000 nm, and more preferably about 200 to 800 nm. Further, the thickness (film thickness) of silica is better because it does not deteriorate the reflective properties of aluminum, and is, for example, about 5 to 100 nm, preferably about 10 to 50 nm, and more preferably about 10 to 30 nm.

<Formation of polymer film containing metal component>
The “polymer film containing a metal component” contains a metal component in the polymer, and the type of metal element may be one type or two or more types. The metal component preferably contains at least one of a metal compound (including a complex and a salt; the same applies hereinafter) and metal fine particles. In general, a method of applying a polymer solution containing a metal compound and / or metal fine particles to a reflective substrate is preferable, and a method of applying a polymer solution in which a metal compound is dissolved to a reflective substrate is particularly preferable.

  The metal compound used in the present invention generates metal fine particles by irradiation with a specific wavelength λ. As such a material, a compound that absorbs light energy and generates metal fine particles (or a metal constituting the metal fine particles) by reduction (that is, a metal compound having a positive oxidation number of metal atoms) is known. Usually, it is often a metal salt.

Examples of such metal compounds include metal oxides, metal hydroxides, metal halides (metal chlorides, etc.), metal acid salts [metal inorganic acid salts (sulfates, nitrates, phosphates, perchloric acid). Salt, oxo acid salt such as hydrochloride), metal organic acid salt (such as acetate) and the like. The form of the metal salt may be a single salt, a double salt, or a complex salt (electrolyte complex or non-electrolyte complex, usually an electrolyte complex), or a multimer (for example, a dimer). The metal compound (metal salt) includes, for example, an acid component [hydrogen chloride (HCl) and the like], a base component (ammonia and the like), water (H ₂ O) and the like (for example, a halogenated hydrogen compound, It may be a hydrate or hydrate). The metal compounds may be used alone or in combination of two or more.

  Moreover, the metal element which comprises a metal compound is not specifically limited. As the metal element constituting the metal compound, Group 8-11 metals of the periodic table (that is, iron, ruthenium, osmium, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, etc.) are preferable, and specific implementation In the form, noble metals (silver, gold, platinum, ruthenium, etc.) are particularly preferable. The metal compound may contain one or more of these metal elements.

Specific examples of the metal compound include Group 8-11 metal compounds (including metal salts) of the periodic table. For example, as Group 8-11 metal salts of the periodic table, inorganic acid salts [for example, noble metal inorganic acid salts such as silver perchlorate (AgClO ₄ ), silver nitrate (AgNO ₃ )], and organic acid salts [for example, acetic acid Palladium (Pd (CH ₃ CO ₂ ) _{2 and the} like), rhodium acetate (noble metal organic acid salts such as noble metal acetates such as [Rh (CH ₃ CO ₂ ) ₂ ] ₂ ) and the like. Further, as a periodic group 8-11 metal halide, noble metal halide [eg, silver chloride (AgCl), gold chloride (AuCl ₃ ), platinum chloride (PtCl ₂ , PtCl ₄ etc.), palladium chloride (PdCl ₂ etc.) Noble metal chlorides such as], acid component-containing metal halides [for example, hydrogen chloride-containing noble metal halides such as chlorinated noble metal acids such as chloroauric acid (HAuCl ₄ etc.), chloroplatinic acid (H ₂ PtCl ₆ etc.)] And hydrates thereof.

  Below, typical metal compounds are illustrated about gold | metal | money, silver, copper, platinum, palladium, and rhodium among periodic table 11 group metals.

Examples of the gold compound include gold halides (AuCl, AuCl ₃ , AuBr ₃ , AuI, AuI ₃ , AuCl (PPh ₃ ), AuCl (SC ₄ H ₈ ), halogenated gold acid or a salt thereof (HAuCl ₄ , HAuCl). _{4 · 4H 2 O, NaAuCl 4} · 4H 2 O, KAuCl 4 · 4H 2 O , etc.), gold hydroxide (AuOH), gold cyanide (AuCN), such as gold oxide _(Au 2 _{O 3),} gold sulfide (Au ₂ S, Au ₂ S ₃ (III), etc.), or trimethyl gold (III) (Au ₂ (CH ₃ ) ₆ ), methyl (triphenylphosphine) gold (I) (Au ₂ CH ₃ ( PPh _3)), 4-ethylbenzene-thio Ratn gold _{(I) (Au {S (} C 6 H 4) C 2 H 5}), {μ-1,8- bis (diphenylphosphino) 3,6 Dioxaoctane} bis {chloroauric _{(I)} ((AuCl)} 2 (μ- {Ph 2 P (CH 2) 2 O (CH 2) 2 O (CH 2) 2 PPh 2}), ( pentafluorophenyl ) (Tetrahydrothiophene) gold (I) ([Au (C ₆ F ₅ ) (SC ₄ H ₈ )]), tris (pentafluorophenyl) (tetrahydrothiophene) gold (III) ([Au (C ₆ F ₅ ) ₃ (SC ₄ H ₈ )]) and the like.

Silver compounds include inorganic salts [for example, silver halides such as AgF, AgCl, AgI, AgBr, silver oxides such as Ag ₂ O, Ag ₂ SO ₄ , AgS, AgCN, AgClO ₄ , Ag ₃ PO ₄ , AgSCN, _{AgNO 3, Ag 2 SO 3,} Ag 2 CO 3, Ag 2 CrO 4, Ag 2 Se, AgReO 4, AgBF 4, AgW 4 O 16, Ag 3 AsO 4, AgSbF 6, AgPF 6, AgHF 2, AgIO 3, Inorganic acid salts such as AgBrO ₃ , AgOCN, AgMnO ₄ , AgVO _3, etc.], organic salts (or complexes) [eg, C ₆ H ₅ CO ₂ Ag, C ₆ H ₁₁ (CH ₂ ) ₃ CO ₂ Ag, CH ₃ CH (OH) CO ₂ Ag, silver trifluoroacetate (CF ₃ CO ₂ Ag), C ₂ F ₅ CO ₂ Ag, C ₃ F ₇ CO _{2 Ag,} carboxylates such as _{AgO 2 CCH 2 C (OH)} (CO 2 Ag) CH 2 CO 2 Ag, p- toluenesulfonate, silver silver trifluoromethanesulfonate _(CF 3 _SO 3 Ag), etc. Sulfonate, (CH ₃ COCH═C (O—) CH ₃ ) Ag, (C ₂ H ₅ ) ₂ NCS ₂ Ag, phenyl silver (I), tetramesityl tetrasilver (I), butyl acetylide silver (I) , Chloro (isocyanocyclohexane) silver, (cyclopentadienyl) triphenylphosphine silver (I), bispyridine silver (I) perchlorate, (η ⁴ -1,5-cyclooctadiene) (1,1, 1,5,5,5-hexafluoro-2,4-pentanedionato) silver (I), bromo (tri-n-butylphosphine) silver (I), bisimidazole silver (I) nitrate, Bis (1,10-phenanthroline) silver (I) perchlorate and nitrate, 1,4,8,11-tetraazacyclotetradecane silver (II) perchlorate, (1,1,1,5,5 , 5-hexafluoro-2,4-pentanedionato) (N, N, N′-trimethylethylenediamine) silver (I) and the like].

Examples of the copper compound include inorganic salts [eg, Cu ₂ O, CuO, Cu (OH) ₂ , CuF ₂ , CuCl, CuCl ₂ , CuBr, CuBr ₂ , CuI and other copper halides, CuCO ₃ , CuCN, Cu (NO _{3) 2, Cu (ClO 4} ) 2, Cu 2 P 2 O 7, Cu 2 Se, CuSe, CuSeO 3, CuSO 4, Cu 2 S, CuS, Cu (BF 4) 2, Cu 2 HgI 4, CuSCN, Inorganic acid salts such as (CF ₃ CO ₂ ) ₂ Cu, (CF ₃ SO ₃ ) ₂ Cu, CuWO ₄ , Cu ₂ (OH) PO ₄ ], organic salts (or complexes) [eg, copper (I) acetate , copper acetate _{(II), [C 6 H} 11 (CH 2) 3 CO 2] 2 Cu, [CH 3 (CH 2) 3 CH (C 2 H 5) CO 2] 2 Cu, (HCO 2) 2 _{u, [HOCH 2 [CH (} OH)] 4 CO 2] carboxylate such as _{2 Cu, (CH 3 COCH =} C (O-) CH 3) Cu, CH 3 (CH 2) 3 SCu, (CH 3 O) ₂ Cu and the like].

Platinum compounds include inorganic salts [for example, platinum halides such as PtO ₂ , PtCl ₂ , PtCl ₄ , PtBr ₂ , PtBr ₄ , PtI ₂ , PtI ₅ , haloplatinic acids such as HPtCl ₆ · 2H ₂ O, PtS _2, Pt _(CN) such as _2], organic salts (or complexes) [Examples thereof _{include (CH 3 COCH = C (O-} ) CH 3) Pt, etc. _{(C 6 H 5 CN) 2} PtCl 2] .

Examples of the palladium compound include inorganic salts [eg, palladium halides such as PdO, PdCl ₂ , PdBr ₂ , PdI ₂ , PdCN ₂ , Pd (NO ₃ ) ₂ , PdS, PdSO ₄ , K ₂ Pd (S ₂ O ₃ ) ₂ · H ₂ O, chloropalladic acid, etc.], organic salts (or complexes) [for example, carboxylates such as Pd (CH ₃ CO ₂ ), palladium (II) propionate, (CF ₃ CO ₂ ) ₂ Pd , (CH ₃ COCH═C (O—) CH ₃ ) Pd, (C ₆ H ₅ CN) ₂ PdCl _2, etc.].

Examples of rhodium compounds include inorganic salts [eg, rhodium halides such as Rh ₂ O ₃ , RhO ₃ , RhCl ₃ , RhBr ₃ , RhI ₃ , RhPO ₄ , Rh ₂ SO _4, etc.], organic salts (or complexes) [eg, , Rh (CH ₃ CO ₂ ) ₂ , (CF ₃ CO ₂ ) ₂ Rh, {[CH ₃ (CH ₂ ) ₆ CO ₂ ] ₂ Rh} ₂ , [(CF ₃ CF ₂ CF ₂ CO ₂ ) ₂ Rh] ₂ , carboxylic acid salts such as {[(CH ₃ ) ₃ CCO ₂ ] ₂ Rh} ₂ , (CH ₃ COCH═C (O—) CH ₃ ) Rh, etc.] and the like.

  Among these metal compounds, silver salt is a metal compound that has high photosensitivity and is easily reduced by light, and silver perchlorate and silver nitrate are preferably used.

  Further, the metal fine particles (here, meaning the metal fine particles contained in the polymer film at the time of step (A)) are preferably those that can move in the film by irradiation with a specific wavelength λ. Metal particles of about 10 nm or less, particularly preferably 2 nm or less, such as particle-like particles are preferred. For example, the thing which metal fine particles precipitated from said metal compound is mentioned. For example, silver fine particles are preferable. Further, it may be a mixture of a metal compound and metal fine particles.

  The ratio of the metal component contained in the polymer depends on the molecular weight of the polymer, but is, for example, 0.5 to 500 parts by weight, preferably 1 to 400 parts by weight, and more preferably 5 parts per 100 parts by weight of the polymer. About 200 parts by weight.

  As the polymer, a polymer that is transparent at a specific wavelength λ and can contain a metal component uniformly dissolved or dispersed (particularly, a polymer that dissolves) is preferably used. In addition, in one embodiment, those that are uniformly dissolved in an organic solvent are preferably used.

  For example, polyesters such as polycarbonate, polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, acrylic polymers such as polymethyl methacrylate, methyl styrene resin, acrylonitrile butadiene styrene (ABS) resin, acrylonitrile styrene (AS) resin, etc. Styrene resin, polyethylene, polypropylene, polyolefins such as polymethylpentene, polyethers such as polyoxetane, transparent polyamides such as nylon 6 and nylon 66, polystyrene, polyvinyl chloride, polyethersulfone, polysulfone, Polyacrylate and cellulose triacetate, polyvinyl alcohol, polyacrylonitrile, cyclic polyolefin, acrylic resin, epoxy Resin, cyclohexadiene based polymers, amorphous polyester resin, transparent polyimide, transparent polyurethane, transparent fluororesin, a thermoplastic elastomer, such as various transparent polymers, including polylactic acid can be cited. In addition, copolymers of monomers that are constituents of these polymers and / or mixtures of these polymers can also be used. Among these, a polymer selected from polymethacrylic acid, polyacrylic acid, a copolymer containing methacrylic acid or an acrylic acid monomer unit, and polyvinyl alcohol is preferably used.

  As the solvent, it is usually possible to use a solvent capable of dissolving or dispersing (particularly, dissolving) the polymer and the metal component. Such a solvent can be appropriately selected according to the type of polymer and metal component, and includes, for example, water (which may be acidic, neutral or alkaline), alcohols (methanol, ethanol, propanol, isopropanol, butanol, isobutanol, etc. Alkyl alcohols, etc.), ethers (chain ethers such as dimethyl ether and diethyl ether, cyclic ethers such as dioxane and tetrahydrofuran), esters (acetic esters such as methyl acetate, ethyl acetate and butyl acetate) , Ketones (such as dialkyl ketones such as acetone and ethyl methyl ketone), glycol ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, cellosolve acetate) , Butoxycarbitol acetate, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), carbitols (carbitol, etc.), halogenated hydrocarbons (methylene chloride, chloroform, etc.), acetals (acetal, Methylal etc.), amides (dimethylformamide etc.), sulfoxides (dimethyl sulfoxide etc.), nitriles (acetonitrile, benzonitrile etc.) and the like. These solvents may be used alone or in combination of two or more.

  The proportion of the solvent is determined in consideration of the thickness (film thickness) of a polymer film containing a metal component intended for film formation on the reflective substrate. The amount is about 10,000 parts by weight, preferably about 30 to 5,000 parts by weight, and more preferably about 50 to 3,000 parts by weight.

  Further, the method for forming the metal component-containing polymer solution on the reflective substrate is not particularly limited as long as film formation is possible, and a conventional coating method such as spin coating (rotary coating), roll coating, curtain Coating methods, dip coating methods, cast methods, etc. can be used. As the coating device, a device corresponding to the above coating method, for example, a spin coater, a slit coater, a roll coater, a bar coater or the like can be used.

  Further, the method for distilling off the solvent of the metal component-containing polymer solution formed on the substrate is not particularly limited, and examples thereof include conventional solvent distilling methods such as evaporation by heating and vacuum drying by various evaporators.

  Thus, the thickness of the polymer film containing the metal component formed on the reflective substrate is not particularly limited, and can be set as appropriate according to the application. For example, it can be formed to a thickness of about 0.5 to 500 μm, preferably 0.5 to 100 μm, and more preferably about 1 to 20 μm.

<Light irradiation>
In the production method of the present invention, the polymer film containing the metal component formed on the reflective substrate is then irradiated with light having a specific wavelength λ. A desired wavelength can be selected as the wavelength λ, but when the above-described metal component receives light of this wavelength, generation of metal fine particles, movement of metal fine particles, and growth of metal particles can occur. It sets from such a wavelength range. Usually, it is selected from a wavelength region having sufficient energy to excite a metal compound and reduce it to metal fine particles, and an ultraviolet to visible light region is preferable. Specifically, it is preferable that one wavelength is selected from a wavelength region of 200 to 600 nm, preferably 300 to 500 nm, more preferably 350 to 500 nm. In such a wavelength range, various metal compounds can be efficiently photoreduced into metal fine particles.

  Examples of light sources to be irradiated include halogen lamps, mercury lamps (low pressure mercury lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, etc.), deuterium lamps, UV lamps, lasers (eg, helium-cadmium lasers, excimer lasers, etc.), etc. Can be used. In one embodiment, an ultra high pressure mercury lamp is suitable. Further, it is preferable to irradiate one wavelength with a narrow half width as much as possible. The full width at half maximum of the irradiation wavelength is preferably 50 nm, more preferably 30 nm or less, particularly preferably 20 nm or less, and most preferably 10 nm or less. In order to reduce the half-value width, it is preferable to combine a commercially available narrow band-pass filter.

Although the light irradiation time largely depends on the ability (irradiation intensity) of the irradiation light source, it is preferable to determine the size of the generated metal particles in consideration of the reaction rate and the movement of the metal component. Although not limited, as an example, when a 500 W ultra-high pressure mercury lamp (irradiation intensity: 165 W / cm ² or more) is used, the irradiation time is 20 minutes to 6 hours, preferably 30 minutes to 3 hours, and particularly preferably 30. Min to 2 hours.

<Metal fine particle alignment film>
By the light irradiation step, metal fine particles are generated from the metal compound in the metal component-containing polymer film, or the metal fine particles move and densely form a layer parallel to the film surface. A multilayer structure. That is, when viewed in the cross-sectional direction of the film, it has a multi-layer structure in which metal fine particle layers in which metals are densely packed and polymer-only layers are alternately laminated.

  FIG. 18 shows a conceptual diagram of an estimation mechanism capable of obtaining such a multilayer structure. As shown in this figure, incident light and reflected light interfere with each other to generate a standing wave having a periodic light intensity distribution, and metal fine particles are generated mainly in a portion having a large light intensity. In addition, since light is an electromagnetic wave, the electric field strength is large in the portion where the light intensity is strong, and the metal fine particles move from the portion where the electric field is weak to the strong portion. As a result, it is presumed that a multilayer structure is formed. . On the other hand, it is presumed that a standing electric field intensity distribution also occurs in the polymer containing metal fine particles, and the metal fine particles move and a multilayer structure is formed by the same mechanism.

  Moreover, in the manufacturing method of this invention, the repetition distance (pitch) of a metal fine particle layer can be adjusted artificially. In accordance with the above theory, the repetition distance (pitch) of the metal fine particle layer is changed by adjusting the period of the light intensity generated in the thickness direction of the polymer film. Typically, it can be adjusted by changing the wavelength λ of the irradiation light. For example, the repetition distance of the metal fine particle layer can be increased by setting the wavelength of the irradiation light to a long wavelength. Furthermore, the repetition distance (pitch) of the metal fine particle layer can also be adjusted by changing the angle of the irradiation light. For example, the repetition distance of the metal fine particle layer can be increased by increasing the incident angle of the irradiation light. The change in the incident angle is a very simple method because it can be realized simply by tilting the substrate or making the irradiation light incident at a certain angle. Furthermore, in this method, the repetition distance of the metal fine particle layer can be adjusted independently from the wavelength of the irradiation light, and therefore, light having a wavelength suitable for the reaction can be selected during production. It is also easy to produce a film that selectively reflects light having a wavelength different from the wavelength of irradiation light. In the metal fine particle film of the present invention, the arrangement of the metal fine particle layer can be determined by artificial control as described above. Note that the film thickness may shrink or increase due to the treatment after the light irradiation, and in this case, the repetition distance (pitch) of the metal fine particle layer may also change.

  Interference is likely to occur in light emitted from one light source and propagated through two different paths, and the position where the strengthening / weakening due to interference is observed is determined by the optical path difference between the two lights. The following theoretical explanation is possible.

  For example, in the present invention, when incident light is irradiated vertically, the incident light having the wavelength λ from the light source interferes with the reflected light from the substrate at a point P where the geometric distance from the reflecting substrate is d ′. I think so. FIG. 19A shows a conceptual diagram for theoretically explaining this phenomenon. In the present invention, since the refractive index of the thin film is larger than that of the reflective substrate, reflection is caused by incidence from a substance having a high refractive index to a small substance, and the phase of light is not reversed by reflection at the point O. That is, in order for the incident light and the reflected light to interfere at this point, the optical path difference between the incident light and the reflected light = 2 × OP needs to be an integral multiple of the incident wavelength in the thin film.

That is, when the geometric distance from the reflective substrate is d ′, λ is the wavelength of the irradiation light, λ ′ is the wavelength of the light in the thin film, and n is the refractive index of the metal component-containing polymer,
2d ′ = mλ ′ = mλ / n (m = 0, 1, 2,...)
Interference occurs at d ′ that satisfies

  Considering the entire thin film, since the interference point is determined by the distance from the reflective substrate, the interference point exists in layers in a direction parallel to the substrate, and the results in the embodiments of the present invention to be described later are theoretically shown. I can explain.

Similarly, if you light irradiated to the thin film at a certain incident angle theta ₁ is considered as follows. FIG. 19B shows a conceptual diagram for theoretically explaining this phenomenon. As in the case of vertical irradiation, in order for the incident light and the reflected light to interfere at this point, the optical path difference between the incident light and the reflected light = OP + OQ needs to be an integral multiple of the incident wavelength in the thin film. When incident on the thin film at an incident angle θ ₁ , the incident angle θ ₂ in the thin film becomes a value satisfying Snell's law shown in the figure. By using the refractive index of the thin film, the incident angle θ ₂ in the thin film can be calculated.

Considering optical path difference = OP + OQ, the optical path difference can be expressed as 2d ′ cos θ ₂ by using the trigonometric theorem. Therefore, the geometric distance from the reflecting substrate is d ′, the incident angle in the thin film is θ ₂ , λ is the wavelength of the irradiation light, λ ′ is the wavelength of the light in the thin film, and n is the refractive index of the metal component-containing polymer. As
2d ′ cos θ ₂ = mλ ′ = mλ / n (m = 0, 1, 2,...)
Interference occurs at d ′ that satisfies

  Considering the thin film as a whole, the interference point is determined by the distance from the reflective substrate as in the case of vertical irradiation, so that the interference point exists in layers in the direction parallel to the substrate. The results in the examples can be explained theoretically.

  The metal fine particles in the metal fine particle layer are extremely small at the time of generation, but the particle diameter becomes large due to the aggregation and consolidation normally observed in the metal fine particles, and the metal fine particles are substantially reduced. It may take the form that can be considered. On the other hand, even in a polymer containing metal fine particles, by increasing the light intensity, the difference between the portion where the electric field strength generated as a standing wave is high and the portion where the electric field strength is small becomes large. growing.

  Thus, although it depends on conditions, it is usually 2 to 100 nm. In a particular embodiment, the majority (eg 80% or more) of the fine particles have a nano-level particle size of 50 nm or less. Various applications of the metal fine particle array film are expected by utilizing the periodic multilayer structure of the metal fine particle layer. Typically, it can be used as a reflective film as described later. The metal fine particle array film thus manufactured may be used in a state where it is formed on the reflective substrate, or may be used after being peeled off.

{Second Embodiment of the Invention}
In the manufacturing method described above (referred to as the first embodiment), since the metal fine particle array film is formed on the reflective substrate, the metal fine particle array film may not be peeled from the reflective substrate depending on the selection of materials and the like. Yes, application is limited. In the second embodiment, a method for obtaining the metal fine particle array film as a self-supporting film will be described. In the description of the second embodiment, the matters (materials, conditions, preferred ranges, etc.) described in the first embodiment are adopted as long as there is no contradiction regarding matters not specifically mentioned.

  In the second embodiment, instead of directly forming a polymer film containing a metal component on a reflective substrate, a release layer is first provided on the reflective substrate. The release layer is a material that does not inhibit irradiation of a specific wavelength λ, that is, a material that is transparent at that wavelength, and can release the metal fine particle array film formed in a later step from the reflective substrate. If there is no particular limitation. For example, a form in which the metal fine particle array film can be peeled off by removing the release layer itself in a later process, and a form in which the adhesive strength between the reflective substrate and the release layer can be peeled off together with the metal fine particle array film in a later process For example, since the adhesive strength between the release layer and the metal fine particle array film is small, the metal fine particle array film can be peeled off in a later step.

  In order to achieve stable peeling, a mode in which the peeling layer itself is removed in a later step is preferable, and a mode in which the peeling layer is removed by dissolving in a solvent is particularly preferable. For this purpose, the release layer is preferably formed of a polymer, for example, a polymer that is insoluble in the solvent of the metal component-containing polymer solution.

  For example, polyesters such as polycarbonate, polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, acrylic polymers such as polymethyl methacrylate, methyl styrene resin, acrylonitrile butadiene styrene (ABS) resin, acrylonitrile styrene (AS) resin, etc. Styrene resin, polyethylene, polypropylene, polyolefins such as polymethylpentene, polyethers such as polyoxetane, transparent polyamides such as nylon 6 and nylon 66, polystyrene, polyvinyl chloride, polyethersulfone, polysulfone, Polyacrylate and cellulose triacetate, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, cyclic polyolefin, acrylic Le resins, epoxy resins, cyclohexadiene based polymers, amorphous polyester resin, transparent polyimide, transparent polyurethane, transparent fluororesin, a thermoplastic elastomer, such as various transparent polymers, including polylactic acid can be cited. In addition, copolymers of monomers that are constituents of these polymers and / or mixtures of these polymers can also be used. Of these, styrene is preferably used.

  The thickness of the release layer is preferably thin so as not to hinder the arrangement of the metal fine particles in the polymer due to light irradiation. For example, 0.01 to 50 μm, preferably 0.01 to 20 μm, and more preferably 0. About 0.01 to 5 μm.

  The layer may be formed, for example, by applying a solution of these polymers and then removing the solvent, or by applying a monomer together with an initiator if necessary, followed by polymerization. As the supplementary coating method, a conventional coating method such as a spin coating method (rotary coating method), a roll coating method, a curtain coating method, a dip coating method, or a casting method can be used. As the coating device, a device corresponding to the above coating method, for example, a spin coater, a slit coater, a roll coater, a bar coater or the like can be used.

  After forming the release layer on the reflective substrate in this manner, a polymer film containing a metal component is formed on the release layer in the same manner as in the first embodiment, and light having a specific wavelength λ is formed. Irradiate. The polymer film is a metal fine particle array film in which metal fine particle layers are arranged in multiple layers.

  Next, the polymer film after being irradiated with light, that is, the metal fine particle array film is peeled off from the reflective substrate. The peeling method depends on the material of the peeling layer. When the release layer is a material that reduces the adhesive strength at the interface, it can be mechanically peeled off.

  When the release layer is a removable material, particularly when the release layer is the above-described soluble material, the release layer is immersed in a solvent in which the release layer can be dissolved and the metal fine particle array film does not dissolve. As a result, the release layer is dissolved and removed. As a result, the metal fine particle array film can be peeled from the reflective substrate.

  The metal fine particle array film peeled from the reflective substrate thus obtained may be used as it is, or may be used after being attached to a suitable base material. For example, when a transparent or opaque film or sheet, in particular, a resin (polymer) film or sheet is used as a substrate and a metal fine particle array film is pasted or laminated thereon, the mechanical flexibility of the metal fine particle array film of the present invention In addition, the mechanical strength and handleability can be improved without impairing the lightness, so that it can be used in various applications.

<Application as reflective film>
The metal fine particle array film of the present invention described as the first embodiment and the second embodiment can be used for various purposes, but is particularly useful as a reflective film. When the reflection characteristics of the metal fine particle array film are measured, as shown in the examples described later, this film has a maximum value of reflection at a wavelength position almost coincident with the wavelength λ when irradiated with light, and is wavelength selective. It became clear that it functions as a reflective film.

Therefore, by calculating a form in which a multilayer is laminated with a period of the optical distance d in the transparent layer, the metal layer (partial reflection / partial transparency) is calculated by simulation.
d = λ / 2
That is, d ′ = λ ′ / 2 = λ / (2n)
(Where d is the optical distance, d ′ is the geometric distance, λ is the reflection wavelength, λ ′ is the wavelength in the polymer, and n is the refractive index of the polymer)
It was shown that the wavelength λ satisfying the above condition is selectively reflected.

  In the metal fine particle array film obtained in the present invention, since the metal fine particle layers are laminated at substantially equal intervals, the metal fine particle layer performs a function similar to a partially reflective / partially transmissive layer. Presumed. When the period of the metal particle layer (the distance from the center to the center of the layer) is expressed by the optical distance d (geometric distance d ′ = d / n, n is the refractive index of the polymer), the maximum position of the reflection spectrum is This is considered to correspond to a wavelength λ that satisfies the equation. However, it is considered that the selectivity such as the half width of the peak and the reflection suppression of other wavelengths is affected by the distribution and density of the metal fine particles.

  Since the metal fine particle array film of the present invention peeled from the reflective substrate is easily bent, the scattered light is suppressed by forming an element sandwiched between transparent substrates such as quartz plates, resin (polymer) films or sheets. By doing so, it is possible to improve the characteristics as a wavelength selective reflection film.

  Moreover, the metal fine particle array film peeled from the reflective substrate can be made into a laminate by stacking a plurality of metal fine particle arrays in close contact with each other by a method such as stacking or folding the thin film. By using a laminated body, the reflection characteristics can be improved. Since the effect of improving the reflection characteristics of the stacked layer due to the stacking tends to be saturated, for example, when stacking the layered metal fine particle films of about 2 μm, for example, 2 to 20, preferably 2 to 15, further Preferably, about 2 to 10 sheets are stacked and used.

  Further, as shown in the examples described later, the repetition distance of the metal fine particle layer is controlled by changing the wavelength and incident angle of the irradiation light, and selectively reflects light having a wavelength different from the wavelength of the irradiation light. It became clear that a film could be produced. Thus, according to the present invention, a film that selectively reflects light of various wavelengths can be easily produced.

  The metal fine particle array film produced in the present invention can be used in place of a conventional optical multilayer reflective film made of an inorganic material or an inorganic oxide. Therefore, weight reduction, transportability, impact resistance, mechanical flexibility, and the like are improved, and a wide range of applications as optical materials to optical components and the like are possible.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to a present Example.

Example 1
A 200 nm aluminum film was formed on soda lime glass by a direct current sputtering method, and a 10 nm silica film was formed by an alternating current sputtering method at 13.56 MHz to obtain a reflective substrate. A solution obtained by dissolving 63.1 mg of silver perchlorate in 5.01 g of a 10 wt% polymethacrylic acid methanol solution was spin-coated (1500 rpm, 10 seconds) on a reflective substrate, and then dried at room temperature for 3 hours. Thereafter, ultraviolet light with a wavelength of 365 nm is vertically irradiated for 1 hour to the thin film on the reflective substrate using an ultra-high pressure mercury lamp (USHIO INC., “Multi Light”) and a narrow band-pass filter. did.

  A transmission electron microscope (TEM) photograph of the cross section of the thin film on the obtained reflective substrate is shown in FIG. In polymethacrylic acid, it was confirmed that silver fine particles were arranged in layers in a direction parallel to the substrate at intervals of about 90 nm (geometric distance). Moreover, it was observed that most of the silver particles have a particle size of 10 nm or less.

(Comparative Example 1)
63.1 mg of silver perchlorate was dissolved in 5.01 g of a 10 wt% polymethacrylic acid methanol solution. The obtained solution was spin-coated (1500 rpm, 10 seconds) on soda lime glass, and then dried at room temperature for 3 hours. Thereafter, the thin film on the soda lime glass was vertically irradiated with ultraviolet light having a wavelength of 365 nm using an ultra-high pressure mercury lamp (manufactured by USHIO INC., “Multi Light”) and a narrow band-pass filter. .

The transmission electron microscope (TEM) photograph of the thin film cross section on the obtained soda-lime glass is shown in FIG. The particle size of the silver fine particles precipitated in the polymethacrylic acid was irregular, and the structure in which the silver particles were arranged in a layered manner in the direction parallel to the substrate, which was observed when the reflective substrate was used, was not seen.

(Example 2)
A 10 wt% polystyrene toluene solution was spin-coated (1500 rpm, 10 seconds) on the reflective substrate prepared in Example 1, and then dried at room temperature for 3 hours. Further, a solution obtained by dropping 2.44 g of a methanol solution of 71.7 mg of silver perchlorate into 2.51 g of a methanol solution of 10 wt% polyacrylic acid on a thin film on a substrate was spin-coated (1500 rpm, 40 seconds). And dried at room temperature for 3 hours. Thereafter, ultraviolet light with a wavelength of 365 nm is vertically irradiated for 1 hour to the thin film on the reflective substrate using an ultra-high pressure mercury lamp (USHIO INC., “Multi Light”) and a narrow band-pass filter. did. The obtained sample was impregnated with xylene to dissolve the styrene layer, and the metal fine particle array film was peeled from the reflective substrate.

  The transmission electron microscope (TEM) photograph of the obtained thin film cross section is shown in FIG. It was confirmed that silver was arranged in layers in the direction parallel to the substrate in the polyacrylic acid. Furthermore, the reflection spectrum of this thin film is shown in FIG. It was found that there was a maximum value of reflection at the irradiation wavelength of 365 nm.

(Example 3)
A solution obtained by dissolving 61.8 mg of silver perchlorate in 5.02 g of a methanol solution of 10 wt% polymethacrylic acid on the reflective substrate prepared in Example 1 was spin-coated (1500 rpm, 10 seconds), and then room temperature. And dried for 3 hours. Thereafter, the thin film on the reflective substrate was irradiated with ultraviolet light having a wavelength of 436 nm vertically for 12 hours using an ultra-high pressure mercury lamp (manufactured by Ushio Inc., “Multilight”) and a g-ray transmission filter. .

  A transmission electron microscope (TEM) photograph of a cross-section of the thin film on the obtained reflective substrate is shown in FIG. Silver fine particles in polymethacrylic acid are arranged in layers in a direction parallel to the substrate at an interval of approximately 110 nm (geometric distance), and the repetition distance of the metal fine particle layer is longer than when using a wavelength of 365 nm. It was confirmed that Moreover, it was observed that most of the silver particles have a particle size of 10 nm or less.

  Thus, the repetition distance (pitch) of the metal fine particle layer can be adjusted by changing the wavelength λ of the irradiation light.

(Reference Example 1)
60.5nm Silica / 3nm Silver / 122.5nm Silica / 3nm Silver /.../ 122.5nm Silica / 3nm Silver / 60.5nm Adopting physical property values corresponding to all 41 layers of multilayer film having the structure of silica. The reflection characteristics were predicted by the optical thin film design software Essential Macleod. The result is expected to have a maximum reflection wavelength at 365 nm as shown in FIG. Here, the distance d (optical length) between the metal layers satisfies d = λ / 2 (λ = 365 nm). From this result, it is presumed that the selectivity of the reflection wavelength occurs in the metal fine particle array film of Example 2 according to the same principle.

Example 4
A solution obtained by dissolving 51.5 mg of silver perchlorate in 4.99 g of a tetrahydrofuran (THF) solution of 10 wt% poly (methyl methacrylate / methacrylic acid) 75:25 random copolymer on the reflective substrate prepared in Example 1. Was spin-coated (1500 rpm, 10 seconds) and then dried at room temperature for 3 hours. Thereafter, ultraviolet light with a wavelength of 365 nm is vertically irradiated for 1 hour to the thin film on the reflective substrate using an ultra-high pressure mercury lamp (USHIO INC., “Multi Light”) and a narrow band-pass filter. did.

  A transmission electron microscope (TEM) photograph of a cross-section of the thin film on the obtained reflective substrate is shown in FIG. It was confirmed that silver fine particles were arranged in layers in the polymer in a direction parallel to the substrate at an interval of approximately 108 nm (geometric distance). Moreover, it was observed that most of the silver particles have a particle size of 10 nm or less.

(Example 5)
A solution obtained by dissolving 98.0 mg of silver nitrate in 5.04 g of an aqueous solution of 10 wt% polyvinyl alcohol on the reflective substrate prepared in Example 1 was spin-coated (3000 rpm, 30 seconds) and then dried at room temperature for 5 hours. . After that, UV light with a wavelength of 365 nm is irradiated vertically for 2 hours to the thin film on the reflective substrate using an ultra-high pressure mercury lamp (USHIO INC., “Multi Light”) and a narrow band-pass filter. did.

  A transmission electron microscope (TEM) photograph of the cross section of the thin film on the obtained reflective substrate is shown in FIG. It was confirmed that the silver fine particles were arranged in layers in the direction parallel to the substrate at intervals of about 120 nm (geometric distance) in the polyvinyl alcohol. Moreover, it was observed that most of the silver particles have a particle size of 10 nm or less.

(Example 6)
A 10 wt% polystyrene toluene solution was spin-coated (1500 rpm, 10 seconds) on the reflective substrate prepared in Example 1, and then dried at room temperature for 3 hours. Further, after spin-coating (1500 rpm, 10 seconds) a solution obtained by dropping 704 mg of a 17 wt% dichloroauric acid aqueous solution into 10.01 g of a 5 wt% polyacrylic acid methanol solution on a thin film on the substrate, Dry at room temperature for 3 hours. Thereafter, ultraviolet light with a wavelength of 365 nm is vertically irradiated for 3 hours to the thin film on the reflective substrate using an ultra-high pressure mercury lamp (USHIO INC., “Multi Light”) and a narrow band-pass filter. did. The obtained sample was impregnated with xylene to dissolve the styrene layer, and the metal fine particle array film was peeled from the reflective substrate.

  A transmission electron microscope (TEM) photograph of the obtained thin film cross section is shown in FIG. It was confirmed that the gold fine particles were arranged in layers in the direction parallel to the substrate at intervals of about 130 nm (geometric distance) in the polyacrylic acid. It was also observed that many of the gold particles have a particle size of about 10 nm.

(Example 7)
A solution obtained by dissolving 64.3 mg of silver perchlorate in 5.02 g of a methanol solution of 10 wt% polymethacrylic acid on the reflective substrate prepared in Example 1 was spin-coated (1500 rpm, 10 seconds) on the reflective substrate. Then, it was dried at room temperature for 3 hours. Thereafter, an ultraviolet light with a wavelength of 365 nm is incident on the thin film on the reflective substrate at an angle of 30 ° using an ultrahigh pressure mercury lamp (manufactured by USHIO INC., “Multi Light”) and a narrow band-pass filter. For 1 hour.

  The transmission electron microscope (TEM) photograph of the thin film cross section on the obtained reflective substrate is shown in FIG. In polymethacrylic acid, it was confirmed that silver fine particles were arranged in layers in a direction parallel to the substrate at an interval of about 105 nm (geometric distance). Moreover, it was observed that most of the silver particles have a particle size of 10 nm or less.

(Example 8)
A solution obtained by dissolving 64.3 mg of silver perchlorate in 5.02 g of a 10 wt% polymethacrylic acid methanol solution on the reflective substrate prepared in Example 1 was spin-coated (1500 rpm, 10 seconds), and then room temperature. And dried for 3 hours. Thereafter, an ultraviolet light with a wavelength of 365 nm is incident on the thin film on the reflective substrate at an angle of 45 ° using an ultra-high pressure mercury lamp (“Multi Light” manufactured by USHIO INC.) And a narrow band-pass filter. For 1 hour.

  A transmission electron microscope (TEM) photograph of a cross-section of the thin film on the obtained reflective substrate is shown in FIG. In polymethacrylic acid, it was confirmed that silver fine particles were arranged in layers in a direction parallel to the substrate at an interval of approximately 109 nm (geometric distance). Moreover, it was observed that most of the silver particles have a particle size of 10 nm or less.

Example 9
A solution obtained by dissolving 52.0 mg of silver perchlorate in 4.00 g of a 10 wt% polymethacrylic acid methanol solution on the reflective substrate prepared in Example 1 was spin-coated (1500 rpm, 10 seconds), and then room temperature. And dried for 3 hours. Thereafter, an ultraviolet light with a wavelength of 365 nm is incident on the thin film on the reflective substrate at an angle of 60 ° using an ultra-high pressure mercury lamp (manufactured by USHIO INC., “Multi-light”) and a narrow band-pass filter. For 1 hour.

  A transmission electron microscope (TEM) photograph of a cross section of the thin film on the obtained reflective substrate is shown in FIG. In the polymethacrylic acid, it was confirmed that the silver fine particles were arranged in layers in the direction parallel to the substrate at intervals of about 122 nm (geometric distance). Moreover, it was observed that most of the silver particles have a particle size of 10 nm or less.

  Thus, the repetition distance of the metal fine particle layer can be increased by increasing the incident angle of the irradiation light. That is, when arranging at the same wavelength λ, the optical path difference between the incident light and the reflected light can be controlled by changing the incident angle of the irradiation light, and the repetition distance (pitch) of the metal fine particle layer is adjusted. Is possible.

(Reference Example 2)
Based on a TEM photograph in Example 7 (incident angle 30 °), 100.0 nm polymethacrylic acid / 10 nm silver / 95.0 nm polymethacrylic acid / 10 nm silver /.. ./100.0 nm polymethacrylic acid / 10 nm Reflecting characteristics were predicted by the optical thin film design software Essential Macintosh using physical property values corresponding to a total of 28 multilayer films having a silver structure. The result is expected to have a maximum reflection wavelength at 326 nm, as shown in FIG. Here, since the refractive index of the polymer at 326 nm is approximately 1.55 as measured by spectroscopic ellipsometry, the distance d (optical length) between the metal layers is d = nd ′ = λ / 2 (λ = 326 nm, Geometric distance d ′ = 105 nm). Similarly, based on TEM photographs in Examples 8 (incident angle 45 °) and 9 (incident angle 60 °), the results of reflecting the reflection characteristics are shown in FIG. Also in Examples 8 and 9, the above relational expression was established, and it was confirmed that the maximum reflection wavelength could be controlled by changing the incident angle. That is, it is presumed that the selectivity of the reflection wavelength can be changed by changing the angle of the irradiation light to adjust the repetition distance (pitch) of the metal fine particle layer.

(Reference Example 3)
On the other hand, based on the interference theory described with reference to FIG. 19A, it is possible to estimate the configuration of the metal fine particle array film when the light of λ = 365 nm is vertically irradiated, 116.0 nm polymethacrylic acid / 3 nm Silver / 116.0 nm polymethacrylic acid / 3 nm silver /... /116.0 nm polymethacrylic acid / 3 nm The optical thin film design software Essential using the physical properties corresponding to 38 layers of multilayer film having the structure of silver. Reflection characteristics were predicted at Macintosh. The results are shown in FIG.

  Further, it is possible to estimate the configuration of the metal fine particle array film when λ = 365 nm light is irradiated at an angle of 60 ° in the same manner, and 141.0 nm polymethacrylic acid / 3 nm silver / 141.0 nm polymethacrylic. By adopting physical property values corresponding to all 38 layers of multi-layer films having the structure of acid / 3nm silver /.../ 141.0nm polymethacrylic acid / 3nm silver, the reflection characteristics are measured with the optical thin film design software Essential Macintosh. I expected. The results are shown in FIG.

(Example 10)
A solution obtained by dissolving 50.1 mg of silver perchlorate in 5.00 g of a tetrahydrofuran (THF) solution of a 10 wt% poly (methyl methacrylate / methacrylic acid) 75:25 random copolymer on the reflective substrate prepared in Example 1. Was spin-coated (1500 rpm, 10 seconds) and then dried at room temperature for 3 hours. After that, UV light with a wavelength of 365 nm is irradiated vertically for 2 hours to the thin film on the reflective substrate using an ultra-high pressure mercury lamp (USHIO INC., “Multi Light”) and a narrow band-pass filter. did. After the metal fine particle array film was peeled from the reflective substrate of the obtained sample, an optical element was produced by sandwiching the thin film between two quartz plates.

  The reflection spectrum of the obtained optical element is shown in FIG. As predicted based on the interference theory shown in Reference Example 3, it was found that the maximum value of reflection was 24.1% at 360 nm, which is very close to the irradiation wavelength.

  Further, FIG. 16 shows a reflection spectrum when a plurality of metal fine particle array films are prepared by the same method, and a predetermined number of these are superposed to form an optical element sandwiched between quartz plates. In the case where 3 sheets and 9 sheets were laminated, it was found that the respective reflection maximum values (3 sheets; 27.6, 9 sheets; 27.1%) were higher than those of one sheet. Thus, it is possible to improve reflection characteristics by laminating a plurality of metal fine particle alignment films.

(Example 11)
A solution obtained by dissolving 50.1 mg of silver perchlorate in 5.00 g of a tetrahydrofuran (THF) solution of a 10 wt% poly (methyl methacrylate / methacrylic acid) 75:25 random copolymer on the reflective substrate prepared in Example 1. Was spin-coated (1500 rpm, 10 seconds) and then dried at room temperature for 3 hours. Thereafter, an ultraviolet light with a wavelength of 365 nm is incident on the thin film on the reflective substrate at an angle of 60 ° using an ultra-high pressure mercury lamp (manufactured by USHIO INC., “Multi-light”) and a narrow band-pass filter. For 3 hours. After the metal fine particle array film was peeled from the reflective substrate of the obtained sample, an optical element was produced by sandwiching the thin film between two quartz plates.

  The reflection spectrum of the obtained optical element is shown in FIG. It turned out that the wavelength which becomes a reflection maximum shifts to 430 nm, and has a reflection maximum value of 30.5%. In this way, by changing the angle of the irradiation light, the repetition distance (pitch) of the metal fine particle layer is adjusted, and the selectivity of the reflected wavelength is changed almost as predicted based on the interference theory shown in Reference Example 3. I confirmed that I was able to.

2 is a TEM photograph of a metal fine particle array film produced in Example 1. FIG. From the bottom, a glass substrate, an aluminum layer, a silica layer, and a silver fine particle array polymer layer are formed. 2 is a TEM photograph of a metal-polymer composite of Comparative Example 1. From the bottom, a glass substrate, metals - has a polymeric composite layer. 4 is a TEM photograph of a metal fine particle array film of Example 2. The lower and upper parts are embedding resins for sample preparation. It is a figure which shows the reflective characteristic of the metal fine particle arrangement | sequence film | membrane of Example 2. FIG. 4 is a TEM photograph of a metal fine particle array film produced in Example 3. From the bottom, a glass substrate, an aluminum layer, a silica layer, and a silver fine particle array polymer layer are formed. It is a figure which shows the optical characteristic prediction in the optical thin film design software Essential Macintosh of the reference example 1. FIG. 4 is a TEM photograph of a metal fine particle array film produced in Example 4. From the bottom, a glass substrate, an aluminum layer, a silica layer, and a silver fine particle array polymer layer are formed. 6 is a TEM photograph of a metal fine particle array film produced in Example 5. From the bottom, a glass substrate, an aluminum layer, a silica layer, and a silver fine particle array polymer layer are formed. 6 is a TEM photograph of a metal fine particle array film produced in Example 6. From the bottom, an embedding resin for preparing a sample and a gold fine particle array polymer layer are formed. 6 is a TEM photograph of a metal fine particle array film produced in Example 7. From the bottom, a glass substrate, an aluminum layer, a silica layer, and a silver fine particle array polymer layer are formed. 6 is a TEM photograph of a metal fine particle array film produced in Example 8. From the bottom, a glass substrate, an aluminum layer, a silica layer, and a silver fine particle array polymer layer are formed. 10 is a TEM photograph of a metal fine particle array film produced in Example 9. From the bottom, a glass substrate, an aluminum layer, a silica layer, and a silver fine particle array polymer layer are formed. It is a figure which shows the optical characteristic prediction in the optical thin film design software Essential Macintosh of the reference example 2. FIG. It is a figure which shows the optical characteristic prediction in the optical thin film design software Essential Macintosh of the reference example 3. FIG. It is a figure which shows the reflective characteristic at the time of producing an optical element by pinching | interposing one metal fine particle array film of Example 10 between quartz plates. It is a figure which shows the reflection characteristic at the time of producing the optical element by producing several metal fine particle arrangement | sequence films | membranes of Example 10, and superposing | stacking a predetermined number of this and pinching it between the quartz plates. It is a figure which shows the reflective characteristic of the metal microparticle arrangement | sequence film | membrane of Example 11. FIG. In the manufacturing method of this invention, it is the conceptual diagram which showed the presumed mechanism in which the multilayered structure by which the metal fine particle layer and the polymer-only layer were laminated | stacked alternately was obtained. It is a conceptual diagram theoretically explaining the conditions under which incident light and reflected light from a substrate interfere when incident light is irradiated vertically. FIG. 3 is a conceptual diagram for theoretically explaining conditions under which incident light and reflected light from a substrate interfere when a thin film is irradiated with light at a certain incident angle θ ₁ .

Claims (15)

A metal component containing a metal compound that is reduced by light to generate metal fine particles on a reflective substrate having a reflecting mirror in which a single layer film or a multilayer film is formed using a material selected from metals and metal oxides on the surface of the substrate (A) forming a polymer film containing
By irradiating the polymer film with light of a specific wavelength having a half-value width of 20 nm or less, a layer in which metal fine particles are densely formed periodically with an interval between adjacent layers in the film thickness direction of the polymer film. And (B) forming a metal fine particle array film having an existing multilayer structure . Film forming process of the polymer film (A) is a sub-step of forming a film of the polymer solution containing the metal components on a reflecting substrate, according to claim 1, characterized in that it has a sub-step of distilling off the solvent Production method. Prior to the step (A), a step of providing on the reflective substrate a release layer that transmits light having a wavelength irradiated in the subsequent step (B),
In the step (A), a polymer film containing a metal component is formed on the release layer,
Furthermore, after the said process (B), it has the process of peeling off the said polymer film after light irradiation from the said reflective substrate, The manufacturing method of Claim 1 or 2 characterized by the above-mentioned. The method according to claim 3 , wherein the step of peeling the polymer film from the reflective substrate includes the step of removing the release layer. The method according to claim 4 , wherein the release layer is removed by dissolving the release layer. The said metal compound is at least 1 sort (s) chosen from silver perchlorate, silver nitrate, and chloroauric acid, The manufacturing method of any one of Claims 1-5 characterized by the above-mentioned. The production method according to claim 1 , wherein the polymer constituting the polymer film is transparent at least at the specific wavelength. Said polymer, polymethacrylic acid, polyacrylic acid, claim, characterized in that copolymers containing methacrylic acid or acrylic acid monomer units, and at least one selected from the group consisting of polyvinyl alcohol 1-7 The manufacturing method in any one of. The manufacturing method according to claim 1 , wherein in the step (B), the repetition distance of the metal fine particle layer in the metal fine particle array film is adjusted by changing the wavelength of the light to be irradiated. . In the step (B), by changing the angle with respect to the reflection substrate of the irradiated light, in any one of claims 1 to 8, wherein adjusting the repeat distance of the metal fine particle layer of the metal fine particle arrangement layer in The manufacturing method as described. A metal fine particle arrangement film having a multilayer structure in which a layer in which metal fine particles generated by light reduction of a metal compound are densely present in a polymer film periodically exists at intervals between adjacent layers in the film thickness direction. A layer produced by the method according to any one of claims 1 to 10 and in which metal fine particles produced by light reduction of a metal compound are densely arranged in a polymer film has a gap between adjacent layers in the film thickness direction. Metal fine-particle array film having a multilayer structure that periodically exists . A step of producing a metal fine particle arrangement layer by the method according to any one of claims 1 to 10, the metal fine particle arrangement is characterized by a step of laminating a plurality of the obtained metal fine particle arrangement layer film A method for producing a multilayer laminate. In a polymer film, a layer in which the metal particles are densely produced by reduction with a light metal compound has a multilayered structure in periodically at intervals between layers adjacent in the thickness direction, claim 13 A multilayer laminate produced by the production method described above. A wavelength-selective reflective film using the metal fine particle array film according to claim 11 or 12 , or the multilayer laminate according to claim 14 .